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i
ASSESSMENT RECORD
% Mark
1. Executive Summary/Abstract 5
2. Introduction
Background to the report (Literature Review, Introduction, 5
Objectives)
3. Technical Content
Material Balance 10
Brief Introduction to task presented
Process flow sheets: BFD, PFD
Basis for calculation defined, SI units consistently used
throughout balance
Product specifications
All assumptions clearly stated, deviation between theory and 10
practice explained, balance presented in a clear methodical
manner
Energy Balance
Brief introduction to task presented
Process flow sheets: BFD, PFD
Basis for calculation defined, SI units consistently used
5
throughout balance
Product specifications
All assumptions clearly stated, deviation between theory and
practice explained, balance presented in a clear methodical
manner 15
P&ID Control
Brief introduction to task presented
P&ID System: Identify the various equipment
Computer generated P&ID produced, all major streams and
equipment labelled/acceptable symbols and notations used
15
Evaluation of Heat Transfer operation of any unit operation
Brief introduction to task presented
Process/plant flow sheet: BFD, PFD
Choice of heat transfer equipment in application justified
ii
Calculations presented in a clear, methodical manner. SI
units consistently used
All assumptions clearly stated and fully justified. Deviation
between actual and design fully discussed
Evaluation of Mass Transfer operation/separation unit
Brief introduction to task presented
Process/plant flow sheet: BFD, PFD
Choice of mass transfer equipment in application justified
Calculations presented in a clear, methodical manner. SI
units consistently used
All assumptions clearly stated and fully justified. Deviation
between actual and design fully discussed
4. Report lay-out and grammar 10
7. References 10
TOTAL 100
iii
Abstract
The production rate of newer technology is higher and almost impossible to stop or slow down,
every year newer electronics and electrics materials (cellphones, computers, etc.) are
produced and everyone want to be updated. But this production has its advantages mostly
economical and its disadvantages. Thus, the higher the rate of production, the higher the
electronic waste generation. To support and connect electronic components, all electronics
use printed circuit boards (PCBs). The PCBs contain a huge concentration of precious and
base metals compared to primary metal resources. The e-waste contains toxic substances,
which can affect human health both indirectly and directly. Therefore, the environment must
be protected by recycling and recovering the metals from e-waste with regard to resource
conservation.
Hydrometallurgy is the preferred method for the recovery of precious metals because of its
low production of gas and dust emissions, and low use of energy (Akcil et al., 2015) and it is
also known as a perfect process for high precious metal recovery. The recovery of gold was
regularly made by the cyanidation, it is an old leaching process for the recovery of the gold
and other valuable metals, but this process is very toxic and has been prohibited in some
countries. Various studies have been conducted recently to find some cyanide alternatives.
Different non-cyanides have been found, but for this investigation, the ammonium thiosulphate
had been chosen as the preferred cyanide alternatives.
The PCBs granules of ±2mm mm were leached in a 700 mL reactor in open atmosphere. The
recovery of gold has be done using copper then an alternative (nickel) has been proposed at
the same recovery condition and it was found More golds are extracted (almost 50%
extraction) using nickel as a catalyst than copper (21%) at the same condition (room
temperature (25 degrees Celsius), 0.03M copper sulphate, 0.1M ammonium thiosulfate, pulp
density: 50 g/L, pH: 10.5, and at and stirring speed of 350 rpm in 6h duration) because of its
low consumption. The effect of different parameters such as copper sulphate concentration,
ammonium thiosulfate concentration, pH was also studied.
iv
Table of Contents
Abstract............................................................................................................................. iv
List of abbreviations ......................................................................................................... vii
List of Symbols ................................................................................................................. viii
List of tables ....................................................................................................................... 3
List of figures ...................................................................................................................... 3
1 Introduction ................................................................................................................ 4
2 Theoretical content ..................................................................................................... 6
2.1 Material and Energy balance ......................................................................................... 6
2.1.1 The use of balance .......................................................................................................................... 6
2.1.2 System ............................................................................................................................................ 7
2.2 Mass balance ................................................................................................................. 8
2.2.1 Permanent Material Balances......................................................................................................... 8
2.2.2 A reactor ......................................................................................................................................... 8
2.2.3 Material balance result ................................................................................................................... 9
2.3 Energy balance .............................................................................................................10
2.3.1 Derivation of the Energy Balance: ................................................................................................ 11
2.3.2 Heat transfer ................................................................................................................................. 12
2.3.3 Activation energy .......................................................................................................................... 16
2.3.4 Heat of reaction ............................................................................................................................ 17
2.3.5 Rate of reaction ............................................................................................................................ 17
2.4 Atomic Absorption Spectrometry (AAS) ........................................................................18
3 TECHNICAL CONTENT ................................................................................................ 19
3.1 Process description .......................................................................................................19
3.1.1 Size Reduction Process ................................................................................................................. 19
3.1.2 Copper ATS Leaching Process with acid pre-treatment................................................................ 20
3.1.3 AAS Process................................................................................................................................... 22
3.1.4 Aqua Regia leaching(Anon, n.d.) ................................................................................................... 23
3.1.5 Block Flow Diagram ...................................................................................................................... 24
3.1.6 Process Flow Diagram ................................................................................................................... 25
Size reduction.............................................................................................................................................. 25
Leaching ...................................................................................................................................................... 25
Extraction .................................................................................................................................................... 25
v
APPENDICE A: Experimental Raw Data ............................................................................. 12
Particle Size Distribution ...........................................................................................................12
Aqua regia leaching ..................................................................................................................12
Cu-ATS leaching ........................................................................................................................14
Ni-ATS leaching .........................................................................................................................15
APPENDICE B: Sample of calculation ................................................................................. 18
APPENDICE B: Mathematical modelling of a batch reactor ............................................... 21
vi
List of abbreviations
AAS: Atomic Absorption Spectroscopy
ATS: Ammonia Thiosulphate
Au: Gold
BFD: Block Flow Diagram
CA: Actual concentration
CD: Diluted concentration
Cu: Copper
H2O2: Hydrogen peroxide
MSDS: Material Safety Data Sheet
ppm: Part per million
NaOH: Sodium hydroxide
Ni: Nickel
PCB: Printing circuit board
PFD: Process Flow Diagram
PI&D: Process Instrumentation Diagram
pH: Potential Hydrogen
WEE: Waste Electronic Equipment
PSD: Particle Size Distribution
vii
List of Symbols
P Pressure Pa
Particle size μm
C Concentration ppm
T Time s
T Temperature K
V Volume m3
viii
List of tables
Table 1 metal content ............................................................................................................. 8
Table 2: PSB on Frequency Basis ........................................................................................ 12
Table 3: PSB Cumulative Basis ............................................................................................ 12
Table 4: Metal content .......................................................................................................... 12
Table 5: Fixed factor ............................................................................................................. 12
Table 6: Actual Copper concentration in ppm ...................................................................... 13
Table 7: Actual gold concentration in ppm ............................................................................ 13
Table 8: Dilute concentration in ppm .................................................................................... 13
Table 9: fixed factors............................................................................................................. 14
Table 10: titration (run and replicate) .................................................................................... 14
Table 11: Responses ............................................................................................................ 15
Table 12: fixed factors ........................................................................................................... 15
Table 13: titration .................................................................................................................. 16
Table 14: Responses ............................................................................................................ 17
List of figures
Figure 1 the top 10 countries that generate most e-waste in the world .................................. 4
Figure 2 Example of a system ................................................................................................ 7
Figure 3 Conduction heat transfer ........................................................................................ 12
Figure 4 Heat flow with convective boundaries: cylindrical wall ............................................ 14
Figure 5: Grinding machine ................................................................................................... 19
Figure 6 copper ATS leaching .............................................................................................. 20
Figure 7: AAS set-up............................................................................................................. 22
Figure 8: Reaction process set - up ...................................................................................... 23
Figure 9 overall BFD ............................................................................................................. 24
Figure 10 overall PFB ............................................................................................................. 3
Figure 11 P&ID of a reactor .................................................................................................... 3
Figure 12 cumulative PSD ...................................................................................................... 4
Figure 13 frequency PSD ........................................................................................................ 4
Figure 14 Cu-ATS leaching ..................................................................................................... 6
Figure 15 Ni-ATS leaching ...................................................................................................... 6
Figure 16 batch reactor ......................................................................................................... 21
3
1 Introduction
New technologies are going so fast that they cannot be stopped. If there is a time when
the world has made great progress in new technologies, it is the era of the present
generation. Progress is palpable at the high-tech level. Every day, researchers make
constant improvements and new research to improve the products and services they
offer, as well as to create new ones. Indeed, all that is possible today was hardly
possible a few years ago. People did not even know that it was possible to imagine or
even create all these things that exist today. Technology has allowed so many
innovations that if we were to list everything the list would go on forever.
Because of the electronic equipment production, this led to the increase of electronic
waste (e-Waste) which invent more opportunities in the economic growth by recycling
of important metals that the waste contains and over 50 million metric tons of e-waste
is generated in the world per year, and China is on top of the list with 7.2 million tons
per annum followed by the US with 6.3 million tons per annum.
Figure 1 the top 10 countries that generate most e-waste in the world
All electronics use printed circuit boards (PCBs) which contain a huge concentration of
precious and base metals to support and connect electronic components. The e-waste
contains toxic substances, which can affect human health both indirectly and directly(Albertyn,
2017). E-waste is made up of a complex mixture of non-ferrous, plastic and ferrous, ceramic
materials. The Association of Plastics Manufacturers in Europe (APME) specified that the main
components of electronic and electric equipment are ferrous (38 %), non-ferrous (28 %) and
(19 %)plastic (Albertyn, 2017). the PCBs which are found in e-waste form are composed 30%
ceramics,30% plastics, 40% metals.
4
These materials can be environmentally unsafe. Therefore, the environment must be
protected by recycling e-waste which provides both economic and environmental benefits
because it contains valuable constituents and also recovering the metals from e-waste with
regard to resource conservation. To extract important metals from e-waste, two main process
are used, which are hydrometallurgy and pyro-metallurgy(Dong et al., 2017). the pyro-
metallurgical processes were used as a main treatment of e-waste, but due to the emission of
toxic gases and low recovery of metals, the hydrometallurgical processes were taken with
more consideration because it is easily controlled and better predictable.
The recovery of gold was regularly made by the cyanidation for many years, but because of
its toxicity, it has been prohibited in some countries. Thus, studies have been conducted
recently to find some cyanide alternatives such as thiourea, thiosulphate, etc. But it has been
proved that thiosulfate is the most used nowadays because it is more environmentally friendly.
The recovery of gold from waste mobile PCB using ammonium thiosulfate is the aim of this
work. Various parameters and their effects such as copper sulphate concentration, ammonium
thiosulphate concentration, pH were also studied.
5
2 Theoretical content
6
2.1.2 System
To establish the balance of matter or energy, one must define and select the part of the
process to be studied that will be called system. So, by definition, a system is the matter
contained in a portion of space, delimited by a boundary which fixes its volume.
S1 S2 S3
7
Extensive quantities, which are functions of the chosen system: mass, number of
moles, volume, flows, etc.
Intensive quantities, independent of the choice of the system: density,
concentration, pressure, temperature, etc.
2.2.2 A reactor
A reactor is any apparatus in which the transformation takes place chemical, meaning the
transformation of molecular species into other species molecular. A reactor is a system that
8
can be, like any other system for this investigation an open system (batch reactor) is used.
The batch reactor is perfectly mixed, usually in the liquid phase.:
Open: when it can exchange matter and energy with the outside
environment.
Closed: when it cannot exchange matter (exchange of energy remains
possible)
Isolated: if it cannot exchange matter or energy with the outside
environment
The overall material balance was conducted on the Cu ATS leaching reactor the production
of metals used. The input amount of 35g of PCBs entered the system and 19.06g left the
system as product. Because the process is not operating under steady-state (batch process)
the input cannot be equal to the output.
9
2.3 Energy balance
The second property to be considered in the general balances on a control volume. The same
way the general mass balance had been obtained, the principle of the conservation of energy
are applied to a control volume fixed in space. The first law of thermodynamics is then
combined with the conservation of energy equation will then to produce the overall energy-
balance equation. The first law of thermodynamics can be written as:
∆𝐸 = 𝑄 − 𝑊
The term "generated energy" is to be considered in the broad sense: energy produced or
consumed. It is the same for the term of accumulation (variation in the time of the energy in
the volume of control).
The generation term, may appear in the following cases:
exothermic or endothermic chemical reactions,
nuclear reactions - viscous dissipation
Joule effect in an electrical resistance
10
2.3.1 Derivation of the Energy Balance:
𝑄̇ + 𝑊𝑆 + ∑ 𝐸𝐽 𝑖𝑛
̇ = ∑ 𝐸𝑗 ̇
𝑜𝑢𝑡
𝑖𝑛 𝑜𝑢𝑡
The energy of a stream is made of made of potential, kinetic and internal energy
𝐸𝐽 = 𝑢 + 𝐸𝐾 + 𝐸𝑝
̂2
𝑉
𝐸𝑗 = 𝑚𝑗 (𝑢̂𝑗 + 𝐽 ⁄2 + 𝑔𝑧𝑗 )
𝑊 = 𝑊𝑆 + 𝑊𝐹𝐿
𝑊𝑖𝑛 = 𝑃𝑖𝑛 ∗ 𝑉𝑖𝑛
𝑊𝐹 = 𝑃𝑖𝑛 . 𝑉𝑖𝑛 − 𝑃𝑜𝑢𝑡 . 𝑉𝑜𝑢𝑡
𝑊𝐹𝐿 = ∑ 𝑚𝑗 . 𝑃𝑗 . 𝑉̂𝐽 − ∑ 𝑚𝑗 . 𝑃𝑗 .̂
𝑉𝐽
𝑖𝑛 𝑜𝑢𝑡
̂2
𝑉 ̂2
𝑉
𝑄 + 𝑊𝑆 + ∑ 𝑚𝑗 (𝑢̂𝑗 + 𝑃𝑗 𝑉̂𝐽 + 𝐽 ⁄2 + 𝑔𝑧𝑗 ) = ∑ 𝑚𝑗 (𝑢̂𝑗 + 𝑃𝑗 𝑉̂𝐽 + 𝐽 ⁄2 + 𝑔𝑧𝑗 )
𝑖𝑛 𝑜𝑢𝑡
𝐻 = 𝑢 + 𝑃𝑉
̂2
𝑉 ̂2
𝑉
𝐽⁄ 𝐽⁄
𝑄 + 𝑊𝑆 + ∑ 𝑚𝑗 (𝐻𝐽 + 2 + 𝑔𝑧𝑗 ) = ∑ 𝑚𝑗 (𝐻𝑗 + 2 + 𝑔𝑧𝑗 )
𝑖𝑛 𝑜𝑢𝑡
For an open system the equation becomes
∆𝐻 + ∆𝐸𝐾 + ∆𝐸𝑃 = 𝑄 + 𝑊𝑆
For a batch system
̂2
𝑉𝐽⁄ ̂
2 ; 𝑔𝑧𝑗 ; 𝑃𝑗 𝑉𝐽 = 0 ( 𝑏𝑒𝑐𝑎𝑢𝑠𝑒 𝑛𝑜 𝑓𝑙𝑜𝑤 𝑖𝑛 𝑜𝑟 𝑜𝑢𝑡 𝑑𝑢𝑟𝑖𝑛𝑔 𝑡ℎ𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠)
∆𝒖 = 𝑸 + 𝑾𝑺
11
2.3.2 Heat transfer
There is heat transfer between two points where different temperatures prevail: the transfer
always takes place from the highest temperature to the lowest temperature. The difference in
temperature is the driving force of heat transfer. There are three types of heat transfer:
2.3.2.1 Conduction:
Conduction is the propagation of heat from molecules to molecules (or from atoms to atoms
or ions to ions) in a body or in several contiguous bodies without there being any movement
of this medium.
Where:
𝑞𝑥 is the heat-transfer rate in the x direction in watts (W)
𝐴 is the cross-sectional area normal to the direction of flow of heat in m2
𝑘 is the thermal conductivity in W/m. K
𝑇 is temperature in K
𝑥 is distance in m
The minus sign indicates that heat transfer is in the direction of decreasing temperatures
12
2.3.2.2 Convection:
Convection is the propagation of heat in a moving fluid. The heat transfer is affected by the
combined action of the conduction within the fluid and the movement of the fluid. The
conduction therefore intervenes in the convection, but the movement of the fluid leads to
different laws of a phenomenon of conduction without displacement of matter.
Forced convection is when the movement of the fluid is affected by external forces (pump, fan,
agitator) and natural convection when the movement is under the influence of differences in
density due to differences in within the fluid.
On a surface, the global phenomenon of heat transfer is expressed in a practical way by
Newton's cooling law:
𝑞 = ℎ𝐴(𝑇𝑠 − 𝑇𝑜 )
Where:
𝑇𝑆 is the temperature of the solid surface in K
𝑇𝑂 is the average or bulk temperature of the fluid flowing by in K
ℎ is the convective heat-transfer coefficient in W 1m2. K
Here are some examples of situations with convection heat transfer: heat exchanger, hair
dryer, fan, .... when you blow on your coffee to cool it!
2.3.2.3 Radiation:
Radiation is the emission by a body of electromagnetic waves that are the vectors of this heat
transfer. The waves are emitted in all directions and belong to the field of infra-red and visible.
No material support is needed for their propagation.
It is a type of heat transfer that is familiar to us: winter in front of a good fire or summer on the
beach in the sun. The heat passes from a body at high temperature to a body at low
temperature in the form of electromagnetic radiation (photon); the two bodies must be in a
transparent medium (like air or emptiness).
The maximum flux density emitted by a surface is given by Stephan-Boltzmann’s law:
𝑞𝑚𝑎𝑥 = 𝜎 𝑇𝑆4
where the Stephan-Boltzmann constant (σ) is 5.669 10-8 W / (m2.K4)
The maximum flux is obtained for an ideal surface (black body). However, the real surfaces
(gray body) have a certain emissivity (ε) that reduces the flux emitted by the surface:
𝑞𝑟𝑒𝑎𝑙 = 𝜀 𝜎 𝑇𝑆4
In the case where this surface is surrounded by another surface at a temperature (T ENV), the
net heat exchange is then:
𝑞𝑛𝑒𝑡 = 𝜀 𝜎 (𝑇𝑆4 − 𝑇𝐸𝑁𝑉
4
)
13
2.3.2.4 The overall heat-transfer coefficient
An overall heat transfer coefficient is used to combine together the effects of convection and
conduction. Consider a pipe with an inside diameter ri and the outside ro, the fluid flows inside
the pipe with a bulk temperature of Ti and t& for the outside bulk temperature of air. This pipe
is made of K material. he convective heat transfer coefficients for the inside and outside are
respectively hi and ho.
A
Ti
ri
T
ro
hi
ho
14
the tank volume is 700ml which is 0.0007m3
𝐴𝑠𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛:
𝐴𝑜 = 0.0343𝑚2
ℎ𝑖 = 1200 𝑤 ⁄𝑚2 . 𝐾
ℎ𝑜 = 22 𝑤 ⁄𝑚2 . 𝐾
𝑘𝑔𝑙𝑎𝑠𝑠 = 0.75 𝑤 ⁄𝑚. 𝐾
𝐿
= 1,3 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑡𝑎𝑛𝑘 𝑐𝑜𝑛𝑓𝑖𝑔𝑢𝑟𝑎𝑡𝑖𝑜𝑛
𝐷
𝐷 2 𝐿 𝐷3
𝑣= +
4 24
1.3𝜋𝐷3 𝜋𝐷3
0.0007 = +
4 24
0.0007 = 1.152𝐷3
𝐷 = 0.0847𝑚
𝐿 = 0.11𝑚 𝐴𝑖 = 𝜋𝐷𝑖 ∗ 𝐿
𝐴𝑖 = 0,0847𝜋 ∗ 0.11
𝐴𝑖 = 0.0293𝑚2
27 − 21
𝑞=
1 0,01715 1
+ 𝑙𝑛 ⁄2𝜋 ∗ 0.11 ∗ 0.75 +
(1200 ∗ 0.0293) 0.01465 22 ∗ 0.0343
𝑞 = 3.62 𝑊
For a batch reactor
∆𝑢 = 𝑄 + 𝑊𝑆
∆𝑢 = 𝑄
∆𝑢 = 3.62𝑤
15
2.3.3 Activation energy
Different relationships have been proposed to explain the temperature dependence of the
constant of speed of a reaction. The expression generally used is the relation established by
Arrhenius in 1889. Arrhenius, a Swedish chemist, has collected large amounts of numerical
data concerning the behavior of many chemical reactions depending on the temperature, to
obtain this relationship. This relationship was confirmed around 1935 as a result of
development in theoretical chemistry, it is why this law is often called the semi-empirical law
of Arrhenius:
𝑑 𝑙𝑛𝐾 𝐸𝑎
=
𝑑𝑇 𝑅𝑇 2
Ea. denotes the molar activation energy; it corresponds (in a simplified way) to the energy to
be supplied to the system for the reaction to take place. It is of the order of a few tens of kJ.mol-
1. On an interval temperature below 100K, it can be considered that the activation energy is
constant. By therefore, the law of Arrhenius can be written in the following integrated form:
𝐾 = 𝐴𝑒 −𝐸𝑎 ⁄𝑅𝑇
A is the preexponential factor, homogeneous to a speed constant, it takes into account the
frequency of collisions and steric effects
𝑅𝑎𝑡𝑒 = 𝐾[𝐴]
1,538.10−5 = 0.03 𝐾
𝐾1 = 1,538.10−5 ⁄0.03
𝐾1 = 5,13.10−4 𝑆 −1
𝐾
−𝑅 .ln(𝐾2 )
1
𝐸𝑎 = 1 1
−
𝑇2 𝑇1
0.00061
−8.3145∗ln(0.000513)
𝐸𝑎 = 1 1
−
300 298
𝑬𝒂 = 𝟔𝟒𝟑𝟔𝟓𝒋⁄𝒎𝒐𝒍
𝑬𝒂 = 𝟔𝟒, 𝟒𝒌𝒋⁄𝒎𝒐𝒍
16
2.3.4 Heat of reaction
Heat of reaction is the total amount of energy released or absorbed during the chemical
reaction. This heat is the sum of the energy released/absorbed by the products minus the sum
of the energy released/absorbed by the reactants.
∆𝐻𝑟𝑥 (𝑇) = 𝐻𝐵 (𝑇) − 𝐻𝐴 (𝑇) = 𝑚𝑐𝑝∆𝑇
∆𝐻𝑟𝑥 = 51.1783 ∗ 4.186 ∗ (27 − 21)
∆𝐻𝑟𝑥 = 1285.4𝐽
∆𝐻𝑟𝑥 = 0.05951𝑊
𝟎, 𝟑𝟗𝟓 − 𝟎, 𝟑𝟓𝟖
𝑹𝒙 =
𝟑𝟔𝟎𝟎 − 𝟏𝟐𝟎𝟎
𝑹𝑿 = 𝟏. 𝟓𝟑𝟖 ∗ 𝟏𝟎−𝟓 𝑴/𝒔
𝐝𝐓
𝑪𝒑(𝐍𝐀 + 𝐍𝐁 ) = ∆𝐇𝐫𝐱 . 𝐫𝐀 𝐕 + 𝐐
𝐝𝐭
𝐝𝐓
𝟒. 𝟏𝟖𝟔(𝟎, 𝟒𝟔𝟏𝟖𝟒 + 𝟎, 𝟎𝟎𝟎𝟓𝟐𝟒) = (𝟎. 𝟎𝟓𝟗𝟓𝟏 ∗ 𝟎. 𝟎𝟎𝟎𝟎𝟏𝟓𝟑𝟖) + 𝟑. 𝟔𝟐
𝐝𝐭
𝐝𝐓
𝟏. 𝟗𝟑𝟓𝟓 = 𝟑. 𝟔𝟐
𝐝𝐭
𝐝𝐓
= 𝟏. 𝟖𝟕
𝐝𝐭
17
2.4 Atomic Absorption Spectrometry (AAS)
Absorption or emission spectroscopy is probably the oldest analytical method used in the
world. It includes two quantitative analysis methods that can be used to measure
environmental concentrations of 70 elements (metals, metalloids and non-metals). The
principle behind these methods of analysis depends on how it is transformed into free atom
analysis (atomization). Molecules are turned or vibrated, in this case only, electronic
transitions take place when the energy is absorbed. Because the transitions are quantized, on
a spectrum of lines and elements detected by optical or mass spectrometry. This technique is
based on the absorption of monochromatic radiation. Atoms in the ground state absorbing the
energy in a long time of a product in a text evaluated in a source. This source of product is
intense electromagnetic radiation with a length similar to that absorbed by atoms. The
sensitivity of this technique is proportional to the number of atoms in the ground state. The
basic components of an atomic absorption instrument are in the following figure.
18
3 TECHNICAL CONTENT
19
3.1.2 Copper ATS Leaching Process with acid pre-treatment
- 300ml were measured and poured into the reactor; the stirrer was switched on and run
at a speed of 350rev/min, a vortex was noticed because of the high speed and also
because of the reactor which was not baffled.
- 28g of PCBs powder were weighed and poured into the same reactor, and the speed
was adjusted to 369rev/min. after the PCBs were well mixed with the water in the
reactor, 5.24g of Cu2+ were added into the solution at the same speed.
- Then 21.8ml of NH4OH were added, precipitation and color changed was noticed, the
color changed from dark green to dark blue, then 10.37g of ammonium thiosulphate
were added to the same solution. Finally, 300ml of water were added to feel the reactor
at 700ml.
- According to the literature, there is a reasonable recovery of gold at PH of 10.5, so the
PH meter was set a 10.5. 30ml more of 20ml of NaOH were added to the solution to
increasing the PH until 10.48 because it was very low.
- The process runs for 4 hours but to stabilize the PH, 1ml of NaOH had been adding
to the solution after every 30min
Titration
1. An initial volume V1 was recorded from the reactor
2. The pH was adjusted on range the of [7 to 7.5]
3. A new volume V2 was recorded afterward
20
4. This volume was place in a burette, and a new volume VT0 was recorded
5. 5mL of iodine plus 2mL of starch solution and 2 mL of acetate were added in the beaker
6. A final volume VTF was recorded after titration. Noted that a colour changed, go from
a dark brown to white milk solution
7. Then the difference between the titration volume L2 was calculated
8. ATS was calculated with all the data recorded
21
3.1.3 AAS Process
all samples must be diluted before testing the actual concentration in the AAS
because of acetylene toxicity the gas must be closed after the usage
when once the application is on the green light have to appear
22
3.1.4 Aqua Regia leaching(Anon, n.d.)
23
3.1.5 Block Flow Diagram
PCBs are collected from more than 50 broken cellphones. Then they are disassembly by
removing all unwanted components. After disassembling them, they are reduced to the
required size for the gold leaching process and finally gold is extracted using the resin
absorption technique. Gold is dissolved by the reagent and then removed from a stirred tank
reactor. It is then extracted from the pregnant leach solution by adsorption on resins.
Size reduction
recovery
Resins loaded
Component disassembly
leaching
PCBs
24
3.1.6 Process Flow Diagram
Figure 12 showed the overall process in details. It can be divided in 3 process which are: size
reduction, leaching and extraction.
Size reduction
The cell phones are collected and disassembled using screwdrivers and others tools to
removed unwanted components(batteries and covers), then the PCBs are collected from the
cell phones(unwanted components are also removed from PCBs). These unwanted
components are impurities which can slow the size reduction process. The size reduction
process is also divided in 3 parts the PCBs are first reduced to 1cm2 granules, then they are
crushed using a hammer mill to ≤ 2mm, finally the sieving part. All granules ≥ 2mm are crushed
recycled for them to have a required size, which will be used for the leaching process.
Leaching
This process is conducted under 25 degrees by using a water bath. pH solution is control
using a pH meter. The solution mixed contains: Copper thiosulphate, ammonium hydroxide,
sodium hydroxide, deionized water and ammonium thiosulphate. The stirrer is running at a
speed of 700rpm and the tank is not baffled, after 4h run, the PCBS slurry fed through the
second rector by passing through a filter where the extraction begins using resin adsorption.
Extraction
the clarified liquor solution fed into the adsorption tank containing resins granules which
absorb the gold and the copper. The parameters are again controlled in this section. This
process removes more gold that the other metals.
25
-heat sinks
-Capacitors
Collection of -Piezo buzzers
broken cellphones -other metals
Cellphones PCBs Component
disassembly disassembly
PCBs granules
-Batteries 2mm
-covers
-NaOH
-Copper thiosulphate
Water at -Amonium hydroxide
25 degree -Amonium thiosulphate
stirrer stirrer
T
Pregnant leach Clear Pregnant Loaded
filter
liquor leach liquor resins
waterbath
3
3.1.7 piping and instrumentation diagram
A piping and instrumentation diagram gives a close view on the system which is used for the
process. Based on the reactor used, the temperature and pH meter of the reaction were placed
in the reactor to control the system. Water was flowing from The cooler, which is the water
bath, to the jacket and back in the cooler. The temperature of the cooler was set at 30 degrees
Celsius, the pH had to be maintained at 10.5 and the inside temperature at 27degrees Celsius.
-NaOH
-Copper thiosulphate
-Amonium hydroxide pH TI
-Amonium thiosulphate
TI
3
4 Results and discussion
CUMMULATIVE PSD
1,00
0,80
MASS FRACTION
0,60
0,40
0,20
0,00
0 500 1000 1500 2000 2500 3000
PARTICLE SIZE (ΜM)
Frequency PSD
0,60
Mass Fraction
0,40
0,20
0,00
0 500 1000 1500 2000 2500 3000 3500
Particle Size (μm)
4
Sieve analysis is used for this investigation as the particle size method, which covers a wide
range of sizes. The sieves were arranged in a way that the sieve with a larger opening size
were placed above the ones having smaller sizes. Therefore the sieve with a diameter of
3000µm was placed at the top followed by 1700µm, 1000µm accordingly.
Frequency particle size distribution curve shows that the mass percentages of the sand
particles of size is initially 0% at 0µm, the mass percentages increases from 0µm until the
peak of approximately 50% at 500µm. this shows that most sand particles and granules before
milling are at or below 500µm. Then the mass percentages decrease with an increase in
particle from 500 to 1700 µm. then there is a small increase in in mass fraction, this just shows
the type of equipment used which is Retsch KG hammer mill crusher.
Frequency particle size distribution curve represents the relative amount at or below particular
size. 50% of the mass fraction is below 520µm and 60% of the amount of particles is at 560µm.
5
4.2 Gold extraction
Cu-ATS
25,00
20,00
gold extraction (%)
15,00
10,00
5,00
0,00
0 50 100 150 200 250 300 350 400
time (mn)
Ni-ATS
50,00
45,00
40,00
35,00
gold extraction (%)
30,00
25,00
20,00
15,00
10,00
5,00
0,00
0 50 100 150 200 250 300 350 400
time (mn)
6
Copper is a good catalyst in gold leaching, but it has a higher thiosulphate consumption which
affect the gold price. Nickel has been studied for the last past years and it was found that
nickel is a perfect alternative catalyst for copper in gold leaching. It has been proved that
thiosulfate consumption was evidently lower during nickel-catalysed leaching than that of
copper catalysed leaching, and the gold and silver extractions with the nickel catalysis were
also comparable (Dong et al., 2017)
Thiosulfate consumption is high because thiosulfate itself is metastable and easily oxidized by
Cu(II), which is a catalyst for gold leaching and, furthermore, certain associated minerals can
accelerate the oxidation; the recovery of dissolved gold in pregnant leach solution is difficult
because of the low affinity of activated carbon for [Au(S2O3)2]3−, the complex composition of
the solution, and the interference of [Cu(S2O3)3]5−. the replacement of traditional cupric-
ammonia catalysis with other metals, such as nickel- and cobalt-based catalysts is the most
optimal approach, because it not only reduces thiosulfate consumption observably by
decreasing the redox potential of the leach solution significantly, but also eliminates the
Fig 14 and fig 15 show the extraction of gold using copper and nickel both at the same
condition (pulp density of 50g/l; ammonia thiosulfate concentration of 0.1M; ammonia
concentration of 0,3M; 25 degrees Celsius temperature; pH of 10,5; speed of 350rpm; for 6
hours). The results has proved that the extraction of gold is higher using nickel as a catalyst,
than copper. However, using copper the recovery of gold is more is more stable, because of
the presence of Ammonia is which modify the pH and stabilize the catalyst of cupric ion.
The highest recovery percentage of gold using copper was found to be 20,82% and for the
consumption 248,1 kg/t-PCB for the run and 132,7 kg/t-PCB. Then using Nickel catalyst the
highest recovery percentage of gold using copper was found to be 44,22% and for the
consumption 54,5 kg/t-PCB for the run and 54.9 kg/t-PCB. It is clear that the choice of a
catalyst has a serious effect on the gold recovery. The higher the consumption, the less the
recovery of gold.
7
4.3 Effect of copper ion concentration
Has a very important role in thiosulphate leaching. The gold leaching rate is very low without
copper ion, the rate is increased with increase in copper concentration, it is difficult for the
leaching rate of gold to increase if the concentration of copper ion is out of the range, the
decreases of gold leaching rate can also be cause by the oxidation of thiosulfates by copper
ions. Copper is used as a catalyst in gold leaching and ammonium thiosulfate consumption.
Thus, the concentration of copper ion is controlled to prevent the use of ammonium
thiosulphate, 0.03 mol/l is the preferable coper ion concentration.
under the fixed factor conditions ((pulp density of 50g/l; 5g mass of solids; 25degrees Celsius
temperature;100ml reaction volume; for 24 hours). Copper (Cu) and Gold (Au) ,which are the
main metals, were tested in the experiment and the initial mass fraction of the base metals
were found. To find the average only the maximum and the minimum concentration of the
metals were needed
As expected from the literature review, the highest concentration was found to be the
Copper(46,18) was found to have the highest concentration compare to gold(0,0524wt%), as
8
stated in the literature, on a rage of 43,53wt% to 48,07wt% for copper and 0,0456wt% to
0,0607wt%. A PCB contains high amounts of precious metals, about 20 % copper, 0.04 %
gold (Xia, 2008)
9
5 Conclusion
After this investigation, it can be concluded that ammonium thiosulphate is a favourable
alternative to cyanide because of its friendship with the environment. Gold can be extracted
from this method effectively using the thiosulphate method from printed circuit boards.
Different parameters such as thiosulfate concentration, ammonia concentration, copper ion
concentration and reaction time can affect the thiosulphate leaching. Copper ions and
ammonia have a very important role of catalysts during the thiosulfate leaching process. But
they also have a big disadvantage of consumption, using copper as a catalyst it leads to a
high consumption and low gold recovery, an alternative such Nickel has been used and a high
recovery of gold has been noticed with a small consumption.
The metal contents were found using the aqua regia process and it was noticed that in PCB,
there is a high concentration of copper(46,18wt%) than gold(0.0524wt%).
10
6 References
Akcil, A., Erust, C., Sekhar, C., Ozgun, M., Sahin, M. & Tuncuk, A. 2015. Precious metal recovery
from waste printed circuit boards using cyanide and non-cyanide lixiviants – A review. Waste
Management, 45: 258–271. http://dx.doi.org/10.1016/j.wasman.2015.01.017.
Albertyn, P.W. 2017. LEACHING OF GOLD FROM by. , (March).
Anon. Jacky Mouyecket - IST Report 2.
Dong, Z., Jiang, T., Xu, B., Yang, Y. & Li, Q. 2017. Recovery of Gold from Pregnant Thiosulfate
Solutions by the Resin Adsorption Technique. Metals, 7(12): 555.
Kasper, A.C. & Veit, H.M. 2018. Gold recovery from printed circuit boards of mobile phones scraps
using a leaching solution alternative to cyanide. Brazilian Journal of Chemical Engineering,
35(3): 931–942.
Lors, E. Réaction chimique et bilan de matière. , 3: 3–6.
Xia, C. 2008. Associated Sulfide Minerals in Thiosulfate Leaching of Gold : Problems and Solutions.
, (September).
11
APPENDICE A: Experimental Raw Data
50 - 60 24 - 5 100
12
Table 6: Actual Copper concentration in ppm
Time
Time (h)
(min)
Run 0 20 40 60 80 100 120 24h
1 0 17905 19745 19750 19680 20360 20810 24035
2 0 19690 19990 19735 20870 21260 22230 23035
3 0 18855 19805 19650 21280 22365 22420 22935
4 0 20510 20310 21040 21675 21500 23215 23690
5 0 20500 20220 22320 22990 23075 23685 21765
13
Cu-ATS leaching
Table 9: fixed factors
Particle
Pulp density NH3 Temp
Size ATS (M) Cu2+ pH Time (h) Rpm
(g/L) (M) (°C)
(µm)
50 500 0,1 0,2 0,03 25 10,5 6 350
Cu Au
Solids Reaction
Mass Mass
Mass (g) Vol (mL)
(g) (g)
Run 35 700 16,16 0,0183
Duplicate 35 700 16,16 0,0183
14
Table 11: Responses
Response 1: Au Extraction
Time (min) 0 60 120 180 240 300 360
Run 0,00 16,50 16,67 16,12 16,38 18,92 20,14
Dup 0,00 18,03 16,32 17,04 18,38 18,30 21,51
Mean 0,00 17,26 16,50 16,58 17,38 18,61 20,82
Std Dev 0,00 1,08 0,25 0,65 1,41 0,44 0,97
Ni-ATS leaching
Solids Cu Au
Reaction
Mass Mass Mass
Vol (mL)
(g) (g) (g)
Run 35 700 16,16 0,0183
Duplicate 35 700 16,16 0,0183
15
Table 13: titration
Run R2: ATS Consumption
V1 V2 Vto Vtf L2 ATS
Time (min) %
(mL) (mL) (mL) (mL) (mL) (M) kg/t-PCB
0 - - - - - - 0 0
60 19 21,2 37,8 44,2 6,4 0,087 12,83 38,0
120 20 22,2 37,4 44,2 6,8 0,082 18,38 54,5
180 18,5 20,7 38,6 45 6,4 0,087 12,58 37,3
240 18,5 20,7 38,6 45,3 6,7 0,084 16,50 48,9
300 19 21,1 38,4 44,8 6,4 0,087 13,24 39,2
360 18,5 20,6 38,2 44,8 6,6 0,084 15,64 46,4
16
Table 14: Responses
Response 1: Au Extraction (%)
Time (min) 0 60 120 180 240 300 360
Run 0,00 31,57 29,62 17,39 22,34 48,95 41,05
Dup 0,00 25,02 24,49 18,81 24,83 44,83 44,22
Mean 0,00 28,29 27,05 18,10 23,59 46,89 42,63
Std Dev 0,00 4,63 3,63 1,01 1,76 2,92 2,24
17
APPENDICE B: Sample of calculation
Size Reduction
Total mass mT = m1(<500um) + m2(500um - 1000um) + m3(1000um - 1700um) +
m4(>1700um)
Total mass mt = 405.28g +152.18g +77.87g +192.99g
Total mass mt = 828.32g
18
Initial thiosulphate concentration
𝑣𝑜𝑙𝑢𝑚𝑒 = 0,7 𝑙
148.95𝑔
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝐴𝑇𝑆 =
𝑚𝑜𝑙
𝑚 = 𝑛 ∗ 𝑀𝑟
𝑚 = 148.95 ∗ 0.7
𝑚 = 10.37𝑔
(112.128∗10.37)
𝑆2 𝑂32− 𝐶𝑜𝑛𝑐 = (148.95∗0.7)
∗ 100
[𝑺𝟐 𝑶𝟐−
𝟑 ] = 𝟎. 𝟏𝟏𝟐𝑴
𝑣𝑜𝑙𝑢𝑚𝑒 = 0,7 𝑙
155.68𝑔
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝐶𝑢𝑆𝑂4 ==
𝑚𝑜𝑙
𝑚 = 5.24𝑔
(63.53∗5.24)
𝑆2 𝑂32− 𝐶𝑜𝑛𝑐 = (155.68∗0.7)
∗ 100
[𝑪𝒖𝟐+ ] = 𝟎. 𝟑𝑴
19
Titration calculation
o Total Thiosulphate Volume = Volume after titration – Volume before titration
L2 = Vtf –Vto
L2 = 46 mL - 38 mL= 8 mL
20
APPENDICE B: Mathematical modelling of a batch reactor
Consider the open system which has been used for the investigation
FAO FBO
V
Q
FA
NA NB
FB
T
𝐴 →𝐵
Figure 16 batch reactor
ASSUMPTION
∗ 𝑨𝒔𝒔𝒖𝒎𝒑𝒕𝒊𝒐𝒏
𝑤=0
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝐶𝑝
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∆𝐻
𝑇𝑖𝑛 = 𝑇𝑜𝑢𝑡
𝑟𝐴 = 𝑟𝐵
𝐻𝐴 (𝑇) = 𝐻𝐴 (𝑇𝑂) + 𝐶𝑝𝑎(𝑇 − 𝑇0)
∗ 𝑼𝒏𝒔𝒕𝒆𝒂𝒅𝒚 𝒔𝒕𝒂𝒕𝒆 𝒆𝒏𝒆𝒓𝒈𝒚 𝒃𝒂𝒍𝒂𝒏𝒄𝒆
𝐴𝐶𝐶 = 𝐼𝑁 − 𝑂𝑈𝑇 + 𝑄
The Q is the heat transfer across the system because there is a cooling jacket around the
reactor.
𝑑
[𝑁 . 𝐻 . (𝑇) + 𝑁𝐵 . 𝐻𝐵 (𝑇)] = 𝐹𝐴𝑂 . 𝐻𝐴 . (𝑇0 ) + 𝐹𝐵𝑂 . 𝐻𝐵 . (𝑇0 )
𝑑𝑡 𝐴 𝐴
− 𝐹𝐴 . 𝐻𝐴 . (𝑇) − 𝐹𝐵 . 𝐻𝐵 . (𝑇) + 𝑄
- No phase change
𝑑 𝐻𝐴 𝑑𝑇
= 𝐶𝑝
𝑑𝑡 𝑑𝑡
𝑑 𝑁𝐴
= 𝐹𝐴𝑂 − 𝐹𝐴 + 𝑟𝐴 𝑉
𝑑𝑡
𝑑 𝑁𝐵
= 𝐹𝐵𝑂 − 𝐹𝐵 + 𝑟𝐵 𝑉
𝑑𝑡
- Substitute it in the general equation
𝑑𝑇
(𝑁𝐴 . 𝐶𝑝𝐴 + 𝑁𝐵 . 𝐶𝑝𝐵 ) = 𝐹𝐴𝑂 . 𝐻𝐴 . (𝑇0 ) + 𝐹𝐵𝑂 . 𝐻𝐵 . (𝑇0 )
𝑑𝑡
−𝐻𝐴 (𝑇)(𝐹𝐴𝑂 − 𝑟𝐴 𝑉)
−𝐻𝐵 (𝑇)(𝐹𝐵𝑂 − 𝑟𝐴 𝑉) + 𝑄
21
𝑑𝑇
(𝑁𝐴 . 𝐶𝑝𝐴 + 𝑁𝐵 . 𝐶𝑝𝐵 ) = 𝐹𝐴𝑂 . 𝐶𝑝𝐴 (𝑇 − 𝑇0 ) + 𝐹𝐵𝑂 . 𝐶𝑝𝐵 (𝑇 − 𝑇0 )
𝑑𝑡
+[𝐻𝐵 (𝑇) − 𝐻𝐴 (𝑇)]. 𝑟𝐴 𝑉 + 𝑄
𝐝𝐓
(𝐍𝐀 . 𝐂𝐩𝐀 + 𝐍𝐁 . 𝐂𝐩𝐁 ) = 𝐅𝐀𝐎 . 𝐂𝐩𝐀 (𝐓 − 𝐓𝟎 ) + 𝐅𝐁𝐎 . 𝐂𝐩𝐁 (𝐓 − 𝐓𝟎 )
𝐝𝐭
+ ∆𝐇𝐫𝐱 . 𝐫𝐀 𝐕 + 𝐐
∗ 𝒃𝒂𝒕𝒄𝒉 𝒓𝒆𝒂𝒄𝒕𝒐𝒓
Because there is no flow in and out of the reactor then the formula can be as follow
𝐝𝐓
(𝐍𝐀 . 𝐂𝐩𝐀 + 𝐍𝐁 . 𝐂𝐩𝐁 ) = ∆𝐇𝐫𝐱 . 𝐫𝐀 𝐕 + 𝐐
𝐝𝐭
22
The system can also be model part by part in other words by considering the jacket and the
reactor.
𝑑 1 1 1
̂𝑖 + 𝑉𝑖2 + 𝑔𝑧𝑖 ) 𝜌𝑖 𝐹𝐼 − ∑ (𝐻
̂ + 𝑉 2 + 𝑔𝑧) 𝑚̇] = ∑ (𝐻
[(𝐻 ̂𝑜 + 𝑉𝑜2 𝑔𝑧𝑜 ) 𝜌𝑜 𝐹𝑂 + 𝑄̇ − 𝑊̇
𝑑𝑡 2 2 2
𝑖𝑛𝑙𝑒𝑡 𝑜𝑢𝑡𝑙𝑒𝑡
ASSUMPTION
- No shaft work
- Insignificant change in 𝐸𝐾 𝑎𝑛𝑑 𝐸𝑃
- Fluid in the reactor is liquid constant 𝐶𝑃
- ̂
Constant 𝐻
Reactor Balance
𝑑
[(𝐻̂
𝑅 . 𝑚̇𝑅 )] = 𝑄 − 𝑞
𝑑𝑡
𝑑
[(𝐶 . 𝑇 . 𝑚̇ )] = 𝑄 − 𝑈𝐴𝑖 (𝑇𝑅 − 𝑇𝑎 )
𝑑𝑡 𝑃 𝑅 𝑅
𝑑𝑇𝑅
𝑚̇𝑅 𝐶𝑃 = 𝑄 − 𝑈𝐴𝑖 (𝑇𝑅 − 𝑇𝑎 )
𝑑𝑡
𝑑𝑇𝑅 𝑄 𝑈𝐴𝑖
= − (𝑇 − 𝑇𝑎 )
𝑑𝑡 𝑚𝑅 𝐶𝑃 𝑚𝑅 𝐶𝑃 𝑅
𝑑
̂𝐽 . 𝑚̇𝑗 )] = 𝐻
[(𝐻 ̂𝑖 . 𝑚̇𝑖 − 𝐻
̂𝐽 . 𝑚̇𝑖 + 𝑞
𝑑𝑡
𝑑
[(𝐶𝑃 . 𝑇𝐽 . 𝑚̇𝑗 )] = 𝐶𝑃 . 𝑇𝑖 . 𝑚̇𝑖 − 𝐶𝑃 . 𝑇𝐽 . 𝑚̇𝑖 + 𝑞
𝑑𝑡
𝑑𝑇𝐽
𝐶𝑃 . 𝑚̇𝑗 = 𝐶𝑃 . 𝑇𝑖 . 𝑚̇𝑖 − 𝐶𝑃 . 𝑇𝐽 . 𝑚̇𝑖 + 𝑈𝐴𝑖 (𝑇𝑅 − 𝑇𝐽 )
𝑑𝑡
23