RECOVERY OF METALS FROM E-SCRAP

TITLE: RECOVERY OF METALS FROM ELECTRONIC WASTE (e-scrap).

INTRODUCTION:
E-Waste i.e. electronic waste is discarded electronic equipments. In other words it
refers to the electronic products nearing the end of their useful life period. It includes a broad
range of electronic devices from computer to hand – held cellular phones, stereos, consumer
electronics, ovens, refrigerator, monitors, etc.
Waste of all sort put together is a major cause of Global Warming and electronic
waste (e-waste) is one of the biggest contributor. E-Waste contains several different
substances and chemicals, many of which are toxic & are not biodegradable and are likely to
create adverse impact on environment and health, if not handled properly. In addition to that
it contains metal values which can be recovered.
Manufacturers, government agencies and users are now looking for
environmentally responsible management of this E-waste. Besides proper
disposal, economical recovery of precious and exhaustible materials is
also a matter of interest.

(Table I -Ref 2)

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AIM OF THE PROJECT:

In all electronic equipment thermosetting materials like epoxy, backelite are present.
In today’s practice it is heated in open environment to get the metal, when it is heated at high
temperature it gives lot of fumes and it becomes charry. It causes environmental and health
problems. Our aim is to make the process eco-friendly, convenient and recover the metal
values almost quantitatively.

OBJECTIVE OF WORK:

If treated properly, electronic-waste is a valuable source for secondary raw material.

However, if not treated properly it is a major source of toxins.
In the present practice, uncontrolled burning, disassembly, and disposal are causing
environmental and health problems, including occupational safety and health effects among
those directly involved, due to the methods of processing the waste.
As the prices of gold, silver, copper, tin and lead continue to rise; recovery of these
metals from e-waste has become more desirable.
At present there are few processes to recover the metal values in an environmentally
safe manner. Hence, through our e-waste metal recovery process, we intend to recover the
metallic values in an environmentally safe manner.

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LIST OF SUBSTANCES CONTAINED IN ENECTRONIC WASTE:

(Table II : Ref 2)
1) Substances in bulk: Epoxy resin, fiber glass, polychlorinated biphenyls,
polyvinyl chloride (PVC) and thermosetting plastics.
2) Elements in bulk: Lead, tin, copper, beryllium, iron and aluminium.
3) Elements in small amount: Cadmium, mercury.
4) Elements in trace amount: Gold, silver, antimony, arsenic, barium, bismuth, boron,
cobalt, gallium, palladium, manganese, platinum.
Although the amount of above elements mentioned are not always present in pcb, in
case of some PCB’s, there is gold and silver present in particular applications, in some
PCB’s they may not be present, but common elements like lead, tin and copper are
always present in pcb

LIST OF APPLICATION OF THE ABOVE ELEMENTS:

Almost all electronics contain lead and tin (as solder) and copper (as wire and PCB tracks).
1) Lead: solder, CRT monitors (lead in glass), lead-acid batteries.
2) Tin: coating on component leads.
3) Copper: copper wire, printed circuit board tracks, component leads.
4) Aluminium: nearly all electronic goods using more than few Watts of power (heat sinks),
electrolytic capacitors
5) Silicon: glass, transistors, ICs, printed circuit boards.
6) Gold: connector plating, primarily in computer equipment.
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EXPERIMENTAL SETUP FOR RECOVERY OF

METALS FROM E-SCRAP

EXPERIMENTAL METHODOLOGY:
The experimental methodology is distributed in three main sections:
I) Selection and preparation of e-scrap.
II) Dissolution of the metals present in e-scrap into prepared solution.
III) Recovery of these dissolved metals from solution by different metallurgical routes.
Selection and preparation of e-scrap for dissolution:
The various type of e-scrap was sorted according to categories as mentioned in
table 1. Only printed circuit boards (PCB’s) were taken from the e-scrap for experimental
work. The capacitor, IC’s, joints, mountings, etc. on PCB’s were removed and sorted

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mechanically. The PCB’s were cut into pieces as small as possible. These PCB’s cut
pieces were weighed.
Dissolution of the metals present in e-scrap into prepared solution:
A] Method 1: Dissolution using nitric acid solution
i) In actual process, 8 liter of distilled water was taken in container, then 400ml
concentrated nitric acid (HNO3) was added and after that 300 gm sodium nitrate
(NaNO3) was added. Two magnetic stirrers were used for homogeneous stirring of the
bath. (Nitric acid was added because it dissolves the metallic value like lead, tin and
copper but it does not dissolve gold. Nitric acid was consumed during the dissolution;
hence nitric acid was added periodically. Sodium nitrate was added in bath because it
maintains the electrical conductivity of bath and furnishes the nitrate ions. Sulphuric
acid could not be used because it does not dissolve copper, and lead forms as a lead
sulphate, which is water insoluble.)
HNO3 H+ + NO3- …….. (1).
NaNO3 Na+ + NO3- …….. (2).
Na+ + H2O NaOH + H2 …….. (3).
H2O H+ + OH- …….. (4).
H2O + 2OH- ½ O2 + H+ …….. (5).

ii) The weighed PCB’s were placed in a cloth bag. Then graphite rod of 25mm
diameter anode (Ti plate can also be used as anode as it is non consumable) was
inserted into the bag and also care was taken that the cut pieces are in maximum
contact with the graphite anode to enhance the dissolution of the metallic values in
the PCB’s by improving the conductivity. This all set-up is called as anode set.
iii)The anode set was connected to positive terminal of the rectifier and stainless steel
mesh was connected to negative terminal of the rectifier (current 0-12A and
voltage 0-15V). Maximum possible current was set to carry out the experiment;
the voltage was maintained such that to achieve maximum current and hence rate
of dissolution was maximum.

iv) The bag was shaken periodically as the metals dissolves and contact may become
loose, due to this it was noted that there was rise in current as conductivity
increases. After some time the current rise was not noticeable. It means that metal

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values are in the solution. Dissolution of metallic values takes place according to
following reactions:

For Copper:
Cu + NO3- Cu(NO3)2 (goes in solution) + 2e- …….. (6).
For Lead:
Pb + NO3- Pb(NO3)2 (goes in solution) + 2e- …….. (7)
For Tin:
Sn + 2NO3- Sn(NO3)2 + 2e- …….. (8.a)
Sn + 4NO3- Sn(NO3)4 + 4e- …….. (8.b)
Sn(NO3)4 + H2O Sn(OH)4 + HNO3 …….. (9)

(Ignite) (Fusion with alkali)

Sn(OH)4 SnO2 Na2SnO3 (water soluble)

v) The remains in the bag were taken out dried and weighed and the weight loss in
the scrap was calculated it means that much amount of metals have gone into
solution.

vi) The current, voltage and time were measured so as to calculate the energy
consumed for dissolution.

OBSERVATIONS:-
Expt. No.1
Weight of PCB before Dissolution=500gm

TIME VOLTAGE CURRENT HNO3 ADDED IN

(Volts) (amp) (ml)
12.05 PM 14.92 8.01 25
12.20 PM 9.02 10.03 -
12.40 PM 7.67 9.92 -
12.55 PM 9.68 10 -

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1.10 PM 7.73 10 50
1.25 PM 7.41 9.98 50
1.40 PM 7.02 9.97 50
1.50 PM 6.78 9.99 100
2.10 PM 6.51 9.99 100
2.30 PM 6.33 9.96 100
3.00 PM 6.07 9.96 100
3.45 PM 5.80 9.93 200
4.35 PM 5.38 9.92 200
5.00 PM 5.34 9.85 -

Weight of PCB after Dissolution =382gm

Expt. No.2
Weight of PCB before Dissolution=500gm
TIME VOLTAGE CURRENT HNO3 ADDED IN
(Volts) (amp) (ml)
11.30 PM 10.63 9.98 -
11.45 PM 9.54 9.90 100
12.10 PM 8.93 9.86 100
12.25 PM 8.97 9.86 50
12.45 PM 8.55 9.85 50
1.30 PM 7.92 9.83 100
1.45 PM 8.04 9.82 50
2.00 PM 7.90 9.82 50
2.15 PM 7.9 9.80 50
2.30 PM 7.83 9.80 50
2.45 PM 7.68 9.79 50
3.00 PM 7.79 9.80 50
3.15 PM 7.57 9.80 -

Weight of PCB after Dissolution =288gm

Expt. No.3
Weight of PCB before Dissolution = (600+500+400) gm = 1500gm
We went on changing the scrap in this trial because it was not possible to dissolve
all the metallic values in one single trial, due to this we were able to increase the
concentration of metallic values in the same bath prepared before.

3.a ) Scrap of wt. 600gm :-

TIME VOLTAGE CURRENT HNO3 ADDED IN
(Volts) (amp) (ml)

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1.30 PM 7.30 11.50 -

2.15 PM 7.25 11.35 200
3.00 PM 7.23 11.34 200
3.20 PM 7.22 11.31 100
3.30 PM 7.01 11.21 -
3.35 PM 7 11.20 100
3.50 PM 6.87 11.16 -
3.55 PM 6.82 11.15 100
4.05 PM 6.08 11.16 -
4.40 PM 6.92 11.13 300
4.50 PM 6.64 11.14 100

PCB’s were removed dried and weighed

Weight of PCB after Dissolution =527gm
pH = 1
3.b) Scrap of wt. 500gm was added:-

TIME VOLTAGE CURRENT HNO3 ADDED IN

(Volts) (amp) (ml)
11.20 PM 7.13 11.62 -
1.20 PM 6.71 11.68 -

PCB’s were removed dried and weighed

Weight of PCB after Dissolution =383gm
pH = 1

3.c ) Scrap of wt. 400gm was added:-

TIME VOLTAGE CURRENT HNO3 ADDED IN

(Volts) (amp) (ml)
2 PM 7.07 11.80 -
2.20 PM 6.95 11.53 -
2.40 PM 7.36 11.45 -
3.30 PM 7.13 11.03 -
4.00 PM 6.85 11.11 -

PCB’s were removed dried and weighed

Weight of PCB after Dissolution =298gm
pH = 1

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 RECOVERY OF METALS FROM E-SCRAP

Total weight of PCB scrap after drying= 527+383+298=1208gm

Weight loss = 1500-1208=292gm

Figure 1: LINE DIAGRAM OF THE SETUP

B] Method 2: Dissolution using Aqua regia solution

The residue from bag is subjected to treatment with 50% aqua regia (1 HNO3: 3 HCl),
and see if any green coloration is obtained. That indicates presence of gold. The metallic

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values which were not dissolved in above mentioned treatment also gets dissolved in aqua
regia. The reaction in aqua regia are:
For Silver:
Ag + HNO3 AgNO3 + H2 ………(10)
For Gold:
HCl + HNO3 NOCl ………(11)
Au + NOCl AuCl3 (water soluble) + NO2 ………(12)

III) Recovery of the dissolved metals from solution by different metallurgical routes:
i) Recovery of copper by electro deposition method:

Cu plate was polished by emery paper; cleaned with acetone. After drying this
plate, initial weight was noted. This copper plate was connected to negative terminal
(cathode) and graphite rod was connected to positive terminal (Anode) of the
rectifier. Both electrodes were dipped in solution and supply was given.
Reaction at Anode:
H2O + 2OH- ½ O2 + H+
2 H+ H2
Reaction at Cathode:
Cu2+ + 2e- Cu (deposited on cathode)

Solution was taken 400 ml from the dissolved bath.

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Bath Voltage Current Current Initial wt. Wt. of Cu plate Time Wt.
no. (V) (A) density of Cu plate after (min) deposited(gm)
(A/m2) (gm) deposition(gm)
1 2.19 0.98-1 272.22 21.2680 21.8097 60 0.1417
2.a 3.4 1 277.77 17.6829 19.0059 120 1.323
2.b 3.4 1 317.46 30.3631 31.3290 55 0.9659
2.c 3.4 1 320.51 38.5673 39.1709 160 0.6036

ii)Recovery of copper by cementation method:

Mild steel plate was polished by emery paper; pickling was done (HCl
100ml+Antimony Trichloride 5%). It removes rust from the plate, this plate is dipped in
solution and copper gets deposited on mild steel plate.
The first two trials of dissolution experiment have been failed while cementation
process as excess time was given for the deposition by cementation due to which the bath
was fully oxidized by iron oxide.
In next three trials of dissolution experiment we gave less time for deposition by
cementation process and got the results as follows:

Weight of M.S Plate = 34.446 gm

Time of dipping in solution = 1 minute
The copper deposited on M.S. plate was scrapped out and weighed.
Weight of copper obtained = 0.152 gm.

POWER CONSUMTION
For dissolution experiment:
Exp. Initial wt. of scrap Net Net Time Power = V*I*t
no. sample (gm) Voltage Current (min) (KWH)
(V) (amp)
1 500 7.55 9.82 295 0.3645
2 500 8.404 9.84 225 0.3110
3.a 600 6.3155 11.24 200 0.2366
3.b 500 6.92 11.65 120 0.1612
3.c 400 7.072 11.38 120 0.1610

For electro deposition of Cu:

Bath Wt. deposited Voltage Current Time Power = V*I*t

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no. (gm) (V) (amp) (min) (KWH)

1 0.1417 2.19 0.98 60 0.0021
2.a 1.323 3.4 1 120 0.0068
2.b 0.9659 3.4 1 55 0.0031
2.c 0.6036 3.4 1 160 0.0091

QUALITATIVE ANALYSIS:

Confirmatory test for Lead:

After electro deposition of Copper, electrolyzed solution was taken for confirmatory
test. In that solution potassium iodide (KI) powder was added, which showed yellow
precipitate. This shows that the lead is present in the solution.

Confirmation of Tin:
While dissolution of e-scrap, tin gets precipitated as metastannic acid, from which tin
can be recovered. (ref 1.). We have separated the precipitate from solution.

RESULT:

1) PCB’s are containing copper, lead and tin along with non metallic particle.
2) We have recovered Copper successfully.
3) Our process is eco-friendly, convenient and recovers the metal values almost
quantitatively.

CONCLUSION:
It is possible to recover the metal values from e-scrap by anodic dissolution using
nitric acid bath.

FUTURE WORK:
1) The recovery of lead is in progress.
2) The recovery of tin is in progress.
3) It has been reported that there is gold and palladium present in PCB. Our aim is to
recover gold and other precious metals as well, along with copper, lead and tin.
We are trying to get the average percentage of each metal.
4) Neutralization of bath for disposal and can be reused.

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2HNO3+Na2CO3 2NaNO3 + CO2 + H2O

pH = 7.

REFERENCES:

1) Leaching and electrochemical recovery of copper, lead and tin from scrap printed circuit
boards. (Journal of chemical technology and Biotechnology); (Chem Technol Biotechnol
77:449-457/ 2002).

2) Metallurgical recycling of electronic scrap EPD Congress 2006 Edited by S.M. Howard,
R.L. Stephens, C.J. Newman, J.-Y.J. Hwang, A.M. Gokhale, T.T. Chen,
TMS (The Minerals, Metals & Materials Society), 2006
T.P. Battle, M.L. Free, B.R. Davis, C.L. Harris, H. Henein, P.N. Anyalebechi, A.C.
Powell, G.K. Krumdick, and C.K. Belt.

3) Printed Circuit Board Recycling:A State-of-the-Art Survey

Jianzhi Li, Puneet Shrivastava, Zong Gao, and Hong-Chao Zhang, (IEEE
TRANSACTIONS ON ELECTRONICS PACKAGING MANUFACTURING, VOL. 27,
NO. 1, JANUARY 2004).

4) Recycling Technology for Electronic Appliances

Jyh-Herng Chen
Department of Materials and Mineral Resources Engineering
National Taipei University of Technology
No. 1, Sec. 3, Zhongxiao E. Rd.
Taipei, Taiwan, ROC

5) http://en.wikipedia.org/wiki/Electronics_waste (pg. no. 1-8)

6) http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TGF-4RSRDNX-4
(Journal of Hazardous Materials, Volume 158, Issues 2-3, 2008, pg. no. 228-256).

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