Pollution Control

Recovery of Copper Particles from Waste Printed

Circuit Boards

Name: Darpan Lakhmani

ID: AU1642001
Branch: Chemical Engineering
Introduction
As electronics moved from vacuum tubes and relays to silicon and integrated
circuits, the size and cost of electronic components began to decrease. Electronics
became more prevalent in consumer goods and the pressure to reduce the size
and manufacturing costs of electronic products drove manufacturers to look for
better solutions. Thus was born the PCB. PCB is an acronym for printed circuit
board. It is a board that has lines and pads that connect various points together.
In the picture above, there are traces that
electrically connect the various connectors and
components to each other. A PCB allows
signals and power to be routed between
physical devices. Solder is the metal that
makes the electrical connections between the
surface of the PCB and the electronic components. Being metal, solder also serves
as a strong mechanical adhesive. A PCB is sort of like a layer cake- there are
alternating layers of different materials which are laminated together with heat
and adhesive such that the result is a single object.

In recent years there has been increasing concern about the growing volume of
end of life electronics and the fact that much of it is consigned to landfill without
any attempt being made to recycle the nonmetallic materials it contains. The
production of electric and electronic equipment (EEE) is growing rapidly in most
developed countries. Waste of electric and electronic equipment (WEEE) is
significantly increasing. A large amount of nonmetallic materials in printed circuit
board (PCBs) are disposed of by combustion and disposal in landfill as the main
method for treating nonmetals in PCBs, but it may cause secondary pollution and
resource wasting. Therefore, it is urgent to develop a proper recycling technology
for waste PCBs. Several recycling technologies and potential reuses of recovered
nonmetallic PCBs were reviewed in this paper. From the review, it can be said
that, PCBs recycling process usually includes three process which is pretreatment,
physical recycling, and chemical recycling and the recovered nonmetals were used
to make models, construction materials and composite boards. The PCB nonmetal
products have better mechanical characteristics and durability than traditional
materials and fillers. Products derived from PCB waste processing have been
brought into industrial production.

Printed circuit board (PCB) form about 3% by weight of the total amount of WEEE
produced. PCBs are electronic circuits created by mounting electronic
components on a non conductive board and creating conductive connections
between them .The creation of circuit patterns is accomplished using both
additive and subtractive methods. The typical circuit board is made of epoxy
resin, fiberglass and copper. They also cited that usually bromine fire retardant is
added to the resin to increase the fire resistance. The conductive circuit is
generally consisting of various metals. Generally PCB scrap contains
approximately 40% metals, 30% plastics and 30% ceramics. The typical metal
scrap in PCB consists of copper, iron, tin, nickel, lead, zinc, silver, gold and
palladium. The copper and other precious metals contained therein make it a
potentially recyclable material. In fact, the copper mainly is the most interesting
metal and it can be use as a secondary raw material because of its relatively high
content compared to the corresponding content in explorable ores. There are
three basic varieties of PCBs which are single-sided, double-sided and multi-
layered. The spatial and density requirement and the circuitry complexity
determine the type of board produced. The choice of manufacturing materials
used for PCBs also depends on the application. PCBs contain nearly 28% metals
and almost 70% non metallic materials. Non metallic materials of PCBs mainly
consist of thermoset resins and reinforcing materials that make it challenging and
problematic to be recovered or recycled. Hence, it has zero values and always
become end wastes that will be dumped at the disposal site. However, this action
will create secondary pollution and cause resource wasting.
Waste printed circuit boards (WPCBs) contain plenty of valuable resources and
hazardous materials considered as attractive secondary resource and an
environmental contaminant. In the current research, a process combined
ammonia leaching and solvent extraction to recover copper from the metal
components of WPCBs, and the production of ultrafine copper particles stripped
from a solution was investigated. Printed circuit boards (PCBs) are typical and
fundamental components of almost all electric and electronic equipment (EEE).
With the rapid development of technology and the society, high-performance
requirements and great demands in make replacement of PCBs more frequent,
resulting in large quantities of waste PCBs (WPCBs) that need to be disposed.
Mechanical and pyrometallurgical methods are the current ways of recycling
WPCBs. Almost all waste recycling enterprises in China use various mechanical
methods (such as multicrushing, grinding, electrostatic separation, gravity
separation, fluidbed separation, density-based separation, and magnetic
separation) to separate metals and non-metals from WPCBs. After the mechanical
separation, approximately 30 wt.% of enriched multi-metal components (Cu, Al,
Fe, Sn, Sb, Pb etc) are separated from the non-metal.

Recycling of Printed Circuit Boards

Recycling process for waste printed circuit board includes three process which is
pretreatment, physical recycling, and chemical recycling. PCBs recycling generally
start from the pretreatment stage, which include disassembly of the reusable and
toxic parts using shredding/separation and then PCBs are treated using physical
recycling process. In the end, materials are finally recovered after chemical
recycling process that consists of pyrolysis process and gasification process. While
metal fraction can be treated by pyrometallurgical, hydrometallurgical, or
biotechnological process. Through shredding and separation process, PCB boards
are reduced into small sized particles and can be separated by various separation
methods such as physical or chemical refining process. In physical recycling
process, magnetic separators, low intensity drum separators are widely used for
the recovery of ferromagnetic metals from non-ferrous metals and other non
magnetic wastes. Corona electrostatic separation are used to separate materials
of different electric conductivity such as non ferrous metals from inert materials.
This Eddy current separation technology is also used to recover metals, which
consists of approximately 28% by weight of a typical PCB scrap. Other than that,
Density based separation of particles such as sink-float separation is also used to
separate metal from nonmetallic materials in PCB scraps. Hence, it can be said
that, physical recycling reported a great potential and a promising recycling
method without environmental pollution, lesser investment, operation cost and
low energy cost. However, the separation between the metallic and nonmetallic
materials in PCB waste has to be enchanced. Typical chemical recycling process
consists of pyrolysis process and gasification process. Pyrolysis actually degrades
the organic part of the PCB waste, making the process of separating and recycling
the organic, metallic and glass fibre in PCB much easier. One of the main
ingredients in PCB scrap, resin is originally produced from crude oil and can be
thermally cracked into fuels or petrochemicals. So, it can be seen that, pyrolysis is
an economical and environmentally sound resource recovery alternative to treat
PCB scraps.

Hydrometallurgical processes are mainly used for recycling of the metallic ferrous
materials in PCB where the extraction of the metal content is profitable has
reported in their studies that different hydrometallurgical processes can be used
depending on the substrate material (ceramic, glass, or polymer). They also stated
that, for nonmetallic substrates, metals are recovered from substrates by the
process of leaching in the resulting solution. While for metallic substrates,
electrochemical processing can be used to recover metals. Thus, a pure metal
recovered can be sold without any further processing while the remaining
nonmetallic substrates still need to be treated thermally prior reusing or dumping
in landfills. Hydrometallurgical method is also said to be more exact, more
predictable and more easily controlled compared to pyrometallurgical processing.
Biometallurgy has been used for recovery of precious metals and copper from ore
for many years [25,26] but biometallurgy used for recycling waste PCBs is still in
its infancy. Biometallurgy is one of the most promising technologies in
metallurgical processing. Microbes have the ability to bind metal ions present in
the external environment at the cell surface or to transport them into the cell for
various intracellular functions. This interaction could promote selective or non-
selective in recovery of metals. Bioleaching and biosorption are the two main
areas of biometallurgy for recovery of metals. Bioleaching has been successfully
applied for recovery of precious metals and copper from ores for many years.
However all the processes mentioned above are being done in order to collect the
precious metals on that board and reuse it for other purposes. The remaining is
the non metallic materials that usually being dumped in landfill.

Hydrometallurgical treatments have more flexibility during the upscaling and

control processes. Sulfuric, hydrochloric and nitric acid solutions are often used as
leaching agents in hydrometallurgical treatments. In these cases, however, the
separation process tends to become complicated because of poor selectivity
during leaching. Hydrometallurgical recovery process to recover copper from
WPCBs. Copper in the waste was first leached as Cu(I) using Cu(II) as oxidizing
agent. Impurities in the solution were then removed by solvent extraction using
LIX 26 (active ingredient: alkyl-substituted 8-hydroxy-quinoline), and the purified
Cu(I) solution was electron in a diaphragm cell. Cu(I) was reduced to metallic
copper at the cathode. The remaining Cu(I) passed to the anode compartment
where it was oxidized to Cu(II). The produced Cu(II) can be recycled at the
leaching stage. The proposed process has the potential of producing high-purity
copper directly from WPCBs with low power consumption. However, even under
optimized conditions, the obtained leaching efficiency was proven to be incapable
of reaching more than 93%, whereas the current efficiency cannot exceed 95%.
The need to crush the PCBs into fine particles to less than 1.5 mm average
diameter and the difficulty in preventing Cu(I) to be oxidized into Cu(II) during the
leaching and electrowinning stages are the two obvious disadvantages that limit
the application of this process into practice.

In the present study, another process is proposed, which combine ammonia-

ammonium sulfate leaching and solvent extraction using LIX 84 (2-hydroxy-5-
nonylacetophenome oxime) as extractant, to recover copper from the metal
components of WPCBs, obtaining ultrafine copper particles stripped from the
solution as end product. This process has been applied for patents in China, and
recently has been authorized by China. The current paper demonstrates that
copper not only can be efficiently recovered from WPCBs but can also be
recovered as more profitable ultrafine copper particles.

Experimental details
Materials

The enriched multi-metals, obtained from Aomeite Resource Recycle Co., China,
were characterized for chemical composition and phase analysis. The dry screen
used for the analysis was about 10 mesh (2mm), and all samples were leached
without further grinding. Chemical analysis of the enriched multi-metals was
conducted by AAS (Atomic Absorption Spectrophotometer), except for the
copper, tin, and zinc contents were analyzed by chemical titration, and the results
are given in Table 1. X-ray diffraction analysis showed that copper was present
mainly as metallic copper (>98%) and as copper oxide (CuO) (b2%) in small
quantity (Table 2). The other chemicals used were of reagent grade. The sodium
hypophosphite, oleic acid, ammonia, LIX 84 (2-hydroxy-5-nonylacetophenome
oxime), and H2SO4 were purchased from Changsha, China, with no further
purification introduced.
Method

The waste printed circuit boards were firstly treated by using mechanical
methods, such as multi-crushing, grinding, electrostatic separation, gravity
separation, and magnetic separation to separate metals and non-metals from
WPCBs.

Ammonia–ammonium sulfate leaching

Ammonia–ammonium sulfate leaching was performed in 500 mL glass flasks by

adding weighed amounts of enriched multi-metal powder, ammonia, ammonium
sulfate, and surfactant to a tap-water solution at the desired temperature and
magnetically stirred at a certain stirring rate. For oxidation, air was continuously
blown into the mixture through a glass pipe linked at the other end to an air
compressor (HYG- 30, Truelab Co., Shanghai). The system temperature was
controlled using an oil bath heater. A condenser was attached to the flask to
prevent vaporization loss. At the end of each experiment, the insoluble leach
residue was filtered and washed with 80 mL tap water. The copper leaching
efficiency was calculated by mass balance from the analysis of the raw materials
and the leach residue.

LIX 84 solvent extraction and H2SO4 stripping

The solvent extraction test procedure was as follows: measured amount of

leached solution and extraction agents was put in a separatory funnel and rapidly
shaken. To ensure proper mixing, the shaking speed was kept constant at 120
r/min in all the experiments. After the solvent extraction, the organic–aqueous
phases were separated by the separatory funnels. The copper extraction extent
was determined by measuring the volume of the leached and the extracted
residual solutions, as well as the metal concentration. Copper stripping
usingH2SO4was performed as follows: ameasured amount of pregnant organic
solution and H2SO4 was put in the separatory funnel and rapidly shaken. To
ensure proper mixing, the shaking speed was kept constant in all the experiments.
After the stripping process, the organic–aqueous phases were separated by the
separatory funnel. The copper stripping rate was determined by measuring the
volume of the pregnant organic and pregnant solutions, as well as the metal
concentration.

Ultrafine copper particle preparation

In the copper particle preparation test, two solutions were first mixed: one was
the above-mentioned CuSO4 stripping solution, and the other was a 0.5 mol/L
oleic acid. The mixture was shaken at normal conditions for 30 min using
ammonia to adjust the pH value to around 12. The resulting aqueous–organic
solvent was subsequently reduced with sodium hypophosphite. The reaction
solution was constantly agitated at moderate speed to ensure uniformity of the
system and to keep the precipitated particles dispersed until the reduction was
completed. After 2 h of aging, the precipitate was separated from the liquid
solution by centrifugation, and the resulting powder was then dried in a vacuum
stove at 333 K for 4 h.

Result and Discussion

 Ammoniacal leaching was first conducted by varying the ammonia concentration
from 0 mol/L to 4 mol/L. The copper leaching efficiency was observed to increase
as the ammonia concentration was increased from 0 M to 2 M. Beyond 2 M,
however, the copper leaching efficiency decreased. The reason can be attributed
that the reaction between OH− and Cu2+ to form Cu(OH)2 become more
predominant than the NH3 chelation with Cu2+ to form Cu(NH3)2+ with the
ammonia concentration increased to 2 M. Thus, a 2 M ammonia concentration
was used for the leaching of Cu(II) in the present research; Similarly, the
concentration of ammonium sulfate in the solution was varied from 0 mol/L to 4
mol/L under the operating conditions shown in Table. It was observed that the
leaching efficiency increases with the addition of ammonium sulfate up to 2 M.
Beyond 2 M, the efficiency decreases, which could be because increasing the
ammonium sulfate caused the dissociated ammonia in the solution to decrease
resulting in the corresponding decrease of the copper–ammonia ligand
concentration. Thus, 2 M ammonium sulfate was chosen as the optimum
ammonium sulfate concentration.

The various magnetic stirring rates employed were 200, 400, 500, 600, and 800
r/min under the operating conditions. The leaching efficiency increased from 9.9%
to 91.9% as the magnetic stirring rate was increased from 200 r/min to 400 r/min,
beyond which no obvious benefit was observed. The reason could be because
copper must be oxidized before being chelated with dissociated ammonia. When
the magnetic stirring rate was increased from 200 r/min to 400 r/min, the contact
between oxygen and copper accordingly increased. However, when the magnetic
stirring rate was continuously increased, a stable value was reached and the
volatility rate of ammonia also increased, causing a decline in the copper leaching
efficiency. Thus, a 400 r/min magnetic stirring rate was chosen as the optimum
stirring rate; The various leaching time employed were 1.0, 1.5, 2.0, 2.5, and 3.0 h
under the operating conditions shown in Table 3. The leaching efficiency
increased as the leaching duration was increased from 1.0 h to 2.0 h; the leaching
efficiency was observed to increase from 57.2% to 93.6%, beyond which no
obvious benefit was observed. Therefore 2.0 h of leaching time was chosen as the
optimum leaching duration; The various solid:liquid ratios (g/cm3) used were 1:5,
1:10, 1:15, 1:20, and 1:25 under the operating conditions shown in Table 3, and it
was observed that the leaching efficiency increased as the solid:liquid ratio was
increased from 1:5 to 1:25. When the solid:liquid ratio reached 1:20, the copper
leaching efficiency almost reached up to 90%; beyond this ratio, no obvious
benefit was seen. Considering the water dosage and copper leaching efficiency,
1:20 was chosen as the optimal solid:liquid ratio.

The effect of leaching temperature on copper leaching efficiency. No obvious

advantages were observed as the leaching temperature was increased from 5 to
35 °C, and the copper leaching efficiency was more than 90%. Beyond this
leaching temperature, the volatility of ammonia increased accordingly, causing a
decrease in the copper leaching efficiency. Thus, 35 °C was chosen as the
optimum leaching temperature. In addition, air ventilation quantity of 12 m3/h
was found to be the optimum condition for copper leaching; quantities lower or
higher than this were adverse to copper extraction. Therefore, 12 m3/h was
chosen as the optimum air ventilation quantity.

Conclusions
 A comprehensive procedure was developed for the separation and
recovery of ultrafine copper particle from enriched multimetal solution of
WPCBs containing mainly Cu, Zn, Pb, Fe, Al, and so on. All process
conditions, including ammonia–ammonium sulfate leaching, LIX 84 solvent
extraction, H2SO4 stripping, and ultrafine copper particle preparation were
optimized. Copper extraction efficiency of 96.7% was obtained at a
temperature of 35 °C over a 2 h-leaching duration using 2 mol/L ammonia
and 2 mol/L ammonium sulfate concentration with a 12 m3/h air
volumetric flow rate and a solid:liquid ratio of 1:10.
  The treatment of leach liquor for the solvent extraction of copper using LIX
84 showed that 50% LIX 84 in kerosene, a 3 min period of equilibration, and
a pH of 10 were sufficient for extraction of Cu(II), and under this condition,
99.3% of copper can be recovered from the leached solution.

The results of the preparation of copper particles from the stripped solution
showed that well-dispersed ultrafine copper particles with approximately 1.5 μm
diameter were obtained from the stripped solution containing 39.25 g/L Cu2+ ion,
using oleic acid used as surfactant and sodium hypophosphite used as reductant.