Resources, Conservation and Recycling 49 (2007) 217–243

Review
Analysis of key patents of the regeneration
of acidic cupric chloride etchant waste and
tin stripping waste
Tiina Keskitalo a,∗ , Juha Tanskanen a , Toivo Kuokkanen b
a Department of Process and Environmental Engineering, Chemical Process Engineering Laboratory,
University of Oulu, PO Box 4300, FI-90014 Oulu, Finland
b Department of Chemistry, University of Oulu, PO Box 3000, FIN-90014 Oulu, Finland

Received 14 December 2005; received in revised form 2 May 2006; accepted 24 May 2006
Available online 11 July 2006

Abstract

Spent acidic cupric chloride etchant waste and tin stripping waste from printed circuit board (PCB)
industry are classified as hazardous wastes. They contain significant amounts of metals and acid.
Usually, spent cupric chloride and tin stripping solutions are shipped off-site for reclamation. At
the moment, a large proportion of acidic cupric chloride etchant waste and tin stripping waste are
treated by neutralization, resulting in metal-bearing sludge that often ends up in special landfills. This
wastes valuable natural resources, which could otherwise be recycled. This paper presents a review
of some patented methods developed for the regeneration of acidic cupric chloride etchant waste
and tin stripping waste. These methods are based on electrowinning, cementation, solvent extrac-
tion, precipitation and membrane technology. The advantages and disadvantages of these developed
processes are summarized. It can be seen that there is still a need to develop more efficient and
economical processes for the regeneration of acidic cupric chloride etchant waste and tin stripping
waste.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Etching; Etchant waste; Cupric chloride; Tin stripping; Regeneration

∗ Corresponding author. Tel.: +358 40 5712523; fax: +358 8 553 2304.

E-mail address: tiina.keskitalo@oulu.fi (T. Keskitalo).

0921-3449/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.resconrec.2006.05.001
218 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
2. Regeneration of acidic cupric chloride etchant waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
2.1. Electrolytic regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
2.2. Regeneration based on cementation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
2.3. Regeneration based on solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
2.4. Regeneration based on the precipitation of copper oxide . . . . . . . . . . . . . . . . . . . . . . . 227
2.5. Regeneration to yield basic copper chloride micronutrient additive . . . . . . . . . . . . . . 228
2.6. Summary of the methods of regenerating acidic cupric chloride etchant waste . . . . 231
3. Regeneration methods of tin stripping waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
3.1. Electrolytic regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
3.2. Regeneration based on solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
3.3. Sustainable technologies for the regeneration of tin stripping waste . . . . . . . . . . . . . 237
3.4. Summary of the methods for the regeneration of nitric acid-based tin stripping
waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
4. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242

1. Introduction

Etching is a process whereby the unwanted copper foil on a printed circuit board (PCB)
is oxidized and then dissolved into a liquid carrier called an etchant. The parts of the foil
intended to act as trackwork are protected from dissolution during etching by being covered
with an etch resist (Fitzpatrick-Brown, 1985). The etch resist must not be affected by the
etchant and vice versa. Resists are available in two different classes. The first class consists
of organic resists based on an organic chemical or mixture. The second class consists of
metallic resists, which are based on a pure metal. When etching innerlayers, the etch resist
is usually an organic compound (photoresist), and when etching outerlayers, the etch resist
is usually a metallic layer.
There are several etchants available. The choice of etchant depends on many things,
such as the structure of the PCB and the availability of suppliers. Cupric chloride (CuCl2 )
became the main etchant for PCBs with non-metallic resists in the 1960s. Up until then,
ferric chloride had been the most common etchant for non-metallic resist PCBs due to its
fast etch rate and high metal holding capacity. Cupric chloride superseded it in popularity
because it is capable of continuous chemical regeneration and can be operated in a steady-
state condition. CuCl2 also became desirable because it could use the copper from the
circuitry as an additional etchant without a need to introduce other metals into the etching
bath (Gurian et al., 2000). Cupric chloride etchant is an acidic solution where hydrochloric
acid keeps the copper soluble. The reason why copper can be etched by using a solution of
copper itself is due to the fact that copper can be easily transformed from one oxidation state
to another. In cupric chloride etching, elemental copper reacts with cupric copper (Cu2+ ) to
form cuprous copper (Cu+ ), as it can be seen in reaction (1) (Chemcut corporation, 2002):
Cu0 + Cu2+ Cl2 → 2Cu+ Cl (1)
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 219

Copper accumulates in the solution during the etching process, while the copper ions respon-
sible for etching are reduced. In order to maintain the etch rate, cuprous copper must be
converted back to the cupric state, so that it can etch more metal. This is done through chem-
ical regeneration of the etchant. From a chemical point of view, the simplest replenisher is
chlorine gas (Cl2 ) (Sedlak, 1995). The reaction between cuprous chloride and chlorine gas
can be seen in the following equation:

2Cu+ Cl + Cl2 → 2Cu2+ Cl2 (2)

However, there are practical difficulties when using Cl2 due to safety issues and legislation.
Therefore, oxidizing chemicals, such as hydrogen peroxide (H2 O2 ) or sodium chlorate
(NaClO3 ), are normally used in the chemical regeneration of the etchant because they react
with hydrochloric acid, producing the chloride ions needed to oxidize Cu+ ions to Cu2+ ions,
as it can be seen in reactions (3) and (4). If sodium chlorate is used as a replenisher, sodium
chloride (NaCl) is a by-product of the regeneration reaction, which means that there will be
an extra component in the etching bath. For continuous operation of etching, also the etched
copper should be removed as it accumulates (Adaikkalam et al., 2002). The concentration
of copper is maintained by occasionally withdrawing a portion of etchant from the etching
bath and replacing it with a fresh solution. The disadvantage is that the excess etchant must
be disposed of in an environmentally acceptable manner.

2Cu+ Cl + H2 O2 + 2HCl → 2Cu2+ Cl2 + 2H2 O (3)

6Cu+ Cl + NaClO3 + 6HCl → 6Cu2+ Cl2 + NaCl + 3H2 O (4)

Analysis of the recovery of ammoniacal etchants was not the target of this paper, but since
they are sometimes processed together with acidic cupric chloride etchant wastes, some
chemistry of ammoniacal etching needs to be examined as well. Ammoniacal etchant is
the other approach to etching of innerlayers. Ammoniacal etchant is a mixture of cuprous
chloride Cu(NH3 )x Cl and cupric ammonium chloride Cu(NH3 )x Cl2 (Queneau and Gruber,
1997). Similarly to the cupric chloride etching, the copper that is already in solution in
the ammoniacal etchant, dissolves the copper metal on the circuit board. However, cuprous
(Cu+ ) compounds are not soluble, except in the presence of ammonia, which is why etching
is facilitated by the ammonia and chloride in the etchant. The overall reaction is shown in
the following equation:

Cu0 + Cu2+ (NH3 )4 Cl2 → 2Cu+ (NH3 )2 Cl (5)

The cuprous salts are then oxidized by the oxygen in the air, which is being pulled through
the etcher, as it can be seen in the following reaction:

2Cu+ (NH3 )2 Cl + 2NH3 + 2NH4 Cl + 1/2O2 → 2Cu2+ (NH3 )4 Cl2 + H2 O (6)

When making an outerlayer, the etch resist is usually a metallic layer of pure tin or tin/lead
alloy. The metal coating protects the copper tracks on the PCB during etching. After etching,
the metallic etch resist must be removed by a process called tin stripping. Nowadays, the
most common tin stripping solutions are nitric acid-based solutions that involve a source of
ferric ions.
220 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

Tin has three different oxidation states, i.e. elemental tin, stannous tin (Sn2+ ) and stannic
tin (Sn4+ ). In the stripping process, tin is oxidized to its stannic form. The reaction for nitric
acid-based tin stripping is shown in equation (7) (McKesson, 1999):

2Sn0 + 2HNO3 → 2Sn4+ O2 + N2 O + H2 O (7)

Once tin has been oxidized, it must be dissolved into the solution. However, most stannic
salts are insoluble in water. In addition to being insoluble in water, the stannic oxide (SnO2 )
formed during the stripping reaction is also insoluble in nitric acid. Therefore, to prevent
the stannic oxide from precipitating out, it must be dispersed in the liquid phase by a
suspending agent. Some other additives are also added into commercial tin strippers for
different purposes, for example, to help to protect the underlying copper surface from the
solution. Spent tin stripper is a milky white acidic solution, and stannic oxide is extremely
difficult to remove from it since it does not form a filterable precipitate (Kerr and Coultard,
2004).
At some point, the tin stripping bath becomes exhausted and needs to be treated and
replaced with a fresh solution. The tin stripping process can be operated either batchwise
or continuously. In batch type operation, there might be as much as 200 g/dm3 of metal in
the final stripping solution. Alternatively, the chemistry may be used on a ‘feed-and-bleed’
basis, which means that it is kept at a steady level by bleeding out a certain amount of
solution and replacing it with fresh chemistry. When these etching solutions are disposed
of, they typically contain over 100 g/dm3 of metal.
Both spent cupric chloride etchant and tin stripping solutions are usually stored in tanks
and shipped off-site for reclamation. They are classified as hazardous wastes, which are
becoming increasingly more expensive to dispose of. Usually spent tin stripping solutions
and often also spent cupric chloride etchant wastes are treated by neutralization, resulting in
metal-bearing sludge, which sometimes has to be discarded in special landfills. Neutraliza-
tion consumes a lot of caustic solution and fails to solve the waste problem. Neutralization
and disposal of the formed precipitate result in a costly waste of raw materials because spent
acidic cupric chloride and tin stripping solutions contain a lot of valuable components that
should be recovered economically. Therefore, at the present, tin stripping waste and cupric
chloride etchant waste constitute a big problem for PCB industry. There is clearly a need
to develop technically and economically feasible regeneration processes for these wastes.
In this paper, some methods developed for the regeneration of spent acidic cupric chloride
etching and tin stripping solutions are described. Certain advantages and disadvantages of
these methods are also discussed.

2. Regeneration of acidic cupric chloride etchant waste

2.1. Electrolytic regeneration

Since the copper concentration is relatively high in spent cupric chloride etching solu-
tions, electrolytic regeneration seems an appealing alternative. There are inventions that
utilize a regeneration process which reverses reaction (1) in such a way that the copper
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 221

metal etched into the system is continuously removed, and the evolution of chlorine and
hydrogen gas is avoided. Since electrolytic recovery from solutions containing chloride
ions by avoiding Cl2 evolution is difficult, there are also methods that involve electrolytic
recovery of copper and use of the generated chlorine gas in the chemical regeneration of the
etchant. However, the use of Cl2 is forbidden in many areas, which makes such methods of
regeneration useless. Several attempts have been made to develop electrolytic processes for
the regeneration of acidic cupric chloride etchant waste. Those methods can be operated in
a closed-loop cycle with the etching process. Many of them, however, suffer from various
drawbacks. A few of the developed methods will be described below.
If regeneration is done by reversing the etching reaction, Cu+ is oxidized to Cu2+ at the
anode and the Cu metal is electrodeposited via the simultaneous reduction of Cu2+ to Cu+
and the reduction of Cu+ to Cu metal at the cathode (Oxley, 1995). This is accomplished
by exceeding the limiting current for the reduction of Cu2+ to Cu+ , forcing the subsequent
reduction of Cu+ to Cu metal to take place. At the same time, the limiting current for the
anodic reaction must not be exceeded, so that the next electrochemical oxidation process,
chlorine evolution, can be avoided. Similarly, in order to avoid H2 evolution at the cathode,
the limiting current for combined cathodic reactions must not be exceeded. H2 or Cl2
evolution can be avoided by careful control of solution mass transfer and current density.
The desired reactions can be achieved by arranging to have a much higher real current
density at the cathode than at the anode. If the real current densities were the same, Cu+
would be oxidized to Cu2+ at the anode and Cu2+ reduced to Cu+ at the cathode without
any net regeneration.
Some of the first efforts to develop a commercial electrolytic system for the regeneration
of acidic cupric chloride etchant waste are the methods patented by Bell Telephone Labour
Inc. (Garn and Sharpe, 1960) and Western Electric Co. (Parikh and Willard, 1974). In those
methods, the real current density is made higher at the cathode than at the anode by using
smaller cathodes than anodes. Copper is recovered as loose, granular deposits that can be
mechanically scraped off of the cathodes. In the former patent, the cathodes have a planar
plating surface area with sharp corners. The sharp corners, however, lead to variable current
density gradients, resulting in uneven copper build-up and looseness or hardness of the
copper on the cathodes. It is also difficult to avoid chlorine gas evolution, especially at the
solution interface, when relatively high operating currents are employed. The latter method
involves an arrangement where the cathode consists of a bundle of cylindrical rods, whereas
the anode is planar graphite. By having no major planar surfaces or sharp edges, the current
density gradient variations at the cathode can be minimized. However, because the anode
and cathode areas remain different, the problem of uneven current distributions is still not
totally solved. The uneven current distribution translates directly into an uneven potential
distribution, also resulting in Cl2 evolution at the anode (Oxley, 1995).
The Electricity Council (Hillis, 1984) patented an electrolytic regeneration method which
employs separate anolyte and catholyte flow loops with different electrolyte compositions
such that the catholyte is approximately 10 times more dilute in copper than the anolyte.
The electrolytic cell is provided with a cell divider slowing down the diffusion of ions
between the anode and cathode compartments. In this method, the need for different anode
and cathode areas can be avoided because the limiting current for the reduction of Cu2+
to Cu+ is exceeded by the difference in electrolyte concentrations. The metallic copper is
222 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

produced at the cathode in a dendritic form, and it readily falls off the cathode to the bottom
of the compartment, from where it can be removed without a need to withdraw the cathode.
Some problems of the aforesaid processes are described in the method patented by Oxley
(1995). One of the problems is the uneven current distribution caused by the different anode
and cathode areas. The uneven current distribution leads to uneven potential distribution,
which may make it impossible to avoid parasitic Cl2 evolution. The methods also suffer from
waste heat generation stemming from IR losses as a direct consequence of high operating
voltages (5–8 V). That leads to a need for heat exchangers, which is an additional operating
cost burden. In the method patented by Oxley (1995), current density is arranged to be higher
at the cathode than at the anode by using a porous flow-through anode instead of a flow-by
anode. A flow-through anode provides the necessary increased surface area internally, so
that the cross-sectional area of the anode and the cathode can remain the same. By using a
porous flow-through anode and a planar flow-by cathode, mass transport and real current
density can be controlled by adjusting flow rate and electrode thickness. In the process,
the coulombic efficiency for copper deposition can be maximized at low flow rates, while
anode efficiency is maximized at high flow rates. This method is less costly because of the
lower operating voltages and the improved on-line process control, operating efficiency and
reliability (Oxley, 1995).
The etching process involves some oxygen ingress, which will consume both CuCl and
HCl, resulting in the formation of CuCl2 and water. That has the effect of driving the redox
potential more positive. It also leads to a net growth in the solution inventory similarly
to chemical regeneration, which electrolytic regeneration seeks to avoid. This effect could
be alleviated to some extent by removing part of the spent etchant and disposing of it for
off-line waste treatment. Alternatively, to reverse the effect of oxygen ingress, Oxley (1995)
suggests an auxiliary cell to be placed before the main electrolytic cell. In the auxiliary cell,
the anode reaction would be oxygen evolution and the cathodic reduction of Cu2+ to Cu+ .
The latter is not difficult to achieve, but it is impossible to exclude chlorine evolution at the
anode, particularly at higher current densities, even though certain materials favour oxygen
evolution.
Although the above method seems advantageous, there is still a need for a more efficient
and productive recovery process. Oxley Research Inc. (Oxley et al., 1998) patented another
electrolytic process for the regeneration of acidic CuCl2 etchant waste, which also includes
two electrolytic cells. In the first electrolytic cell, the spent etchant containing a high fraction
of Cu2+ ions is converted into a solution containing a high fraction of Cu+ ions. In the second
electrolytic cell, the monovalent form of the metal is converted into metallic copper in a
marketable slab form. It has been found that plating copper from a solution containing a
high fraction of Cu+ ions is the key to producing an even, dendrite-free copper deposit. In
both cells, the anodic reaction consists of the oxidation of Cu+ to Cu2+ . Another advantage
of the method is that plating copper from a solution containing a high level of Cu+ ions
allows intermittent operation since the already plated copper will not redissolve when the
plating current is turned off and the cathode remains submerged in the catholyte. Especially
for smaller PCB shops, this is a major advantage.
The above methods seem attractive because the etchant can be regenerated in a closed-
loop system integrated with the etching bath. The electrolytic regeneration methods, how-
ever, seek to avoid chemical regeneration, which is very common these days. In practice,
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 223

too, it may be very difficult to avoid especially chlorine evolution whenever chloride ions
are present in the solution.
There are also some regeneration methods that include chlorine gas evolution and use
the formed Cl2 for the chemical regeneration of the etchant. However, as earlier mentioned,
the use of chlorine gas is limited, which makes these regeneration methods less relevant.
Therefore, only one regeneration method of that kind is briefly described here. Nittetsu
Mining Co. (Mikami et al., 1995) patented a method that includes electrolytic treatment
of either cupric chloride or ferric chloride etchant waste, using a diaphragm to withdraw
deposited copper in a cathode cell and supplying the generated chlorine gas in the anode
cell into the etching bath to oxidize the etchant. The used etchant is conducted first to the
cathode cell, from where the solution is conducted to the anode cell in order to oxidize the
Cu+ ions to Cu2+ ions along with the generation of chlorine gas. Chlorine is supplied to
the absorbing tower, from where it can be introduced into the etching bath. The process is
operated in a closed system.

2.2. Regeneration based on cementation

Cementation reaction is a spontaneous electrochemical reaction that involves electro-

chemical precipitation of a noble metal from solutions of its salts on a more electronegative
metal, which correspondingly dissolves. The common chemical equation is shown in the
following reaction:

Me1 (s) + Me2 2+ (aq) ↔ Me1 2+ (aq) + Me2 (s) (8)

Cementation is a feasible method when the concentration of the metal needed to be recov-
ered is not very high. A few methods based on cementation have been developed for the
regeneration of cupric chloride etchant waste. By cementation methods, copper ions can
be replaced with ions of a metal other than copper. Copper can be recovered in the form
of metallic copper precipitate. A valuable chloride of a metal other than copper can be
produced as well. For example, Densan KK (Watanabe and Mori, 1988) patented a method
where metallic aluminium is added into the spent cupric chloride etching solution. The
precipitate that forms is a mixture of metallic copper and copper oxide, which can be sepa-
rated by filtration. The aluminium chloride filtrate can be utilized as a starting material for
polyaluminium chloride (PAC) production or for other purposes.
Also Nikko Fine Product Co. (Narisawa et al., 1994) patented a method where metallic
copper powder and a useful chloride of a metal other than copper are recovered from
spent acidic cupric chloride etchants. First, the spent etchant is mixed with active carbon
to remove adsorbable impurities from the solution, followed by removal of active carbon.
Then, a powder of an additive metal that has a larger ionization tendency than copper
(for example, manganese, zinc, cobalt, nickel or tin) is mixed with the solution to cause
replacement of copper ions with ions of the additive metal in such a way that elementary
copper is formed. Besides the cementation reaction, another reaction takes place between
the additive metal and free hydrochloric acid with hydrogen gas evolution. These reactions
define the amount of additive metal to be added into the waste solution. The amount of
additive metal should be as closely as possible equivalent to the total amount of chloride
224 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

ions in the solution. If the amount is too small, part of the copper remains unconverted and
remains as an impurity in the chloride of the additive metal. On the other hand, if the amount
is too large, part of the additive metal remains unutilized and remains as a metallic impurity
in the recovered copper precipitate. The temperature should be between 40 and 100 ◦ C. If
the reaction temperature is too low, the reaction proceeds very slowly. It is important to
agitate the reaction mixture, to facilitate rapid removal of the precipitate of metallic copper
deposited on the surface of the additive metal, so that it will not inhibit the progress of
the reaction. The finely divided copper particles can be removed by, for example, filtration
followed by washing and drying of the product. The aqueous filtrate contains the chloride of
the additive metal in a quite high concentration and purity. The solution can be used as such
for the intended application. For example, zinc chloride can be used as a constituent of dry
batteries, cobalt chloride as an ingredient in drying agents and tin chloride, nickel chloride
and manganese chloride as ingredients in catalysts, etc. The metal chloride solution can
also be concentrated by evaporating part of the water, or optionally, the metal chloride can
be crystallized.
However, metal chloride by-products do not necessarily have a sufficient market. For
example, some regeneration methods based on cementation involve replacement of copper
ions by the addition of iron or aluminium powder. The aqueous solution of iron or aluminium
chloride can be utilized as an inorganic flocculant in water treatment. However, no further
increase can be expected in the demand for these flocculants, because they have been under
continuous replacement in the recent years with flocculants based on organic polymers
(Narisawa et al., 1994). Also, it has not been taken into account that sodium, mainly in
the form of sodium chloride, is also very often present in the etchant waste nowadays if
sodium chlorate has been used as an oxidizer in the etching bath. Since sodium is more
electronegative than any of the suggested metals used in cementation, it will not be reduced
but stays as an impurity in the chloride solution. That will further decrease the use of
by-product chloride solution.

2.3. Regeneration based on solvent extraction

Copper recovery by solvent extraction (SX) has progressed from a technology with lim-
ited applications to a technology with broad applicability for a variety of solutions. Several
methods for the regeneration of spent acidic cupric chloride etching solution based on sol-
vent extraction have been developed. In most cases, the final copper recovery is done by
electrowinning (EW). Solvent extraction utilizes the differences in the solubilities of the
components. Since solubility depends on chemical properties, extraction exploits chemical
differences. Two phases must be brought into good contact to permit transfer of material and
then be separated. By combining several extraction stages, the desired component can be
concentrated into the other phase. The phase leaving a liquid–liquid contactor is called the
extract. The raffinate is the liquid phase left from the feed after being contacted by the other
phase. A successful copper extractant has certain properties. It should, for example, extract
copper selectively from the other species present, be soluble in an inexpensive diluent (usu-
ally kerosene), not transfer acid from strip to extraction and be safe to use (Kordosky, 1992).
Jensen (1981), for example, patented a method for selective extraction and ultimate recov-
ery of copper from spent cupric chloride etchant. A flow chart of the process is shown in
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 225

Fig. 1. A flow chart of acidic cupric chloride regeneration based on solvent extraction (Jensen, 1981, modified
from Fig. 1).

Fig. 1. In the copper extraction units, the copper-containing solution and the organic extrac-
tant flow countercurrently between the extraction stages. In each stage, the active organic
extractant selectively extracts copper from the solution, resulting in a copper-loaded organic
phase and a raffinate from which copper has been removed. In the first extraction unit, copper
is extracted as copper chloride by a copper chloride extractant. The extractant is dissolved
in an inert organic solvent, such as kerosene. After extraction, the loaded organic extractant
is transported into the first stripping unit, where it is brought into contact with a suitable
aqueous stripping solution, which actively strips copper chloride from the loaded extractant.
The stripped extractant is recycled into the first copper extraction unit, and the pregnant
stripping solution containing copper chloride is transported into the second copper extrac-
tion unit. In that unit, the solution is contacted with a hydrogen ion exchange extractant,
which selectively extracts copper. Hydroxy oximes, tertiary amines and beta diketones are
examples of active and selective organic extractants. As the extractant selectively extracts
copper from the stripping solution by hydrogen ion exchange, hydrochloric acid is also
formed. The acid can be neutralized by the addition of a suitable base. The resulting spent
stripping solution can be recycled into the first copper-stripping unit. The loaded hydrogen
ion exchange extractant is transported into the second copper-stripping stage, where the
loaded extractant is contacted with an aqueous, acidic stripping solution, such as sulphuric
acid. The copper can be recovered from the stripping solution by electrowinning as metallic
copper or by crystallization as copper sulphate.
However, the above process suffers from a complicated sequence of steps involving
repeated extraction and stripping stages under different operating conditions. A simpler
approach to the recovery of metals from chloride solutions was patented by Inst Injen-
erna Chimia (Kyuchoukov et al., 1989). In that method, copper is first extracted with an
organic extracting agent from the chloride solution as a copper chloride complex. After the
extraction, the raffinate obtained is separated from the organic phase. The organic phase
is freed from chloride ions by washing it with water, an aqueous ammonia solution or an
aqueous ammoniacal ammonium sulphate solution. After that, the copper is stripped from
the organic phase by contacting the organic phase with aqueous sulphuric acid to yield an
aqueous solution of a copper sulphate. The organic phase can be returned to the extraction
stage after regenerating it with a chloride ion-containing aqueous solution. Copper can be
recovered from the copper sulphate solution as copper sulphate by crystallization or as
metallic copper by electrowinning. This regeneration method is simpler to carry out and
226 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

does not require many repeated stages of extraction and stripping, but it is still chemical
consuming, which might make the process economically less feasible.
Another interesting method based on solvent extraction was patented by Phibrotech Inc.
(Edelstein, 2002). The method involves the use of cupric chloride etchant solution in a
solvent extraction electrowinning copper refinery to improve the recovery of copper and to
reduce material costs. In a SX-EW copper refinery, copper is obtained by first mining acid-
soluble copper-containing ore and piling the ore into a heap. Then, in the acid leaching step,
usually sulphuric acid is sprayed over the heap, dissolving copper in the ore and forming
a copper-containing solution. Acid leaching is followed by solvent extraction and, finally,
electrowinning. The patented method has shown that an acidic cupric chloride etchant
solution can be an effective substitute for sulphuric acid in the acid leaching step, which
reduces the need for purchased sulphuric acid and thereby reduces the costs. At the same
time, it is possible to improve the copper yield without additional ore mining. Typically, SX
plants cannot use spent acidic cupric chloride etchant solutions because the EW process has
a low tolerance for chloride ion concentration. Therefore, the SX step should include one
or more water washing stages to prevent or to minimize entry of chlorides into the EW step.
After the extraction, the copper-free acid phase is returned to the acid leaching step. This
method sounds tempting. However, it was developed to improve copper recovery and to
reduce material costs in a SW-EX copper refinery and not as a method for the regeneration
of acidic cupric chloride etchant waste. Therefore, on a larger scale, this method could not
be a solution for the regeneration of acidic cupric chloride etchant waste.
Racing raw material costs have accelerated efforts to produce inexpensive low-grade
feedstock from secondary sources. Queneau and Gruber (1997) discuss the production
of major copper chemicals from secondary sources in their article ‘The U.S. production
of copper chemicals from secondary and by-product sources’. In the United States, the
major copper chemicals produced are derived almost entirely from by-product sources,
including spent etchant solutions. Some of these processes include regeneration based on
solvent extraction. The companies that use etchants as feedstock, process usually spent
ammoniacal etchants together with spent acidic cupric chloride etchants. Final products of
such processes are copper sulphate and reconstituted ammoniacal etchant.
In those regeneration methods, ammoniacal etchant is processed at ambient temperature
by SX. The organic extractant is dissolved in an inert organic solvent and copper is extracted
almost completely from the NH4 Cl raffinate. Free ammonia is formed during extraction
(pH ∼ 8), as it can be seen in reaction (9) (Queneau and Gruber, 1997). Therefore, sufficient
amount of acidic cupric chloride etchant waste can be added to the first extraction stage
to convert the acidic cupric chloride etchant to ammoniacal etchant. The loaded organic
phase is scrubbed with weak acid. Scrubbing the loaded organic phase removes loaded or
physically entrained NH3 as (NH4 )2 SO4 . The copper sulphate stripping solution can then
be crystallized.

Cu(NH3 )4 Cl2 + R2H+ → R–Cu2+ + 2NH4 Cl + 2NH3 (9)

Spent copper etchant recyclers can actually produce more NH4 Cl than the circuit-board
industry needs. The excess of recovered ammoniacal etchant is related to the quantity of
processed acidic cupric chloride etchant waste (see reaction (9)). Therefore, in the long run,
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 227

Fig. 2. The principle for the regeneration of cupric chloride etchant waste based on precipitation of copper oxide
(Allies et al., 1996).

there is still a need to develop more advantageous processes for the regeneration of acidic
cupric chloride etchant waste. Moreover, the capital costs of these kinds of SX plants are
high and some carryover of the organic phase into the aqueous phase is likely to occur.

2.4. Regeneration based on the precipitation of copper oxide

Some methods of regenerating acidic cupric chloride etchant waste based on copper
oxide (CuO) precipitation have also been developed. For example, Training ‘N’ Technol-
ogy Inc. (Allies et al., 1996) patented a process whereby cupric chloride etchant waste
is converted into non-hazardous material consisting of copper oxide and saline solution.
The principle of the method is shown in Fig. 2. A preheated spent cupric chloride etchant
stream is combined with a preheated caustic solution stream. When the streams are mixed,
an exothermic neutralization reaction begins, producing copper hydroxide precipitate and
saline solution. The reaction continues and becomes endothermic as the formed blue copper
hydroxide is converted to black copper oxide in the saline solution. Fine copper oxide can be
separated by filtration, for example. The copper oxide can be used as feedstock for mining
operations, and the saline solution can be discharged for standard waste waster treatment.
The disadvantage of this method is the big caustic solution consumption, which makes the
process economically less viable. Additionally, fine copper oxide slurry is difficult to filtrate.
Another method where copper oxide precipitation is utilized in the recovery of waste
cupric chloride etchant is a method patented by Myung Jin Chemical Co. (Seo et al., 2003).
Compared to the previously described method, the caustic solution is slowly added to the
etchant waste, while keeping the temperature relatively low, at about 10–30 ◦ C. Since waste
etchant contains free hydrochloric acid, the neutralization reaction generates a large amount
of heat, which leads to an instant increase of reaction temperature, even up to 80 ◦ C. The
formed copper hydroxide is instantly dehydrated at high temperatures to form black copper
228 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

oxide. If the temperature is not kept at a low level, the produced copper oxide is platy-shaped
and therefore more difficult to filtrate than, for example, needle-shaped copper oxide. If the
temperature is kept at a low level during neutralization, a blue-coloured copper hydroxide
slurry is obtained first. Subsequently, when the slurry is heated and sintered at 100–400 ◦ C
for 1–3 h, the slurry is converted to copper oxide, which has needle-form crystal morphology
and can thus be easily filtered. Even though the copper oxide formed by this method has
better features than the copper oxide produced with the previously described method, a lot
of caustic solution is still consumed. Also, energy consumption is higher in the latter method
due to the cooling of the copper hydroxide slurry and the energy needed for sintering the
copper oxide precipitate. The advantage of these two precipitation methods is that it does
not matter if there is also sodium chloride present in the etchant waste since sodium chloride
is formed in the neutralization reaction, anyway.
There are also similar methods that apply cupric oxide recovery by adding caustic solution
into spent ammoniacal etchant. In addition, approximately 20 vol.% acidic cupric chloride
etchant can be processed together with the ammoniacal etchant. Aqueous caustic soda is
added to oxidized ammoniacal etchant (‘Ammo’) at above 85 ◦ C. Also limited quantities of
oxidized acidic cupric chloride etchant (‘CCE’) can be added to the reactor together with
ammoniacal etchant. The final product is black CuO. In addition, aqueous sodium chloride
and gaseous ammonia by-products are formed. The ammonia is usually absorbed by using
hydrochloric acid to produce aqueous ammonium chloride. The process is introduced in
Fig. 3 (Queneau and Gruber, 1997).
This kind of method, however, could not be a solution for the regeneration of acidic
cupric chloride etchant waste on a larger scale, since the amount of acidic cupric chloride
etchant waste processed by these methods has to be limited. If too much acidic cupric
chloride is added, the formed product is useless, slimy hydroxide-contaminated precipitate.
Furthermore, still a relatively high amount of caustic solution and energy are consumed by
the regeneration process.

2.5. Regeneration to yield basic copper chloride micronutrient additive

There are also inventions that relate to manufacturing of copper-based micronutrient

additives for feed products from waste etchant streams. Those inventions incorporate ‘basic
copper chloride’ Cu(OH)x Cl(2−x) as a mineral supplement for feed products. The products
are valued both for their biological availability to animals and for their low reactivity with
organic constituents in the feed mix. Often copper sources suffer from a variety of problems,
including low bioavailability or destabilizing effects on vitamins in feed mixes. Furthermore,
in manufacturing copper-based micronutrient additives for feed products, controlling the
particle size of the additive might present problems. Also background salts may contribute,
for example, to poor physical characteristics of the micronutrient additive.
Heritage Environmental Services Inc. (Steward, 1995), for example, patented a method
that provides a process for producing basic copper chloride from a source of copper and
chloride ions. Spent etchant streams are suitable copper and chloride ion sources. In this
method, spent etchant streams are regenerated to yield basic copper chloride and reusable
ammonium chloride liquor which can be converted into fresh ammoniacal etchant by addi-
tional processing. A spent cupric chloride etchant stream and a spent alkaline etchant stream
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 229

Fig. 3. The caustic boiling of spent ammoniacal and acidic etchant (Queneau and Gruber, 1997).

are combined to form copper-containing slurry. The self-neutralization reaction is shown in

equation (10). From the copper-containing slurry, basic copper chloride can be recovered
for use as a micronutrient supplement or as a copper source in other products.

Cu(NH3 )4 Cl2 + CuCl2 + HCl + 3H2 O → Cu2 (OH)3 Cl + 4NH4 Cl (10)

A flow chart of the process is shown in Fig. 4. First feed stream is spent copper-containing
alkaline etchant solution and second feed stream is spent copper-containing acidic etchant
solution. Quality assurance procedures, such as checking for acidity/alkalinity, copper and
230 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

Fig. 4. A flow chart of the regeneration to yield basic copper chloride (Steward, 1995, modified from Fig. 1).

trace metallic impurities and specific gravity, must be performed before the etchant is
pumped from the storage tanks. If the spent etchant streams contain high levels of soluble
arsenic, they can be treated separately in pre-treatment reactors before being fed to the
primary reactor. By adding calcium compounds and magnesium compounds into the alkaline
etchant solution, arsenic can be precipitated in the form of low solubility calcium magnesium
arsenates. To reduce the levels of soluble arsenic in the acidic etchant solution, the pH of
the stream can be raised to the point where precipitation begins to occur.
After precipitation, the streams are fed to the primary reactor where the residence time
varies. The reaction products, which are basic copper chloride and soluble background
salts, are pumped from the primary reactor to settler. The settler separates the reaction
products into a supernatant brine and copper-containing slurry. The brine consists primarily
of ammonium chloride liquor and dissolved copper, whereas the slurry comprises basic
copper chloride along with a variety of background salts. A certain amount of the slurry is
withdrawn for use as a seed stream for seeding the crystallization of basic copper chloride
in the reactor. It is important to maintain an appropriate concentration of feed slurry in the
reactor because seeding affects to the final product particle size distribution. The supernatant
brine from the settler passes directly to a finishing operation, whereas the remaining portion
of the slurry is pumped to a drying operation, which includes a filter, a dryer and a sieve.
A water wash is provided to assist in removing ammonium chloride from the solids. The
effluent wash water is sent to disposal. Appropriately sized fractions pass through the sieve
as final products to be used as a micronutrient supplement or as a copper source in other
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 231

products. According to the patent, the product is substantially free of background salts and
contaminants and that the product has high bioavailability.
Ammonium chloride liquor recovered from the product filter is fed together with the
supernatant ammonium chloride liquor to polishing operation, which includes a polishing
reactor and a filter press. A metal scavenger is fed to the polishing reactor to reduce the
levels of dissolved copper and other metals. The by-product cake can be processed by a
copper smelter for the recovery of copper values. The clear ammonium chloride can be
finished into fresh ammoniacal etchant.
The method seems appealing since the spent etchants can be recovered as valuable
products. The disadvantage is the careful control of the process such that the quality of the
final product is appropriate.

2.6. Summary of the methods of regenerating acidic cupric chloride etchant waste

There are both advantages and disadvantages in the methods developed for the
regeneration of acidic cupric chloride etchant waste. The advantages and disadvantages
are summarized in Table 1. It can be seen that there is still an obvious need to develop
more efficient and economical recovery processes for treating acidic CuCl2 etchant waste
solutions.

3. Regeneration methods of tin stripping waste

3.1. Electrolytic regeneration

Because the metal concentration is relatively high in spent tin stripping solutions, elec-
trolytic regeneration would seem reasonable. However, electroplating is possible only from
electrolyte systems that are true solutions. Because of the peculiar nature of tin dispersion,
tin values cannot be electroplated from this system without further treatment of the spent
tin stripper.
There are several developed methods that are based on electrolytic regeneration. For
example, Scott et al. (1997) studied electrochemical recycling of all metals from spent nitric
acid-based tin stripping solutions as well as the combination of electrochemical deposition
of copper and precipitation of tin and lead, followed up by furnace recycling. Their study
turned out to have two limitations in the attempts to recycle commercial stripping solutions.
Firstly, tin tends to deposit with both copper and lead to form alloys, which makes clear
separation of metals impossible. Secondly, since there are additives in commercial stripping
solutions, the current efficiency for the deposition of metals is much lower from commercial
stripping solutions than from stripping solutions consisting exclusively of nitric acid and
metals. Also, the deposition potentials relating to commercial stripping solutions are more
negative, leading to higher energy consumption. Scott et al. (1997) used a simple aqueous
nitric acid stripping solution in their experiments because it was more compatible with the
electrochemical recycling process. Nitric acid concentration was also lower (∼1.4–2.1 M)
in their experiments than in commercial nitric acid-based tin stripping solutions (∼5 M).
They found that a more dilute stripping solution still selectively stripped tin from the PBC
 232
Table 1
Summary of the advantages and disadvantages of the methods for the regeneration of acidic CuCl2 etchant waste
Regeneration method Advantages Disadvantages

T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

+ + + + − − − −
Electrolytic By electrochemically Reversing the Recovery of Avoiding waste Possibility to Several problems related High operating Electrolytic Not reliable or
regeneration reversing the etching etching reaction metallic copper formation regenerate the to electrowinning; due to voltages, regeneration efficient
reaction and restoring the etchant in a the difficulty of avoiding leading to seeks to avoid enough
etching capacity closed-loop chlorine gas evolution, waste heat oxidizing
system with the etc. generation chemicals that
etching process are used in
chemical
regeneration
With chlorine gas Restoring the Recovery of Possibility to Using the Safety, health and
evolution etching capacity metallic copper regenerate the generated environmental issues;
etchant in a chlorine gas for use of chlorine gas is
closed-loop regeneration of forbidden in many area
system with the the etchant
etching process
Regeneration based on Recovery of Metal chloride The amount of additive There is not The case with sodium present in
cementation metallic copper other than copper metal has to be necessarily a the etchant waste has not been
chloride is formed controlled carefully; if sufficient taken into account. Since sodium
as a by-product the amount is too small, market for the is highly electronegative, it will
part of the copper metal chloride not be reduced but remains as an
remains unconverted, produced impurity in the chloride solution
and if the amount is too
large, part of the additive
metal remains unutilized
Regeneration based on Copper is In the methods There is often quite a Relatively high Some High capital
solvent extraction eventually where spent complicated sequence of chemical carryover of costs
recovered as ammoniacal steps involving repeated consumption the organic
metallic copper or etchants are extraction and stripping phase into the
copper sulphate processed together units under different aqueous phase
with spent acidic operating conditions is likely to
CuCl2 etchants, occur
ammoniacal etchant
can be recovered
Regeneration based on Copper is recovered Sodium can be In the methods Acid is not recovered, A lot of caustic Platy-shaped A lot of
precipitation of as copper oxide present in the where a limited and a lot of saline solution is copper oxide energy is
copper oxide etchant waste since amount of spent solution discharged into consumed in is difficult to required in the
sodium chloride is acidic CuCl2 standard waste water neutralization filter regeneration
formed in the etchant can be treatment is formed process if
neutralization processed needle-shaped
reaction together with copper oxide

T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

ammonical with better
etchant, features than
ammonical platy-shaped
etchant can be copper oxide
recovered is produced

Regeneration to yield Copper is recovered Spent acidic CuCl2 Process has to be

basic copper as basic copper etchant and controlled carefully such
chloride chloride to be used ammoniacal that the quality of the
micronutrient as a micronutrient etchant are final product is sufficient
additive supplement or as a processed together;
copper source in ammoniacal etchant
other products can be recovered

233
234 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

at a considerably high speed and with very little attack on the copper underneath the metal
resist layer. After the stripping process, stannic oxide precipitated out from the solution.
Complexing agents were not considered necessary to keep the tin in solution.
In their experiments, Scott et al. (1997) first separated stannic oxide from the stripping
solution by filtration. The precipitate obtained could be dissolved in HCl when heated.
Since no Cl2 was found to escape from the solution, it could be assumed that tin was in the
form of H2 SnCl6 in the solution. Tin can be electrodeposited onto stationary stainless steel
electrodes. However, the process of recovering tin is somewhat complicated and energy
consumption is considerably higher than that for copper. After stannic oxide is filtered,
the solution contains mainly copper and also lead, if a tin/lead alloy has been used as a
metallic resist. Copper can be electrodeposited with high current efficiency at an acidity
level as high as 2.5 mol/l, because the reduction potential of nitrate ion (NO3 − ) is much
more negative than that of copper. The deposition of copper is also highly selective in the
presence of lead because the electrodeposition potential of lead is much more negative
than that of copper. High purity of the copper deposit can be achieved. After the recovery
of tin and copper, lead can be electrodeposited onto stationary stainless steel electrodes.
However, the current efficiency to electrodeposit lead is much lower because the powdered
lead deposit tends to fall off from the electrode and redissolve in the solution. One option
would be to separate the deposit from the substrate continuously. There is also a draw-
back in the chemical recycling of metals from the waste tin stripping solution because
Pb(II) tends to form an oxide deposit on the anode. Therefore, an ionic exchange mem-
brane must be applied to separate the cathodic and anodic compartments when copper or
lead is electrodeposited, which increases the costs. The principle of the process is shown
in Fig. 5.
As an alternative, Scott et al. (1997) studied a process that incorporates electrochemical
recycling of copper and furnace recycling of tin and lead. In this procedure, tin and lead are
precipitated from spent stripping solution as stannic oxide and lead sulphate. The precip-

Fig. 5. The principle of electrochemical recycling of tin, copper and lead (Scott et al., 1997).
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 235

itation of tin and lead can be combined in one step or be done separately, depending on the
final use of the precipitate. The precipitate can, for example, be sent to furnace refineries
specialized in secondary metals. Scott et al. (1997) found that the precipitation of stannic
oxide is enhanced by aeration, especially when the nitric acid concentration in the stripping
solution is low. Lead can be precipitated as PbSO4 by adding an appropriate amount of
H2 SO4 into the solution. After the precipitation, copper can be recovered by electrodepo-
sition. In copper electrowinning, the use of an ionic-exchange membrane is not necessary
because lead can be removed before copper recovery. This method is relatively simple and
also economical, but needs to be integrated to a furnace refinery that accepts the formed
precipitate.
The problem with the above methods is that Scott et al. (1997) studied stripping wastes
with lower nitric acid concentrations than those in commercial stripping solutions. Also,
there were no additives in the stripping solution used by Scott et al. (1997) in their experi-
ments. In order to arrange recycling in line with the described schemes, it would be necessary
to change the commercial stripping solutions. However, it would be much more reasonable
to develop a recycling process for spent commercial tin stripping solutions.
RD Chemical Company (McKesson et al., 2001) also patented an electrolytic recovery
method for treating tin stripping waste. The principle of the method is that tin is made
soluble by adding a strongly caustic solution, such as sodium hydroxide, into the spent tin
stripping solution. By adding the caustic solution, the insoluble stannic oxide is converted to
soluble stannate form. In the reaction, the tin remains in the Sn4+ oxidation state. By adding
complexing agent, the other metal ions can be kept in the solution, and their precipitation
can be avoided. The complexing agent should complex with metal ions other than tin. A
suitable complexing agent would be gluconate. The treated waste solution can be used in
an electroplating system to recover metals. Plating speed and efficiency can be improved by
heating the treated waste solution (70–80 ◦ C) during electroplating. After the electrolytic
treatment and pH adjustment, the final solution can be generally disposed of by discharging
it into most sanitary sewage systems.
The method seems appealing since all the metals can be recovered. The disadvantage is
that nitric acid cannot be recovered by this method. Also a large volume of chemicals is
consumed. Electrowinning was not described in detail, but as pointed out earlier, it will not
be simple.
Amia Co. and Persee Chemical Co. (Chen et al., 2004) patented a regeneration method-
based partially on electrolytic treatment. A flow chart of the method is shown in Fig. 6. First,
copper ions are electrolytically reduced to metallic copper at as low a temperature as possible
without ice formation (−5 to 40 ◦ C). This will suppress the hydrogen and nitrate ions being
reduced to hydrogen gas and nitrogen oxides. Tin is mostly present in spent tin stripping
solutions in a Sn4+ form, but some Sn2+ ions might also be present. After copper recovery,
Sn2+ and Pb2+ ions are electrolytically oxidized to Sn4+ and Pb4+ at a high temperature
(about 100 ◦ C) to form solid tin and lead oxides and hydroxides. The temperature should
be as high as possible, but yet such that no vigorous boiling of nitrogen oxides occurs. If
there is lead present in the tin stripping waste and the efficiency of the oxidization of Pb2+
is poor, sulphate ions can be added to the solution during or after electrolytic oxidation to
form lead sulphate precipitate. The formed precipitate can then be filtrated. The resulting
filtrate can be used to prepare a fresh tin stripping solution. The separated tin and lead oxides
236 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

Fig. 6. Flow chart of the electrolytic method to treat spent nitric acid-based tin stripping solution (Chen et al.,
2004).

and hydroxides and optional lead sulphate can be dissolved in a strongly alkaline or acidic
solution, from which metallic tin and lead can be recovered by electrolytic reduction at a
high temperature (50–105 ◦ C).
The advantage of the above method is that all the metals in the solution can be recovered.
Also, a fresh tin stripping solution can be prepared from the filtrate. However, electrolytic
reduction is difficult to carry out directly on spent stripping solutions in such a way that
hydrogen gas and nitrogen oxides will not be generated. Also, if the tin and lead oxide and
hydroxide precipitate are dissolved in hydrochloric acid, it is difficult to prevent the forma-
tion of chlorine gas in electrolytic recovery. Furthermore, the big temperature elevations
and the need for refrigeration consume a lot of energy.

3.2. Regeneration based on solvent extraction

Lee et al. (2003) studied the regeneration of nitric acid-based tin stripping waste based
partially on solvent extraction. Besides the solvent extraction, they also applied stripping,
electrowinning, precipitation and cementation in the recovery process. In their experiments,
Lee et al. (2003) used a synthetic solution chemically similar to the actual waste. First, nitric
acid can be selectively extracted by tri-n-butyl phosphate (TBP) dissolved in kerosene. TBP
is known to have selectivity for nitric acid over metal ions. Ninety-five percent extraction
of nitric acid was possible by 50% TBP in five counter-current stages at a threefold volume
of the organic phase compared to the aqueous phase. After extraction, by using distilled
water as a stripping agent, most of the nitric acid could be stripped from the loaded organic
phase.
After nitric acid recovery, copper can be recovered by electrowinning. Electrowinning
should be performed after nitric acid recovery because it is impossible to electrodeposit
metal ions directly from spent stripping solutions due to their high acidity. Very pure
copper metal can be selectively reduced at the cathode, whereas electrowinning of iron,
tin and lead is difficult from the thermodynamic point of view because their reduction
potentials are lower than the reduction potential of hydrogen ion. According to Lee et al.
(2003), after copper has been recovered, the pH of the solution can be adjusted to 1.5
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 237

with Pb(OH)2 , whereupon most tin ions will be precipitated as Sn(OH)2 . In order to pre-
vent co-precipitation of iron, it is important to control the solution pH. The tin precipitate
can be separated by filtration. Lead can be recovered from the filtrate by cementation,
accomplished by adding iron powder into the solution. Because of the oxidizing nature
of nitric acid, cementation of metal ions is very difficult to achieve from the nitric acid
solution. In order to suppress the oxidizing properties of nitric acid, sodium pyrosulphate
(Na2 S2 O5 ) can be added into the solution, and a reduction reaction of nitric acid to nitro-
gen dioxide will occur. The solution pH should also be adjusted to 2 by sodium hydroxide
because the reduction potential of hydrogen ion is higher than that of lead ion, which means
that the cementation percentage of lead increases as the concentration of hydrogen ion
decreases. According to Lee et al. (2003), lead can be recovered by this method with 99%
purity.
The method has major advantages because all the metals and also nitric acid can be
recovered. The disadvantage is the high chemical consumption especially in the solvent
extraction stage. Additional chemicals are also needed in the precipitation and cemen-
tation stages. These reasons might lower the profitability expectations of the recovery
process.

3.3. Sustainable technologies for the regeneration of tin stripping waste

Kerr (2004) discusses in his article ‘sustainable technologies for the regeneration of acidic
tin stripping solutions used in PCB fabrication’ fully sustainable regeneration of tin stripping
waste by using ion exchange membrane technology in combination with other techniques.
The process can be divided into three operations: (1) acid reclamation, (2) metal recovery
(electrowinning) and (3) filtration. Acid recovery would be performed by diffusion dialysis.
Diffusion dialysis is a process that requires a two-compartment cell. One compartment
would contain water and the other acidic tin stripping waste. The compartments should be
separated by an ion exchange membrane, which blocks the transport of metal ions while
allowing the passage of hydrogen and nitrate ions, as shown in Fig. 7. Diffusion dialysis
is based on a concentration gradient between the two compartments, which makes the
overall efficiency of the process directly dependent on the surface area of the ion exchange
membrane. On an industrial scale, several two-cell compartments are stacked to enable
large volumes of solution to be treated. One major advantage of this process is that energy
is required only to drive the circulatory pump. The recovered acid could be reused in tin
stripping after the addition of small quantities of additives into the solution to optimize the
performance of the new tin stripping chemistry.
Once the acid has been recovered, Kerr (2004) suggests membrane filtration for the
removal of stannic oxide. Membrane filtration is the separation of components of a pres-
surized fluid by a polymer or inorganic membrane. The class of the filter is defined by its
pore size. Since stannic oxide particles are very fine (20 nm–1 ␮m), ultrafiltration (UF, pore
size 20–50 nm) and microfiltration (MF, pore size 1 ␮m) would be suitable for removing tin
oxide. It is known that filters are easily blocked when filtering solutions containing stannic
oxide particles are used. Therefore, the filtering requires some modifications, which could
be achieved by using cross-flow filtration (Kerr, 2004). That would prevent the build-up
of particles at the pore site. The separated stannic oxide can be sold, which would make it
238 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

Fig. 7. A two-compartment diffusion dialysis cell (Kerr, 2004).

an important marketable commodity rather than a waste product. Stannic oxide has several
applications. It is used, for example, for polishing cabochons, in the manufacturing of lead
crystal glass and as an opacifier in ceramic glazes.
To make the process fully sustainable, the third step would be to recover the metals
other than tin dissolved in the stripper. This could be done by electrowinning. The copper
electrowinning technology is well established. The removal of ferrous/ferric ions by elec-
trowinning is technically possible, but unlikely because the level of iron is very low in a
waste tin-strip solution (Kerr and Coultard, 2004).
However, the above technology is still relatively expensive, but in the future, the rising
cost of landfills and the increasingly stringent legislation may force PCB manufacturers to
adopt regeneration technologies out of economic necessity.

3.4. Summary of the methods for the regeneration of nitric acid-based tin stripping
waste

Similarly to the regeneration of cupric chloride etchant waste, the advantages and disad-
vantages of the methods applied to spent tin stripping solution are summarized in a tabular
form. The advantages and disadvantages are shown in Table 2. With regard to tin stripping,
it seems even more obvious than in the case of cupric chloride, that there is a need to develop
an efficient regeneration process.
Table 2

T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

Summary of the advantages and disadvantages of the methods for the regeneration of nitric acid-based tin stripping waste
Regeneration method Advantages Disadvantages
+ + + − − − − −
Electrolytic Method Recovery of metallic tin, Alternatively The tin Electrowinning Filtered tin oxide Electrowinning is High energy Can be applied
regeneration introduced by copper and lead precipitating tin as stripping cannot be done precipitate is solubilised difficult from the consumption in tin only to more
Scott et al. SnO2 and lead as solution directly from used in hyrdrochloric acid. solution containing electrowinning dilute tin
(1997) PbSO4 , which are can be tin stripping However, filtration is hydrochloric acid and difficulties in stripping
sent to furnace regener- solutions because tin difficult due to the very in such a way that lead solutions than
refineries. Copper ated for is not truly soluble in small particle size of tin chlorine gas is not electrowinning commercial
can be recovered as reuse the solution. Before oxide generated solutions, which
metallic copper electrowinning, makes the
some further method
treatment of the impractical
spent tin stripper
must be done

Method Recovery of metallic tin Sodium hydroxide is Tin stripping solution in

patented by and copper consumed when itself cannot be
RD Chemical solubilising the tin. regenerated; after metal
Company Complexing agents are also recovery, the bath is
(McKesson et consumed when keeping pH-adjusted and can be
al., 2001) the other metal ions in a discharged into most
soluble state effluent systems

Method Recovery of metallic tin, The filtrate from Copper ions are Electrowinning of tin High energy
patented by copper and lead the filtration step electrolytically reduced and lead is difficult consumption
Amia Co. and can be used to directly from used tin
Persee prepare fresh tin stripping solution, which is
Chemical Co. stripping solution very difficult
(Chen et al.,
2004)

239
 240
T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243
Table 2 (Continued )
Regeneration method Advantages Disadvantages
+ + + − − − − −
Regeneration based Copper can be recovered Abundant chemical Low profitability
on solvent electrolytically as consumption in, for expectations
extraction metallic copper, tin example, the solvent
precipitated and lead extraction and cementation
recovered by steps
cementation as metallic
lead powder

Regeneration based Copper can be recovered Acid recovery Avoiding Acid recovery by Membrane fouling
on sustainable as metallic copper and waste diffusion dialysis and
technologies tin as metallic tin or as formation membrane filtration of
tin oxide precipitate tin oxide are too
expensive, while
neutralization is still
possible
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 241

4. Discussion

Since the metal concentration is relatively high in spent cupric chloride etching solutions
and tin stripping solutions, electrolytic regeneration seems a reasonable alternative for the
regeneration of those wastes. For cupric chloride etchant waste, there are inventions that
utilize a regeneration process which reverses reaction (1) in such a way that the evolution
of chlorine and hydrogen gas is avoided. Those methods can be operated in a closed-loop
cycle with the etching process. However, the methods suffer from several drawbacks. Since
electrolytic recovery from cupric chloride etchant waste solutions containing chloride ions
by avoiding chlorine gas evolution is difficult, there are also electrolytic inventions that
involve recovery of copper and use of the generated Cl2 in the chemical regeneration of
the etchant. These methods, however, are impractical because the use of Cl2 is forbidden in
many areas. For the regeneration of nitric acid-based tin stripping solutions, there are also
inventions that are based on electrolytic regeneration. However, some further treatment of
the spent tin stripper must be done before electrowinning because tin is not truly soluble
in nitric acid-based tin stripping solutions. In addition, electrowinning of tin and lead has
proven to be complicated.
For the regeneration of cupric chloride etchant waste, there are also some methods
based on cementation. Copper can be recovered as metallic copper, whereas metal chloride
other than copper is formed as a by-product. However, metal chloride by-products do not
necessarily have a sufficient market. Some methods based on precipitation of copper oxide
have also been developed. A lot of caustic solution is consumed in the neutralization reaction.
Additionally, a lot of saline solution that must be discharged into waste water treatment is
formed. These reasons make the methods uneconomic.
There are also inventions based on solvent extraction for the regeneration of both acidic
cupric chloride etching and nitric acid-based tin stripping solutions. Those inventions
involve usually a quite complicated sequence of steps involving repeated extraction and
stripping stages. They are also very chemical consuming. For spent tin stripping solutions,
also ion exchange membrane technology in combination with other techniques has been
studied. For this purpose, however, ion membrane technology is still too expensive.

5. Conclusions

Both spent cupric chloride and tin stripping solutions are classified as hazardous wastes.
They are usually shipped off-site for reclamation, which is becoming increasingly more
expensive. These wastes are a significant problem for PCB industry. Usually, spent tin
stripping solutions, and often also spent cupric chloride solutions, are treated by neutral-
ization, resulting in sludge which is discarded in special landfills. There have been several
attempts to develop technically and economically feasible processes for the regeneration of
spent cupric chloride and tin stripping solutions. The developed methods are based on such
techniques as electrowinning, cementation, solvent extraction, precipitation and membrane
technology. Some of the methods suffer from technical difficulties and complexity. Some,
on the other hand, are technically very appealing but not so economical, while neutralization
is still possible. In the future, however, the increasingly stringent legislation and rising land-
242 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243

fill costs might force PCB industry to adopt such technologies out of economic necessity.
Meanwhile, it would be very important to develop technically and economically satisfactory
solutions for the treatment of spent acidic cupric chloride and tin stripping solutions.

References

Adaikkalam P, Srinivasan GN, Venkateswaran KV. The electrochemical recycling of printed-wiring-board etchants.
JOM 2002;54:48–50.
Allies VR, Lloyd MF, McCarron JM. Process and apparatus for converting spent etchants. US Patent
5,560,838;October 1, 1996 to Training ‘N’ Technology Inc., USA, p. 12 [Appl. US 350198, December 5,
1994].
Chemcut Corporation. Technical Information: Process Guidelines for Cupric Chloride Etching; October 10, 2002
[web document]. Available: http://www.chemcut.net/pdf/Cupric-Chloride.pdf.
Chen K-C, Chang C-H, Lin Y-F, Yuan, T-S, Wang H-M, Wu J-F, et al. Method for treating spent tin/lead stripping
solution. US Patent 6,685,820; February 3, 2004 to Amia Co. Ltd. & Persee Chemical Co. Ltd., Taiwan, p. 5
[Appl. US 132143, April 26, 2002].
Edelstein P. Use of cupric chloride etchant solution in a solvent extraction electrowinning copper refinery. US
Patent 6,375,713; April 23, 2002 to Phibrotech Inc., USA, p. 4 [Appl. US 734706, December 13, 2000].
Fitzpatrick-Brown AJ. Printed circuits: etching processes. Electr Prod 1985;14:28–30.
Garn PD, Sharpe LH. Etching bath for copper and regeneration thereof. US Patent 2,964,453; December 13, 1960
to Bell Telephone Labor Inc., USA, p. 8 [Appl. US 692889, October 28, 1957].
Gurian M, Gilleo K, Murray J. Etched in our memories. Printed Circuit Fabricat 2000;23:116–26 [Chapter 2].
Hillis MR. Method for the electrolytic regeneration of etchants for metals. US Patent 4,468,305; August 28, 1984
to The Electricity Council, GB, p. 7 [Appl. US 145948, May 2, 1980].
Jensen WH. Selective extraction and recovery of copper. US Patent 4,272,492; June 9, 1981 to Jensen, W.H., USA,
p. 19 [Appl. US 044080, May 31, 1979].
Kerr C. Sustainable technologies for the regeneration of acidic tin stripping solutions used in PCB fabrication.
Circuit World 2004;30:51–8.
Kerr C, Coultard F. Sustainable technologies for the tin stripping process used in printed circuit board fabrication.
UK Report STI3-029; 2004, p. 77.
Kordosky GA. Copper solvent extraction: the state of the art. JOM 1992;44:40–5.
Kyuchoukov GDS, Mihaylov IO, Elenkov DG, Boyadjiev LA, Fletcher AW. Method for the recovery of metals
from chloride solutions. EP Patent No. 0301783; February 1, 1989 to Inst Injenerna Chimia, BG, p. 7 [Appl.
EP 306804, July 25, 1988].
Lee M-S, Ahn J-G, Ahn J-W. Recovery of copper, tin and lead from the spent nitric etching solutions of printed
circuit board and regeneration of the etching solution. Hydrometallurgy 2003;70:23–9.
McKesson D. Miracles in tin stripping. Printed Circuit Fabricat 1999;22:34–8.
McKesson Jr, Douglas W, Sedlak RP. Treatment of waste from printed circuit board production for recovery of
tin and environmentally safe disposal. US Patent 6,290,835; September 18, 2001 to RD Chemical Company,
USA, p. 7 [Appl. US 498694, February 7, 2000].
Mikami Y, Iosaki M, Shibasaki M. Method for treating etchant. US Patent 5,393,387; February 28, 1995 to Nittetsu
Mining Co. Ltd., JP, p. 7 [Appl. US 960992, October 14, 1992].
Narisawa T, Kato R, Nakamura M, Yamaguchi H. Method for concurrent production of copper powder and a metal
chloride. US Patent 5,279,641; January 18, 1994 to Nikko Fine Products Co. Ltd, JP, p. 5 [Appl. US 005980,
January 19, 1993].
Oxley JE. Electrolytic regeneration of acid cupric chloride etchant. US Patent 5,421,966; June 6, 1995 to Oxley,
J.E., USA, p. 13 [Appl. US 159517, December 1, 1993].
Oxley JE, Smialek RJ, Putt RA. Apparatus and a process for regenerating a CuCl2 etchant. US Patent 5,705,048;
January 6, 1998 to Oxley Research Inc., USA, p. 8 [Appl. US 624825, March 27, 1996].
Parikh G, Willard W. Methods of electrolytic regenerative etching and metal recovery. US Patent 3,784,455;
January 8, 1974 to Western Electric Co., USA, p. 16 [Appl. US 212911, December 28, 1971].
 T. Keskitalo et al. / Resources, Conservation and Recycling 49 (2007) 217–243 243

Queneau PB, Gruber RW. The U.S. production of copper chemicals from secondary and by-product sources. JOM
1997;49, 34–37, 49.
Scott K, Chen X, Atkinson JW, Todd M, Armstrong RD. Electrochemical recycling of tin, lead and copper from
stripping solution in the manufacture of circuit boards. Resour Conserv Recycl 1997;20:43–55.
Sedlak, R. Etching innerlayers; 1995 [web document]. Last updated September 12, 1999. Available:
http://www.pcbfab.com.
Seo KB, Uh YS, Kim YH, Han JY, Kim SJ, Kim MH. Preparation of highly pure copper oxide from waste etchant.
US Patent 6,649,131; November 18, 2003 to Myung Jin Chemical Co. Ltd., Korea, p. 4 [Appl. US 767950,
January 24, 2001].
Steward FA. Micronutrient supplement. US Patent 5,451,414; September 19, 1995 to Heritage Environmental
Services, Inc., USA, p. 7 [Appl. US 214804, March 15, 1994].
Watanabe N, Mori K. Treatment of spent cupric chloride solution. JP Patent No. 63014883; January 22, 1988 to
Densan KK, JP, p. 2 [Appl. JP 155096, July 3, 1986].