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Journal of Cleaner Production 113 (2016) 17e27

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Journal of Cleaner Production


journal homepage: www.elsevier.com/locate/jclepro

Review

Sustainability assessment of the recovery and utilisation of acid from


acid mine drainage
Yvonne Nleya, Geoffrey S. Simate*, Sehliselo Ndlovu
School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, P/Bag 3, Wits 2050, South Africa

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 13 April 2015
Received in revised form
2 November 2015
Accepted 2 November 2015
Available online 12 November 2015

Acid mine drainage (AMD) presents serious threats to the environment due to its toxic constituents.
Traditional wastewater treatment methods such as neutralization, precipitation, membrane processes,
ion exchange and biological sulphate removal, etc., have been applied to remediate AMD and reduce its
negative impact on the receiving environment. However, the challenge with most of these methods is
that the constituents of AMD have not been viewed as valuable resources. The constituents, though toxic
can be recovered and transformed into valuable materials which could be marketed. Amongst the
various AMD constituents, is sulphuric acid which has an appreciable market in the chemical and
metallurgical industry. The acid value could be recovered from AMD and used to meet the demands of
various sulphuric acid consumers. The nancial benets obtained could then be used to offset the overall
AMD treatment cost. Hence, this paper reviews some of the techniques used to recover sulphuric acid
from various wastewater solutions. The techniques reviewed include: rectication, membrane separation, solvent extraction, crystallization and acid retardation. The technical and economic feasibility of
each process for application to AMD is also evaluated. Subsequently, the acid retardation and crystallization technologies are recommended as the most promising technologies for acid recovery from AMD.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Acid mine drainage
Sulphuric acid
Wastewater treatment
Environmental effect

Contents
1.
2.
3.
4.

5.
6.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Occurrence and composition of acid mine drainage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Utilization of sulphuric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Recovery of sulphuric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1.
Rectification process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.2.
Membrane processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.3.
Solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.4.
Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.5.
Acid retardation process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Economic evaluation of the proposed processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Summary and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Disclaimer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

1. Introduction

* Corresponding author. Tel.: 27 11 717 7570, 27 76 112 6959 (cell); fax: 27 11


717 7599.
E-mail addresses: simateg@yahoo.com, simateg@gmail.com (G.S. Simate).
http://dx.doi.org/10.1016/j.jclepro.2015.11.005
0959-6526/ 2015 Elsevier Ltd. All rights reserved.

Acid mine drainage (AMD) is a severe environmental problem


which results from the oxidation of pyrite and other sulphide
minerals found in mining tailings, rock stock piles and

18

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27

underground mine workings (Evangelou, 1995; Johnson and


Hallberg, 2005). The AMD is highly acidic and is enriched with
sulphate, iron, nickel, manganese, lead and many other heavy
metals (Evangelou, 1995). The acidic nature of AMD provides a
desirable medium for heavy metals to remain in solution rendering
the water highly toxic and corrosive. Although naturally occurring
systems found in association with some geological strata are able to
neutralize the formed acid and precipitate the heavy metals either
as carbonates or hydroxides (Johnson and Hallberg, 2005; Dold,
2010), they are overwhelmed in most cases. Excess quantities of
acid that are beyond the natural neutralizing systems are produced.
Therefore, the release of the toxic water onto land and water
streams is unavoidable thus, causing dire environmental consequences. For example, massive sh eradication, ecological imbalance, plant poisoning, equipment scaling and corrosion are some of
the consequences (Earle and Callaghan, 1998; Jennings et al., 2008;
Yadav, 2010).
Over the past 50 years, assiduous efforts have been directed at
remediating AMD through acid and metal removal so as to reduce
the impact of the acidic water on the environment and produce
water suitable for re-use (Johnson and Hallberg, 2005; Simate and
Ndlovu, 2014). A conventional and popular method used to treat
AMD is neutralization by limestone. However, the main drawback
of this method is the huge amount of sludge produced which
presents serious disposal challenges (Johnson and Hallberg, 2005).
Furthermore, valuable resources such as sulphuric acid which could
otherwise be recovered are lost in the process. Other methods such
as adsorption, ion exchange, membrane processes and electrowinning have also been used in the past. However, the downside of
all these efforts is that the constituents of AMD have not been
viewed as valuable resources.
In a world where environmental protection and rehabilitation
are fast becoming a priority, economic sustainability and technical
feasibility become key drivers in determining the suitability of any
proposed method or system for any application. Methods that can
transform undesirable waste materials to useful products are highly
preferred. Therefore, research in the recent years has focused on
the recovery and marketing of valuable AMD constituents such as
iron oxides, water and sulphuric acid, etc., (Hedin, 2002; Buzzi
et al., 2013; Mart-Calatayud et al., 2013). Of growing interest is
the recovery of sulphuric acid from AMD (Mart-Calatayud et al.,
2013) which is partly due to its appreciable market in the chemical and metal industries. The recent growth in uranium, nickel
laterites and copperecobalt oxide industries has also played a
major role in the demand for sulphuric acid used for leaching.
Therefore, alternative methods for meeting the chemical demand,
apart from sulphur and pyrite burning in a smelter, are being
considered. This approach could prove to be useful in developing
countries like South Africa where power supply challenges can
possibly cause cutbacks in the operation of smelters and other facilities that produce sulphuric acid. In such cases, the recovery and
usage of sulphuric acid from AMD could provide an alternative
solution to the increasing demand. Furthermore, from an environmental standpoint, the recovery of the sulphuric acid from AMD
provides the benet of a water by-product which is signicantly
less harmful to the environment. Hence, this paper focuses on the
recovery of sulphuric acid from AMD and its possible utilization in
various processes. The paper brings to light a number of technologies that have been studied or applied to acid recovery from
aqueous and other waste water solutions including AMD. Each
technology is reviewed and evaluated with the perspective of
application to AMD solutions. The successful recovery of sulphuric
acid from AMD will go a long way in alleviating problems associated with AMD. Apart from the production of re-usable water, the
recovery of the valuable sulphuric acid would be used to offset the

treatment cost of AMD (Simate and Ndlovu, 2014). In this regard,


what has been long recognized as an environmental hazard could
be transformed into a lucrative business.
This paper is organized as follows: the occurrence and composition of AMD is discussed rst, followed by the utilization of sulphuric acid. The technologies used for acid recovery, economic
evaluation of each process and future prospects are outlined in the
last three sections, respectively.

2. Occurrence and composition of acid mine drainage


Underground mine workings, mine waste dumps, tailings and
ore stockpiles are the major sources of AMD. The AMD results from
a series of reactions starting with the oxidation of pyrite in the
presence of oxygen and water to form ferrous iron and sulphuric
acid (Singer and Stumm, 1970) as shown in Equation 1.

2FeS2 s 7O2 g 2H2 Ol/2Fe2 aq 4SO2


4 aq
4H aq

(1)

In sufciently oxidising environment (dependant on O2 concentration, pH greater than 3.5 and bacterial activity) the ferrous
iron released in Reaction 1 may be oxidised to ferric iron, according
to the following reaction (Blowes et al., 2003; Ackil and Koldas,
2006).

4Fe2 aq O2 g 4H aq/4Fe3 aq 2H2 Ol

(2)

At pH values between 2.3 and 3.5, ferric iron precipitates as


Fe(OH)3 as shown in Equation (3) (Ackil and Koldas, 2006). This
causes a further drop in pH and leaves little ferric iron in solution.
The remaining ferric iron reacts directly with pyrite to produce
more ferrous iron and acidity as illustrated in Equation (4) (Ackil
and Koldas, 2006; Jennings et al., 2008).

4Fe3 aq 12H2 Ol/4FeOH3 s 12H aq

(3)

FeS2 s 14Fe3 aq 8H2 Ol/15Fe2 aq 2SO2


4 aq
16H aq
(4)
Upon consideration of the reaction schemes above (Equations
(1)e(4)), Reaction 2 has been found to be the slowest and consequently termed the rate limiting reaction of pyrite oxidation (Singer
and Stumm, 1970). However, the presence of acidophilic bacteria
such as Thiobacillus ferroxidans greatly accelerates the abiotic
oxidation rate of ferrous ions by a factor of hundreds to as much as
millions. This maintains a high concentration of ferric iron in the
system (Singer and Stumm, 1970; Blowes et al., 2003; Sanchez,
2008), thus resulting in highly oxidizing conditions. These acidic
oxidizing conditions provide a desirable environment for the
leaching of other minerals such as galena, sphalerite, chalcopyrite,
etc., which are usually found in association with pyrite (Blowes
et al., 2003). The result of the overall process is a solution that is
highly acidic and enriched with sulphate, iron, aluminium, nickel,
lead and other toxic heavy metal ions. As already stated, discharge
of this acidic solution onto land and eventually into rivers and lakes
poses an instant threat to the biota and ecological balance
(Evangelou, 1995; Dold, 2010). Hence, it is imperative that the
acidity is removed in order to minimize the environmental impact.
However, the removal of the acid should be a holistic process with
the focus being on the recovery and reutilization. Recovery of the
acid will not only produce potable water suitable for other purposes, but will also recover a valuable resource which could be used

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27

19

Table 1
Applications of sulphuric acid.
Application

References

Leaching
Electroplating
Acid pickling
Steel making
Automobile batteries
Paper bleaching
Fertilizers
Gasoline
Sugar bleaching
Water treatment
Sulphonation agent
Colouring agent
Amino acid intermediates
Regeneration of ion exchange resins
Cellulose bres
Pharmaceuticals

McDonald and Whittington, 2008; Venter and Boylett, 2009; Zhao et al., 2014
Hudson, 1994
Parujen, 1997, Sheedy, 1998
Martin, 2014
ATSDR, 1998
Martin, 2014
ICF, 2012; Hudson, 2012; IHS, 2014
Hudson, 2012
Manzoor et al., 2012
Inyo, 2013
ATSDR, 1998
HSBD, 2010
ICF, 2012
Robinson et al., 1998
Manzoor et al., 2012
Hudson, 2012

to offset the treatment cost of AMD (Simate and Ndlovu, 2014). In


other words, when the treated water and the revenue from the
sulphuric acid exceed the cost of treatment, it is feasible to create
enterprises that will provide economic benets whilst providing a
solution to the environmental problem (Simate and Ndlovu, 2014).
3. Utilization of sulphuric acid
Sulphuric acid is the cheapest inorganic acid and has found
widespread applications. It is referred to as a universal chemical or
king of chemicals due to its numerous applications as a raw material or processing agent (Martin, 2014). Table 1 gives the various
applications of sulphuric acid, clearly indicating that it is the most
utilized chemical in the world. In fact, the Information Handling
Services (IHS) consulting company has estimated a moderate increase in the consumption of sulphuric acid of about 2% per year for
the forecast year of 2014e2019 (IHS, 2014). The production of
phosphate fertilizer materials, especially wet-process phosphoric
acid is the major end-use market for sulphuric acid, accounting for
over 58% of the total world consumption in 2014 (IHS, 2014).
Moreover, the growth in population and an increased need in
developing countries to switch to more nutritious foods which
require more fertilizer continue to be key drivers to the increasing
demand.
The chemical industry has also played a role in the consumption
of acid in electroplating (Hudson, 1994), acid pickling (Parujen,
1997; ATSDR, 1998), ion exchange regeneration and, in the manufacture of colouring agents, sulphonation agents, etc. (ATSDR, 1998;
HSDB, 2010). Sulphuric acid has also found wide spread application
in hydrometallurgy. It has been used for leaching of most oxidic
ores such as nickel laterite ores, vanadium pentoxide, uranium ores,
chromite ores (McDonald and Whittington, 2008; Simate, 2009;
Venter and Boylett, 2009; Tavakoli et al., 2014; Zhao et al., 2014)
and copperecobalt oxide ores (Seo et al., 2013), amongst various
other applications. In addition to the existing market, the growth in
the demand for sulphuric acid in Africa, owing to the increase in
copperecobalt and uranium production (Hiji et al., 2014) is expected to play a major role in the future demand of the chemical.
Hence, a readily available market for the recovered acid could be
anticipated.
4. Recovery of sulphuric acid
Direct neutralization using limestone has been traditionally
used to treat waste solutions containing sulphuric acid. The problem with this approach is that bulky sludge is produced which

presents serious disposal challenges (Johnson and Hallberg, 2005).


In addition, neutralization removes the acid value which could
otherwise be recovered for future use. Efforts have, therefore, been
directed towards the recovery of sulphuric acid due to the economic and environmental benets of this approach. Several
methods have been developed for the recovery of sulphuric acid
from industrial waste solutions including membrane processes (Lin
and Lo, 1998; Jeong et al., 2005; Cifuentes et al., 2006), ion exchange
(Nenov et al., 1997), solvent extraction (Gottliebsen et al., 2000a,b;
Agrawal et al., 2007; Haghshenas et al., 2009), rectication (Song

et al., 2013), crystallization (Kim, 2006; Ozdemir


et al., 2006) and
acid retardation (Hatch and Dillon, 1963; Brown et al., 1987;
Sheedy, 1998). Table 2 is a summary of the methods used to
recover sulphuric acid from waste streams showing the recoveries,
advantages and disadvantages of the processes. This section reviews a number of these processes and critically evaluates the
technical and economic feasibility of their application to sulphuric
acid recovery from AMD.

4.1. Rectication process


Rectication also known as slow distillation is a promising
process for the recovery of high purity sulphuric acid from waste
acid solutions (Song et al., 2013). This process which works by
separating mixtures based on differences in volatilities of components in a boiling liquid mixture can concentrate and purify products in one step (Qian et al., 2011). In a study by Song et al. (2013),
the rectication method was used to recover high purity sulphuric
acid from the waste acid generated in toluene nitration process. The
results showed that ve nitro compounds could be removed and
high purity acid recovered at the same time. The recovered sulphuric acid with a concentration reaching 98.2% had a comparable
quality with commercial acid and hence could be recycled back into
the toluene nitration process. Although distillation has been used in
the recovery of other acids (Cheetham and Rothrock, 1941; Xu et al.,
1999; Mahajan et al., 2008), it is not favoured because of the high
costs associated with energy for vaporisation. However, slow
distillation (rectication) offers the benets of simultaneous
removal of impurities and recovery of high purity acid. A possible
ow diagram for the recovery of sulphuric acid from AMD through
rectication is shown in Fig. 1. It can be seen that large quantities of
heat energy are required for both pre-heating and rectication
processes. In the rectication unit, the water component is vaporized while the sulphuric acid remains in solution and is recovered
separately.

20

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27

Table 2
Summary of methods used for sulphuric acid recovery.
Method

Solution content

H2SO4 recovery

Advantages

Disadvantages

References

Rectication

H2SO4, nitro
compounds
H2SO4, Al
H2SO4, Fe, V
H2SO4, Ni
H2SO4, rare earth
sulphates
H2SO4, Ni
H2SO4, Fe
H2SO4, Cu, Sb, As
H2SO4, Fe, Na
H2SO4, Fe
H2SO4, Fe
H2SO4, Ni
H2SO4, Fe

R 98.3%

Recovery of high purity acid

High energy consumption


High operating cost
Not efcient at low acid
concentration

Song et al. (2013)

Diffusion dialysis

Electrodialysis

Acid retardation

Crystallization
Solvent extraction

H2SO4, Cu
H2SO4, Fe, Mn
H2SO4, Zn

R
R
R
R

R
R
R
e
R
R
R

Lin and Lo. (1998)


Wei et al. (2010)
Jeong et al. (2005)
Tang et al. (2006)

82e90%
84%
80%
70e80%

High acid recovery


Low pay back period
Strong salt rejection

80e90%
90%
Up to 99%

Clean acid product


Reduced solid waste for disposal

High operating cost


Membrane fouling

74e96%
96%
70e95%

Low operating cost


High acid recovery
Small equipment size and space
Low cost
Reduced waste for disposal
Can manage great volumes
of solutions
with high content of toxic solutes
Clean acid product
Only physical separation
High throughput with compact
equipment

Increases product volume


High consumption of fresh water
Dilute acid product
Risk of scale formation in crystallizer.
High energy consumption
Chemicals used are hazardous
Pre-treatment is required to remove
impurities
Difculties in stripping from Cyanex 923
Co-Extraction of Fe and Zn

E 75e79%
E 90%
E 90%

Baltazar et al. (1992)


Cattoir et al. (1999)
Cifuentes et al. (2006)
Mart-Calatayud et al. (2013)
Neuman et al. (1987)
Parujen (1997)
Sheedy and Parujen (2012)
Regel-Rosocka (2010)
Gottliebsen et al. (2000a,b)
Agrawal et al. (2007)
Agrawal et al. (2008)
Haghshenas et al. (2009)
Regel-Rosocka (2010)

R recovery; E percentage extraction.

However, when the rectication process is considered in the


context of AMD, it might not be a suitable recovery process because
the sulphuric acid content in AMD might be too low for any substantial economic benets. Technical grades of sulphuric acid have a
range between 70 and 93% (ICF, 2012), hence for the process to be
considered economically viable, the quality of the recovered acid
should be in this range. For low acid concentration, the cost of operation may supersede the nancial benets derived from the rectication process hence, making the process economically unattractive.
Furthermore, in AMD, both sulphuric acid and the heavy metals are in
the aqueous phase, thus effective separation might be virtually
impossible, as rectication requires a signicant difference in boiling
points for efcient separation to take place. The conversion of one of
the components (heavy metal or acid) into a different phase followed
by rectication might increase the attractiveness of the process.
4.2. Membrane processes
Membrane separation processes have increased dramatically
since their development in the 1950s (Sata, 1989). A membrane is a
semi-permeable barrier through which selected chemical species
can migrate from one region to the other. Typical membrane processes currently in use include diffusion dialysis (Lin and Lo, 1998,
Jianejun, 2006), electrodialysis (Baltazar et al., 1992; Liu and
Covington, 1994), membrane distillation (Tomaszewka et al.,
2000), membrane electrolysis (Kerney, 1994; Csicsovszki et al.,
2005) and, anion and cation exchange membranes (Oztekin and
Yazicigil, 2007; Mario et al., 1997). Traditional membranes have
been used for the desalination of brackish water and the recovery of

table salt from sea water. However, advancements in the processes


have seen the application of membranes in the recovery of acids
from metallurgical plant efuents. Of all the membrane separation
methods, diffusion dialysis and electrodialysis are the two most
commonly used methods in these efuents. The popularity of these
membrane techniques appears to emanate from the low-energy
consumption, high proton permeability and strong salts rejection
of the processes (Lin and Lo, 1998; Wei et al., 2010). Diffusion
dialysis makes use of a series of anion exchange membranes to
selectively attract the anion in the acid while electrodialysis uses an
electric eld to allow ions of one electrical charge to enter and pass
through (perm-selectivity).
Several research studies have been carried out on the recovery
of acids from solutions using diffusion dialysis. For example, hydrochloric acid (Bonner and Donatelli, 2001), nitric acid and hydrouoric acid (Negro et al., 2001) have been successfully recovered
using diffusion dialysis. Recovery of sulphuric acid from waste
aluminium surface processing solution (Lin and Lo, 1998), rare
earth
sulphate
solutions
(Jianejuan,
2005),
diamond
manufacturing waste solutions (Jeong et al., 2005), acid leach solutions (Wei et al., 2010; Zhang et al., 1999) have also been exten
 (2004a) investigated the
sively investigated. Palat and Z
akova
separation of sulphuric acid from a sulphate acid system by diffusion dialysis. In their study, sulphuric acid was found to permeate
well through the anion exchange membrane while cupric sulphate
was rejected. Similar results were also observed in the separation of

sulphuric acid from zinc sulphate solution (Palat and Z
akov
a,
2004b). In all these studies, high purity acid solutions were obtained. Furthermore, preliminary economic evaluation conducted

Vapour

Heated
solution
Pre-filtered
AMD

Boiler unit

Cooling tower

Rectification unit (complete


with rectification and pumping
system)

Recovered
water

Clean H2SO4
output

Fig. 1. Proposal ow diagram for the recovery of sulphuric acid from acid mine drainage using rectication process.

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27

reported low pay back periods for diffusion dialysis, ranging from
slightly over a year to 27 months (Lin and Lo, 1998; Jeong et al.,
2005) making the method economically attractive.
Electrodialysis has also been studied for the recovery of acid
from waste solutions. As already indicated, perm-selectivity is
supported by use of an electric eld. Several studies on the recovery
of organic acids from waste solutions have been published, e.g.,
tartaric acid (Audinos and Paci, 1992), glutonic acid and lactic acid
(Yu et al., 2003; Novalic et al., 2000), etc. Yu et al. (2003) also found
that, apart from many other factors which can be determined
experimentally, the concentration of the recovered organic acid
was mainly inuenced by the current density. Thus, by optimizing
the current density, it is possible to obtain high organic acid concentrations from waste solutions. The recovery of inorganic acids
has also been studied. Ali et al. (2004) recovered nitric acid from
ammonium nitrate solutions. High purity sulphuric acid and sodium hydroxide were obtained from an aqueous sodium sulphate
solution using a three-compartment redox potential (Eh) cell
(Tzanetakis et al., 2002). However, the operating cost of the process
was high compared to the method that used a two-compartment
cell. Cattoir et al. (1999) also found that 90% of the sulphuric acid
present in stainless steel decontamination waste could be recovered using the electrodialysis method. Sulphuric acid recovery from
an acidic nickel sulphate solution (Baltazar et al., 1992), copper
containing solutions (Cifuentes et al., 2006) and recently AMD
(Mart-Calatayud et al., 2013) has also been studied. MartCalatayud et al. (2013) found that an effective recovery of sulphuric acid with no Fe3 species present was obtained in the anodic
compartment as a result of the co-ion exclusion mechanism in the
membranes. This is a very promising technology for acid recovery
from AMD due to its ability to produce high purity acid. However,
the performance of the process with respect to real AMD solution
containing various heavy metal ions still remains to be explored.
Furthermore, the formation of precipitates at the surface of the
membrane related to an abrupt increase in cell voltage was found to
limit the process performance (Mart-Calatayud et al., 2013).
Membrane distillation is one of the most promising membrane
technologies for the recovery of acids (Tomaszewska et al., 1995,
1998, 2000; Tang and Zhou, 2006; Tomaszewka and Mientka,
2009; Wang and Chung, 2015). It involves the use of a hydrophobic membrane which separates two aqueous solutions at different
temperatures and composition to get a concentrated solution
containing the acid and the salts. As a result, fresh water and
concentrated acid or salt are obtained. Membrane distillation is
considered a highly selective operation for both non-volatile
(Regel-Rosocka, 2010) and volatile (Tomaszewka et al., 2000) solutions. It also offers advantages of low energy consumption, high
efciency and operation at low temperatures to recover fresh water
and concentrate the acid and metals (Tomaszewska et al., 1998,
2001). However, the process has been mostly tested at laboratory
scale and its success in the recovery of sulphuric acid from industrial efuents still needs further investigation.
Membrane electrolysis has been investigated for the recovery of
acids from waste solutions. For example, high purity hydrochloric

De-ionized water

Pre-filtered AMD
solution

Diffusion dialysis membranes

Clean H SO product

Acid barren water

Fig. 2. Proposal ow diagram for the recovery of sulphuric acid from acid mine
drainage using diffusion dialysis method.

21

H SO product

Pre-filtered AMD
solution

Electrodialysis unit

Acid barren water

Fig. 3. Proposal ow diagram for the recovery of sulphuric acid from acid mine
drainage using electrodialysis method.

acid has been recovered from spent pickling liquors using a combination of ion exchange and membrane electrolysis (Csicsovszki
et al., 2005). In this study, zinc was recovered in the rst step using anion exchange and the acid recovered in the second step by
membrane electrolysis. The process also appears to be a prospective technique for the recovery of sulphuric acid from waste solutions due to its simplicity and ability to signicantly reduce solid
waste. However, the evolution of hydrogen gas at the cathode was
noted as a drawback to this process (Csicsovszki et al., 2005).
Furthermore, the high cost associated with the energy demand of
the process could reduce interests in exploring the technology
further.
Figs. 2 and 3 are proposed ow diagrams for the recovery of acid
from AMD using diffusion dialysis and electrodialysis, respectively.
In both ow diagrams, the pre-ltered AMD solution is passed
through a membrane unit where a clean acid and an acid barren
water product can be obtained. In general, it can be seen that most of
the membrane separation processes are environmentally attractive.
Apart from signicantly reducing the solid waste, high purity acid
product can be obtained in most cases. Nevertheless, the high capital
cost as well as the running cost associated with heating the solutions
and membrane replacement (due to fouling) might be too high to
make it economically viable for AMD treatment. Furthermore, since
sulphuric acid is well known to be the cheapest inorganic acid
available, the revenue realized from the sale of the product might be
too low to compensate for the overall treatment cost. The development of new membranes which can possibly compensate for high
cost by having high permeability and less fouling could nd their use
in AMD more justiable. Furthermore, reducing costs by employing
low cost energy sources such as solar or wind to drive processes like
electrodialysis could promote their use.

4.3. Solvent extraction


Solvent extraction process has long been used in the recycling of
waste acids. This process is principally used for large-scale operations where the concentrations of contaminants are high (Agrawal
and Sahu, 2009). Solvent extraction processes are concerned with
the removal of specic constituents by transfer from the aqueous
phase into an immiscible non-aqueous phase. In the recovery of
acids, a non-aqueous phase that has a high afnity for the acid is
chosen. In the recent past, several studies have been conducted to
test the feasibility of using solvent extraction to recover various
acids. Shin et al. (2009) examined the use of tri-butyl phosphate
(TBP) extractant to recover nitric acid from waste etching solutions.
Nitric acid with a purity of 99.8% was obtained. The recovery of
phosphoric acid, acetic acid and hydrouoric acid using solvent
extraction has also been explored (Kim et al., 2005, 2007). Sulphuric acid recovery from aqueous solutions has also been extensively studied (Gottliebsen et al., 2000a, 2000b; Agrawal et al.,
2008; Haghshemas et al., 2009). Gottliebsen et al. (2000a)
compared tris (2-ethylhexyl) amine (TEHA) and cyanex 923 in the
recovery of sulphuric acid from copper electrolyte bleeds and found
that both extractants were able to extract close to 80% of the acid
with no iron or copper detectable in the product. Furthermore,

22

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27


Organic
extractant

AMD solution

Sulphate loaded extractant

Extraction stages at
ambient temperature

Recovered H SO

Stripping stages at
ambient temperature

Raffinate
Stripped extractant

Stripping agent

Fig. 4. Proposal ow diagram for the recovery of sulphuric acid from acid mine drainage using solvent extraction method.

Haghshemas et al. (2009) found the recovery of sulphuric acid


using TEHA to be more thermodynamically feasible compared to
that of cyanex 923. Agrawal et al. (2008) also showed that the
extraction of sulphuric acid with Alamine 336 was close to 90%.
However, nding a suitable stripping agent proved to be a challenge since the extractant used strongly binds the acid and hence, it
could not be completely stripped from the loaded organic with
water.
In view of various studies discussed above, solvent extraction is
a promising technology that can be extended to the recovery of
sulphuric acid from AMD (Fig. 4). The main advantage is that it is a
clean and proven technology (Gottliebsen et al., 2000a). Furthermore, the organic extractants tested have good selectivity for the
acid; hence high recoveries can be expected (Gottliebsen et al.,
2000a; Agrawal et al., 2008). However, solvent extraction has
been found to be effective for large operations where the concentrations of the contaminants are high (Agrawal and Sahu, 2009).
Hence, the recovery of low concentrations of acid in large volumes
of solutions such as AMD could hinder the effectiveness of the
process making it economically unattractive. Furthermore, the
hazardous nature of the extractants used in solvent extraction is the
major factor that could diminish the attractiveness of the process.
4.4. Crystallization
Crystallization has also been used for acid recovery from waste
acid solutions. For example, highly puried phosphoric acid with
negligible metallic content has been obtained using melt crystallization (Kim, 2006). Ozdemir et al. (2006) also studied the recovery
of hydrochloric acid from waste pickling liquor using crystallization. The results showed that ferrous chloride could be removed by
crystallization and this enabled the recycling of the remaining acid
back to the pickling bath. Tjus et al. (2006) investigated a combination of nanoltration and crystallization for the recovery of
hydroouric acid and nitric acid from two stainless steel plants. The
results indicated that it is possible to use the hybrid technique for
the continuous removal of excess metals in the form of uorides
that can form oxides after pyrometallurgical treatment. Pilot plant
investigations on the process have shown some advantages such as
reduction in environmental impact at landlling sites and downstream water areas, reduced waste processing as well as savings in
chemical costs. However, having to allow some of the acid to ow
out of the system in order to avoid high nickel concentrations in the
product stream has been found to be a challenge in this technique
(Tjus et al., 2006). Crystallization has also been used in the recovery
of acid from spent liquor solutions based on the solubility differences between the water, sulphuric acid and iron sulphate (Agrawal
and Sahu, 2009). Iron is more soluble at higher temperatures and
crystallizes out by indirect cooling crystallization, cyclone crystallization or vacuum crystallization. This avoids the need to
neutralize the free acid and also pure salt is produced. With crystallization, signicant water releases and salt load reduction can be
achieved (Agrawal and Sahu, 2009). However, this method has
been found to have the following drawbacks, (1) a large amount of

energy is required for crystallization, (2) the removal of heavy


metallic ions such as iron from waste acids is difcult, and (3) an
economical method for treating the crystals is not available.
For the optimization of heat energy in the process, freeze crystallization has emerged as a promising technology for the recovery
of sulphuric acid from waste solutions (Etter and Langill, 2006;
Cullivan, n.d). Actually, freeze crystallization is currently a commercial applied technology for the recovery of sulphuric acid from
waste pickling solutions at Deacero Company in Mexico (Cullivan,
n.d). In this technology, reducing the temperature of the solution
results in the removal of iron in the form of ferrous sulphate heptahydrate crystals. Sulphuric acid remains in the solution and can
be recovered separately. The ferrous sulphate crystals are sold as
commodity and the revenue is used to offset some of the operational costs. The clean acid output is recycled back into the pickling
plant thus, saving the company a lot of money in operating
expenditure.
Freeze crystallization has promising application for sulphuric
acid recovery from AMD. In addition to the acid, AMD also contains
high quantities of ferrous ions which can also be recovered as
crystals, puried and marketed as a commodity. A proposed ow
diagram for the recovery of sulphuric acid via freeze crystallization
is shown in Fig. 5. In this diagram, pre-ltered AMD solution is
chilled in a heat exchanger unit using the cold sulphuric acid
product. After the solution is pre-chilled, it enters the reactor where
it is agitated and chilled further until the ferrous sulphate heptahydrate crystals are formed. The settled crystalline solution is
pumped to the centrifuge, where the crystalline product and the
sulphuric acid solution are separated. The cooled sulphuric acid
product is pumped back to the primary heat exchanger where it
cools the incoming AMD solution and then collected for storage.
The overall benet of the process is acid recovery which leads to
reduced solid waste and, subsequently, reduced environmental
risk. The process is also presumed to be technically feasible since it
has shown great success in commercial applications such as at the
Deacero Company. The economics of the process are expected to be
within reasonable costs considering the reduced energy
requirements.
Another crystallization technology which can be explored for
sulphuric acid is the eutectic freeze crystallization technology,
which has already demonstrated considerable success in the recovery of other valuable materials from AMD solutions (Randall
et al., 2011). Research is required to investigate which of the two
technologies is more technically and economically applicable to
acid recovery from AMD.
4.5. Acid retardation process
The acid retardation process was initially introduced by Hatch
and Dillon (1963). The process is based on the adsorption of the
undissociated acid as it passes through a bed of ion exchange resins
while dissolved metal salts are rejected. The resin has a greater
afnity for the acid than for the metallic salts resulting in chromatographic separation of metallic salts from the acid whose

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27


Clean H2SO4
product

Pre-filtered
AMD solution

23

FeSO4. 7H2O
crystals
Reactor and crystal settler
unit

Heat exchanger unit

Centrifuge unit

Chilled H2SO4
product

Fig. 5. Proposal ow diagram for the recovery of sulphuric acid from acid mine drainage using freeze crystallization technology.

movement is retarded (Sheedy, 1998). When backwashed with


water, the adsorbed acid is released. Despite its wide application
(Hatch and Dillon, 1963; Brown et al., 1979; Brown et al., 1980;
Brown et al., 1987; Dejak, 1994; Parujen, 1997; Sheedy, 1998;
Sheedy and Parujen, 2012), the mechanism of the process is not
very well understood, thus various postulations have been suggested to explain the phenomenon. Gulbas et al. (1987) suggested
that the reason for acid retardation is due to the different rates of
diffusion of metal ions, dissociated acids and acid molecules,
respectively. Sheedy and Parujen (2012) indicated that the process
is driven by the acid concentration difference between the interior
of the resin phase and the surrounding uid. Agrawal and Sahu
(2009) suggested that the release of the acid from the resins by
water is a result of the difference in osmotic pressure.
Although the process was introduced in 1963, it was not successfully commercialized at that time due to the limitations of
conventional ion exchange equipment design. In 1978, acid retardation was successfully commercialized and applied as the RECOFLO acid purication system (Brown et al., 1987). The design
incorporated the use of ne mesh resin beads to increase surface
area and improve reaction kinetics (Dejak, 1994), short resin bed to
reduce pressure drop and equipment size, full packing to minimize
intermixing and dilution of feed and regenerant streams, and
nally counter current ow to maximize chemical efciency
(Brown et al., 1987). Typically, greater that 90% of the sulphuric acid
was recovered in the product stream and could be recycled when
desired (Brown et al., 1987; Sheedy, 1998). Hundreds of similar
units have since been installed worldwide for the recovery of hydrochloric, sulphuric and nitric acid from metal nishing wastes.
The widespread application of the acid retardation process in metal
nishing industry emanates from its low cost, simplicity and superior performance (Dejak, 1994; Brown, 1996). However, despite
being effective in reducing ionic contaminants to acceptable levels,
the resins used in the process normally suffer from lack of selectivity. Therefore, over the years, research has been directed towards
improving the selectivity and efciency of the resins. For example,

Concentrated
acid solution

Acid barren
water

AMD

Acid retardation
system

Nenov et al. (1997) separated arsenic and sulphuric acid from


aqueous solution containing arsenic using a strong acid cation
exchanger in the Na-form. Kraus et al. (1953) and Shamritska et al.
(1972) extracted sulphuric acid from metal sulphate solutions using
Dowex 1 anion exchange resin. Petkova et al. (1981) studied the
separation and recovery of sulphuric acid from metal cations
coexisting in the waste plating solution using Wofatit SBW anion
exchanger and showed that the process is effective until the relative
acid concentration in the efuents reaches C/Co 0.55 (where C is
the concentration of acid at a given moment and Co is the initial
concentration of the solution).
The acid retardation process is a promising technique for the
recovery of sulphuric acid from AMD. As already pointed out, the
process is simple and has high efciencies. Furthermore, only water
is used for elution, hence eliminating the need for expensive
regeneration chemicals as is the case in conventional ion exchange
systems. In addition, the quantity of waste is drastically reduced
through the recovery of the valuable acid. The drawback to this
process, however, is the production of a dilute solution which adds
to the solution volume. Nevertheless, this problem could be eliminated by concentrating the solution to obtain water of re-usable
quality in addition to the concentrated acid. A ow sheet for
application of the acid retardation process in the recovery of sulphuric acid from AMD is proposed in Fig. 6.
From the acid retardation system, a dilute stream of acid is obtained which can then be concentrated using a vacuum evaporator.
Water of a quality suitable for recycling back to the system can also
be obtained. A study on the sulphuric acid/water system by De
Dietrich processing systems indicated a large separation factor
when using a vacuum evaporator (De Dietrich, 2013). Furthermore,
a vacuum evaporator reduces the boiling point of the mixture
which, subsequently, minimizes the cost of heating. In the study,
there was nearly no sulphuric acid was in the water vapour up to an
acid concentration of 70%. Obtaining higher concentrations of the
acid compromised the purity of both acid and product water. This
concept could, therefore, be used to concentrate the acid to only

Diluted acid
solution

Vacuum
evaporator

Re-usable water

Elution water
Fig. 6. Proposed acid retardation set up for sulphuric acid recovery from acid mine drainage.

24

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27

Table 3
Assumptions used in the economic evaluation calculations.
Description

Units

Value

Annual working hours


Plant estimated downtime
Plant available time
Plant capacity
Plant efciency
Cost of 70% H2SO4
Cost of FeSO4$7H20

Hour/year
Hour/year
Hour/year
Litre/hour
%
$/tonne
$/tonne

8760
1560
7200
1500
95
560
130

70% and market it to consumers requiring such levels of acid concentration. The benets derived from this proposed process not
only include reduction in energy required for evaporation, but
production of a marketable grade of sulphuric acid. Nevertheless,
research is required to test the feasibility of the proposal ow sheet
for acid recovery.
5. Economic evaluation of the proposed processes
To establish sustainability assessment, an economic evaluation
of the proposed processes is essential. Therefore, a conceptual
economic evaluation of the proposed processes was conducted
based on cost information of available plants. The assumptions
used in the calculations are summarized in Table 3.
The capital and operating costs in the order of magnitude were
estimated using the sixth tenth rule (Equation (5)).


Cf C1

S2
S1

0:6
(5)

Where C1 is the capital cost of the plant with capacity S1 and Cf is


the capital cost of the proposed plant with capacity S2. Where there
was no existing plant, the capital cost was estimated based on
factors of the purchased equipment cost available in traditional
design textbooks and technical literature (Peters and Timmerhaus,
1991; Sinnott, 2005; ETSAP , 2010). All inationary adjustments
were done using the 2015 Chemical Engineering Plant Cost Index
(CEPCI) as well as those available in literature (Vatavuk, 2002).
The capital cost of the proposed acid retardation unit was based
on information of an acid sorption plant (Dejak and Munns, 1987),
the crystallization unit cost was derived from a freeze crystallization plant in Mexico (Etter and Langill, 2006; Cullivan n.d) and, the
electrodialysis and diffusion dialysis were based on cost information by Schoeman and Steyn (2000). The capital costs of the rectication and solvent extraction units for sulphuric acid recovery
were estimated based on similar existing systems (Ricker and King,
1980; ETSAP, 2010). The capital costs estimated include the location
and site requirements, building requirements, raw material and
product handling facilities. The cost for engineering and services is
also included in the estimate. However, it is unlikely that any capital
would be allocated to building and land requirements since the
units would be built on existing AMD treatment plants. A signicant amount of the capital cost will be spent on contractors' fees
and plant installation. The probable accuracy of this cost information presented herein may be in the range of 30 percent of the

actual cost; hence it is termed an order-of magnitude estimate


(Peters and Timmerhaus, 1991). The operating expenditure of the
proposed acid retardation, crystallization and rectication processes was estimated using the factors found in technical literature
(Sinnott, 2005; Peters and Timmerhaus, 1991). For the solvent
extraction, diffusion dialysis and electrolysis the operating costs
were estimated based on cost information available in existing
plants (Ricker and King, 1980; Shoeman and Steyn, 2000). The acid
recovery system efciency was assumed to be 95%, and the quantity
of product was estimated using simple mass balance. The revenue
was then estimated based on prevailing market prices.
The order of magnitude estimates of the capital and operating
expenditures of each proposed process for recovering sulphuric
acid from AMD are summarized in Table 4. The estimated revenue
obtained in the processes is also shown in the table. It can be seen
that the rectication and the electrodialysis plants have the highest
capital costs owing to complexity of the equipment used. Although,
a higher quality of acid can be obtained in these processes, it can be
seen that the annual operating costs are also quite high. This is due
to the high electrical energy requirements associated with the
processes. The cost of the annual membrane replacements also
greatly increases the annual operating cost for the electrodialysis
plant. Less energy intensive technologies such as the acid retardation, crystallization, solvent extraction and diffusion dialysis have
lower capital and operating costs, in comparison to the rectication
and electrodialysis processes. However, the annual operating costs
for diffusion dialysis are substantially higher than that of for the
other three technologies owing to the high costs of membrane
replacement and spare parts for pumps. With adequate preltration, the ion exchange replacement rate in the acid retardation process is expected to be low, since the resins are known to
have a life span of approximately 5e10 years (Cullivan and Cullivan,
2013).
Assuming 95% acid recovery, approximately US$9800 can be
obtained each year from each of the proposed technologies. Additional revenue of about $600 can also be realized for iron heptahydrate crystals obtained in the crystallization technology.
Although, the revenue is small it can be used to offset some of the
operational cost. Generally, if the gures of revenue versus the
operational costs presented in Table 4 are considered in an economic context, it may be concluded that the approach is not profitable. However, most AMD treatment methods that produce
potable water have high operating costs comparable to technologies such as electrodialysis in Table 4. A signicant percentage of
this cost is allocated for sludge disposal, which also continues to
pose as a potential environmental hazard even in the secured
landlls. In addition, no revenue is realized (except that of the
treated water) since all valuable products are lost in the processes.
Sulphuric acid recovery from AMD on the other hand, though costly
to set up, offers several advantages if used in conjunction with
these techniques. Firstly, the sludge burden is signicantly reduced
and, subsequently, the disposal costs and environmental hazards
are eliminated. Secondly, the main processes receive less contaminated water (due to acid removal) resulting in less energy requirements. The overall effect of this is substantial reduction in
operating costs. With proper design and optimization, it is possible

Table 4
A summary of capital and operating expenditures of proposed process routes.
Cost (US$)

Rectication

Diffusion dialysis

Electrodialysis

Solvent extraction

Crystallization

Acid retardation

Fixed capital cost


Total estimated CAPEX
Total estimated Annual OPEX
Estimated Annual revenue

1 193 165
1 372 140
427 789
z9800

381 780
439 047
247 752
z9800

1 523 478
1752 000
266 809
z9800

442 956
509 399
125 124
z9800

407 268
468 368
154 798
z10 320

307 973
354 169
124 810
z9800

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27

to obtain a protable process where the cost of the treated water


and sulphuric acid exceeds the cost of AMD treatment. Furthermore, the use of cheaper energy alternatives and energy optimization will greatly increase the nancial viability of such a project.
6. Summary and future prospects
Many countries, including South Africa and other Sub-Saharan
states, typically produce sulphuric acid from sulphur (Tzoneva,
2008). The production of sulphuric acid through pyrite smelting
has also been considered due to the abundance of pyrite in the
region (Hiji et al., 2014). While these sources have been able to meet
the demand, there are concerns such as the high cost of procuring
raw material, and the possibility of failing to meet demand due to
some cutbacks in operation resulting from power supply challenges. In such instances, it might be more economically attractive
to consider a readily available source, such as sulphuric acid obtained from waste industrial solutions such as AMD.
This acid could be recovered and upgraded to technical grades
using well developed methods. If the quality of the acid is comparable to industrial grades, it is possible that some consumers
would switch to the utilization of a by-product of AMD or to use the
acid to complement their demands. Hence, the recovery of sulphuric acid from AMD could provide some nancial benets which
could be used to compensate for the cost of AMD treatment. Mining
companies would also benet through the production of a water
product which meets the stringent environmental regulations.
Presently, the future of acid recovery from AMD is promising.
Table 2 shows a summary of the methods that have been applied
for sulphuric acid recovery. It can be seen that methods such as
diffusion dialysis, crystallization, solvent extraction and acid
retardation appear to be the most promising of all the reviewed
techniques for acid recovery. However, based on technical and
economic feasibility, the freeze crystallization and acid retardation
processes are expected to be the best technologies for acid recovery
from AMD. Several studies on these processes have been conducted
and their fundamentals are well documented. Furthermore, their
use in commercial applications is widely recognized. However,
further work needs to be done to test the feasibility of using such
processes for acid recovery from AMD. Future research must
explore ways of addressing challenges currently associated with
the technologies and make suitable modications to suit AMD
treatment needs. For example, ways of tackling challenges such as
purication of crystals and high energy cost will have to be incorporated in the process designs that will be developed. Economic
and environmental benets will largely depend on the proper designs of such systems. In other words, designs which can signicantly reduce the environmental impact of discharged waste and
also bring some nancial returns will be highly preferred.
Disclaimer
The contents of this paper reect the views of the authors who
are responsible for the facts and accuracy of the data presented
herein and do not necessarily reect the ofcial views or policies of
any agency or institute. This paper does not constitute a standard,
specication, nor is it intended for design, construction, bidding, or
permit purposes. Trade names were used solely for information and
not for product endorsement.
References
Ackil, A., Koldas, S., 2006. Acid mine drainage (AMD): causes, treatment and case
studies. J. Clean. Prod. 14, 1139e1145.

25

Agrawal, A., Sahu, K.K., 2009. An overview of the recovery of acid from spent acidic
solutions from steel and electroplating industries. J. Hazard. Mater. 171, 61e75.
Agrawal, A., Kumari, S., Ray, B.C., Sahu, K.K., 2007. Extraction of acid and iron values
from sulphate waste pickle liquor of a steel industry by solvent extraction route.
Hydrometallurgy 88, 58e66.
Agrawal, A., Kumari, S., Sahu, K.K., 2008. Liquid-liquid extraction of sulphuric acid
from zinc bleed stream. Hydrometallurgy 92, 42e47.
Ali, B.M.A., Rakib, M., Laborie, S., Viers, P., Durand, G., 2004. Coupling of bipolar
membrane electrodialysis and ammonia stripping for direct treatment of
wastewaters containing ammonium nitrate. J. Membr. Sci. 244, 89e96.
ATSDR (Agency for Toxic Substances and Disease Registry), 1998. Toxicological
Prole for Sulfur Trioxide 409 and Sulfuric Acid. Available at: http://www.atsdr.
cdc.gov/toxproles/tp117.pdf (accessed March 2015).
Audinos, R., Paci, S., 1992. Direct production of pure concentrated tartaric acid from
its salts by electromembrane processes. Indian J. Chem. Sec. A 31, 355e360.
Baltazar, V., Harris, G.B., White, C.W., 1992. The selective recovery and concentration
of sulphuric acid by electrodialysis. Hydrometallurgy 30, 463e481.
Blowes, D.W., Ptacek, C.J., Jambor, J.L., Weisener, C.J., 2003. The geochemistry of acid
mine drainage. Treatise Geochem. 9, 149e204.
Bonner, F.J., Donatelli, A.A., 2001. Diffusion dialysis and acid recovery in metal operations. In: Technical Report No. 49. The Massachusetts Toxics Use Reduction
Institute, University of Massachusetts Lowell.
Brown, C.J., 1996. The Flourex process for regeneration of nitric/Hydrouoric
stainless steel pickle liquors. In: 2nd International Symposium on Ion Control in
Hydrometallurgy, Ottawa.
Brown, C.J., Davey, D., Simmons, P.J., 1979. Purication of sulfuric acid anodizing
solutions. Plat. Surf. Finish 54e57 (January Heft1).
Brown, C.J., Davey, D., Simmons, P.J., 1980. Recovery of nitric acid from solutions
used for treating metal surfaces. Plat. Surf. Finish 67 (2), 60e62.
Brown, C.J., Russer, A., Sheedy, M., 1987. New Ion Exchange Processes for Brine
Purication. US Patent 1564492.
rio, J.A.A., 2013.
Buzzi, D.C., Viega, L.S., Rodrigues, M.A.S., Bernardes, A.M., Teno
Water recovery from acid mine drainage by electrodialysis. Min. Eng. 4, 82e89.
Cattoir, S., Smets, D., Rahier, A., 1999. The use of electro-electrodialysis for the
removal of sulphuric acid from decontamination efuents. Desalination 121,
123e130.
Cheetham, H.C., Rothrock, D.A., 1941. Recovery of Organic Acids by Distillation. US
Patent 2267269.
Cifuentes, L., Garcia, I., Ortiz, R., Casas, J.M., 2006. The use of electrohydrolysis for
the recovery of sulfuric acid from copper-containing solutions. Sep. Purif.
Technol. 50, 167e174.
ro
k, T.I., 2005. Selective recovery of Zn and Fe from
Csicsovszki, G., Kekesi, T., To
spent pickling solutions by the combination of anion exchange and membrane
electrowinning techniques. Hydrometallurgy 77, 19e28.
Cullivan, n.d. An Ecological Sound Solution to Dumping Waste Pickling Acid. Beta
Control Systems. Available at: http://www.betacontrol.com/sites/default/les/
uploads/le/H2SO4_Literature/An%20Ecologically%20Sound%20Solution%20to%
20Dumping%20Waste%20Pickling%20Acid_0.pdf (accessed October 2015).
Cullivan, J., Cullivan, B., 2013. Economic and Chemical Comparisons of Hydrochloric
Acid Recovery Technologies for Iron Pickling Operations. Beta Control Systems,
Inc., Technical Paper, USA.
De Deitrich, 2013. Concentration of Sulphuric Acid and its Application. Available at:
http://www.qvf.com/qvf-process-systems/mineral-acids/concentrationing-ofsulfuric-acid.html (accessed August 2015).
Dejak, M., 1994. Acid purication and recovery using resin sorption technology- an
update. In: AESF/EPA Pollution Prevention Conference.
Dejak, M., Munns, K., 1987. Acid purication and recovery using resin sorption
technology e a review. Environmental II (F) 1e20.
Dold, B., 2010. Basic concepts in environmental geochemistry of sulphide mine
waste management. In: Kumar, E.S. (Ed.), Waste Management. In-tech, Rijeka,
pp. 173e198.
Earle, J., Callaghan, T., 1998. Impacts of Mine Drainage on Aquatic Life, Water Uses,
and Man-made Structures. Department of Environmental Protection (Chapter 4,
4.1e4.10).
ETSAP (Energy Technology Systems Analysis Program), 2010. Industrial Combustion
Boilers. Available at: www.etsap.org (accessed 15.11.15.).
Etter, K., Langill, P.D., 2006. Acid Recycling-process and Design Notes on Hot-dip
Galvanizing.
Available
at:
http://www.galvanizeit.org/images/uploads/
memberGalvanizingNotes/AcidRecycling,KurtEtter(GalvanizingNotes,2006Feb).
pdf (accessed October 2015).
Evangelou, V.P., 1995. Pyrite Oxidation and its Control. CRC Press, New York,
pp. 1e32.
Gottliebsen, K., Grinbaum, B., Chen, D., Stevens, G.W., 2000a. Recovery of sulfuric
acid from copper tank house electrolyte bleeds. Hydrometallurgy 56,
293e307.
Gottliebsen, K., Grinbaum, B., Chen, D., Stevens, G.W., 2000b. The use of pulsed
perforated plate extraction column for recovery of sulfuric acid from copper
tank house electrolyte bleeds. Hydrometallurgy 58, 203e213.
Glbas, M., Kammel, R., Lieber, H.W., 1987. Improvements of Hydrometallurgical
Processes by Application of the Acid Retardation Procedure-actual Situation and
Developments. Inst. Metall., Technical University of Berlin, Germany.
Haghshenas, D.F., Darvishi, D., Raeipour, H., Alamdari, E.K., Salardini, A.A., 2009.
A comparison between TEHA and Cyanex 923 on the separation and the
recovery of sulfuric acid from aqueous solutions. Hydrometallurgy 97,
173e179.

26

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27

Hatch, M.J., Dillon, J.A., 1963. Acid retardation. A simple physical method for separation of strong acids from their salts. Ind. Eng. Chem. Proc. Des. Dev. 2 (4),
253e263.
Hedin, R.S., 2002. Recovery of marketable iron oxide from acid mine drainage in the
USA. In: National Meeting of the American Society of Mining and Reclamation,
Lexington KY, June 9e13.
Hiji, M.F., Ntalikwa, J.W., Vuai, S.A., 2014. Producing sulphuric acid in Tanzania and
potential sources: a review. Am. J. Chem. Appl. 1 (4), 40e44.
HSDB (Hazardous Substances Data Bank), 2010. Sulfuric Acid. Available at: http://
toxnet.nlm.nih.gov (accessed March 2015).
Hudson, R.M., 1994. ASM Handbook, vol. 3. ASM International, Material Park, OH,
pp. 67e69.
Hudson, R., 2012. Common Uses of Sulphuric Acid. Available at: http://www.
thechemicalblog.co.uk/common-uses-of-sulphuric-acid/
(accessed
March
2015).
ICF (Inner City Fund), 2012. Sulphuric Acid. Technical Evaluation Report. Available
at: http://www.ams.usda.gov/AMSv1.0/getle?dDocNameSTELPRDC5101325
(accessed February 2015).
IHS (Information Handling Services), 2014. Sulfuric Acid. Chemical Economics
Handbook. Available at: https://www.ihs.com/products/sulfuric-acid-chemicaleconomics-handbook.html (accessed March 2015).
Inyo, 2013. Concentrated Sulfuric Acid 93e98%. Available at: http://www.
inyoprocess.com/chemicals-mainmenu-6.html?id11 (accessed March 2015).
Jennings, S.R., Neuman, D.R., Blicker, P.S., 2008. Acid Mine Drainage and Effects on
Fish Health and Ecology: a Review. Reclamation Research Group Publication,
Bozeman, MT.
Jeong, J., Kim, M.S., Kim, B.S., Kim, S.K., Kim, W.B., Lee, J.C., 2005. Recovery of H2SO4
from waste acid solution by a diffusion dialysis method. J. Hazard. Mater.
230e235.
Johnson, D.B., Hallberg, K.B., 2005. Acid mine drainage remediation options: a review. Sci. Total Environ. 338, 3e14.
Kerney, U., 1994. New recycling technologies for Fe/Zn waste acids from hot dip
galvanizing. In: Proceedings of Intergalva, Paris.
Kim, K.-J., 2006. Purication of phosphoric acid from waste acid etchant using layer
melt crystallization. Chem. Eng. Technol. 29 (2), 271e276.
Kim, H.S., Ahn, J.W., Kim, J.Y., Kim, J.Y., Shin, C.H., 2005. Method for Treating of
Etching Acid Waste Containing Phosphoric Acid, Acetic Acid and Nitric Acid.
Korean Patent, KR50003996.
Kim, J.Y., Lee, H.S., Shin, C.H., Kim, J.Y., Kim, H.S., Ahn, J.W., 2007. A study on the
separation of acetic acid, nitric acid, and hydrouoric acid from waste etching
solution of Si wafer manufacturing process. J. Korean Inst. Res. Rec. 16, 59e67.
Kraus, K.A., Nelson, F., Baxter, J.F., 1953. Anion-exchange studies. Separation of
sulphuric acid from metal sulfates by anion exchange. J. Am. Chem. Soc. 75,
2768e2770.
Lin, S.H., Lo, M.C., 1998. Recovery of sulfuric acid from waste aluminum surface
processing solution by diffusion dialysis. J. Hazard. Mater. 60, 247e257.
Liu, H., Covington, J., 1994. Acid recovery from synthetic Cu, Fe, Ni solution using
electrodialysis. J. Cheng. Univ. Sci. Technol. 80 (6), 73e79.
Mahajan, Y.S., Shah, A.K., Kamath, R.S., 2008. Recovery of triuoroacetic acid from
dilute aqueous solutions by reactive distillation. Sep. Purif. Technol. 59 (1),
58e66.
Manzoor, A., Khokhar, Z., Hussain, A., Ahmad, U., Syed, Q., Baig, S., 2012. Dilute
sulfuric acid: a cheap acid for optimization of bagasse pretreatment. Sci. Int.
(Lahore) 24 (1), 41e45.
Mario, B., Nancy, T., Virginie, G., Agnes, C., Gerald, P., Roger, S., Claude, G., 1997.
Recovery of spent acid by electro-dialysis in the zinc hydrometallurgy industry:
performance study of different cation-exchange membranes. Hydrometallurgy
45 (1/2), 137e160.
n, M., Ortega, E., Bernardes, A.M.,
Mart-Catalayud, M.C., Buzzi, D.C., Garca-Gabaldo
 rio, J.A.S., Perez-Herranz,
_
Teno
2013. Sulfuric acid recovery from acid mine
drainage by means of electrodialysis. Desalination 2013, 1e8.
Martin, R., 2014. 10 Major Industrial Applications of Sulfuric Acid. Available at:
http://www.slideshare.net/bejoybj/10-major-industrial-applications-ofsulfuric-acid# (accessed March 2015).
McDonald, R.G., Whittington, B.I., 2008. Atmospheric acid leaching of nickel laterites review. Part 1, Sulphuric acid technologies. Hydrometallurgy 91, 35e55.
Negro, C., Blanco, M.A., Lopez-Mateos, F., DeJong, A.M.C.P., LaCalle, G., Erkel, J., van
Schmal, D., 2001. Free acids and chemicals recovery from stainless steel pickling
baths. Sep. Sci. Technol. 36, 1543e1556.
Nenov, V., Dimitrova, N., Dobrevsky, I., 1997. Recovery of sulphuric acid from waste
aqueous solutions containing arsenic by ion exchange. Hydrometallurgy 44,
43e52.
Neuman, R.P., Rudge, S.R., Ladisch, M.R., 1987. Sulfuric acid-sugar separation by ion
exclusion. React. Polym. 5, 55e61.
Novalic, S., Kongbangkerd, T., Kulbe, K.D., 2000. Recovery of organic acids with high
molecular weight using a combined electrodialytic process. J. Membr. Sci. 166,
99e104.

Ozdemir, T., Oztin,


C., Kincal, N.S., 2006. Treatment of waste pickling liquors: process synthesis and economic analysis. Chem. Eng. Commun. 193, 548e563.
Oztekin, Y., Yazicigil, Z., 2007. Recovery of acids from salt forms of sodium using
cation-exchange membranes. Desalination 212 (1e3), 62e69.
a
kova
, A., 2004a. Separation of H2SO4 CuSO4 mixture by diffusion
Palaty', Z., Z
dialysis. J. Hazard. Mater. 114, 69e74.

kova
, A., 2004b. Separation of H2SO4 ZnSO4 mixture by diffusion
Palaty', Z., Za
dialysis. Desalination 169 (3), 277e285.

Parujen, P., 1997. Anodizing acid purication using resin sorption technology at
pioneer metal nishing. Eco-Tech Tech. Pap. 24.
Peters, M.S., Timmerhaus, K.D., 1991. In: Clark, B.J., Morris, J.M. (Eds.), Plant Economics for Chemical Engineers, fth ed.
Petkova, E., Vassilev, H., Shkodrova, V., 1981. Separation of waste plating solution
sulphuric acid from metal cations by anion exchange. Hydrometallurgy 6,
291e297.
Qian, Q.L., Wang, H.X., Bai, P., Yuan, G.Q., 2011. Effects of water on steam rectication
in a packed column. Chem. Eng. Res. Des. 89, 2560e2565.
Randall, D.G., Nathoo, J., Lewis, A.E., 2011. A case study for treating a reverse osmosis
brine using eutectic freeze crystallization e approaching a zero waste process.
Desalination 1e3 (266), 256e262.
Regel-Rosocka, M., 2010. A review on methods of regeneration of spent pickling
solutions from steel processing. J. Hazard. Mater. 177, 57e69.
Ricker, L.N., King, J.C., 1980. Solvent Extraction of Wastewaters from Acetic-acid
Manufacture. United States Environmental Protection Agency (USEPA) e 600/280-064.
Robinson, R.E., Barnard, R., Le Riche, J.J., 1998. The treatment of acid efuent from
Grootvlei mine using novel IX techniques. J. S. Afr. Inst. Min. Metall. 343e353.
Sanchez, J., 2008. Acid mine drainage in the Iberian pyrite belt: an overview with
special emphasis on generation mechanisms, aqueous composition and associated mineral phases. Conf. Invit. S
anchez Espana, Macla 10, 34e43.
Sata, T., 1989. Application of ion exchange membranes to hydrometallurgy. In:
Extraction Metallurgy '89. Inst. Min. Metall., London, p. 977.
Schoeman, D.J., Steyn, A., 2000. Evaluation of bipolar electrodialysis for the treatment of industrial efuents. In: WISA Biennial Conference and Exhibition, Sun
City, South Africa.
Seo, S.Y., Choi, W.S., Kim, M.J., Tran, T., 2013. Leaching of a Cu-Co ore from Congo
using sulphuric acid-hydrogen peroxide leachants. J. Min. Metall. Sect. B Metall.
49 (1), 1e7.
Shamritska, I.P., Meleshko, V.P., Poluhina, L.A., 1972. Theory and practice of sorption
processes. Voronezh 5, 76.
Sheedy, M., 1998. Recoo ion exchange technology. In: TMS Annual Meeting. San
Antonio, Texas.
Sheedy, M., Parujen, P., 2012. Acid separation for industry control and acid cycle
using short bed ion exchange. In: T.T. Chen Honorary Symposium on Hydrometallurgy, Electrometallurgy and Materials Characterization, TMS.
Shin, C.H., Kim, J.Y., Lee, H.S., Kim, H.S., Mohapatra, D., Ahn, J.W., Bae, W., 2009.
Recovery of nitric acid from waste etching solution using solvent extraction.
J. Hazard. Mater. 163, 729e734.
Simate, G.S., 2009. Bacterial Leaching of Nickel Laterites Using Chemolithotrophic
Microorganisms. MSc (Eng) Dissertation. University of the Witwatersrand,
Johannesburg.
Simate, G.S., Ndlovu, S., 2014. Acid mine drainage: challenges and opportunities. J.
Environ. Chem. Eng. 2 (3), 1785e1803.
Singer, P.C., Stumm, W., 1970. Acid mine drainage: the rate determining step. Science 167, 1121e1123.
Sinnott, R.K., 2005. Coulson & Richardson's Chemical Engineering In: Chemical
Engineering Design, fourth ed., vol. 6. Elsevier.
Song, K., Meng, Q., Shu, F., Ye, Z., 2013. Recovery of high purity sulphuric acid from
waster acid in toluene nitration process by rectication. Chemosphere 90,
1558e1562.
Tang, J., Zhou, K., 2006. Hydrochloric acid recovery from rare earth chloride solutions by vacuum membrane distillation. Rare Met. 25, 287e292.
Tang, J.J., Zhou, K.G., Zhang, Q.X., 2006. Sulfuric acid recovery from rare earth sulphate solutions by diffusion dialysis. Trans. Nonfer. Met. Soc. China 6, 951e955.
Tavakoli, M.R., Dornian, S., Dreisinger, D.B., 2014. The leaching behaviour of vanadium pentoxide using sulfuric acid and sulte as reducing agent. Hydrometallurgy 141, 59e66.
m, R., Fortkamp, U., Forsberg, K., Rasmuson, A., 2006. Development
Tjus, K., Bergstro
of a recovery system for metals and acids from pickling baths using nanoltration and crystallization. In: Report of Swedish Environmental Research
Institute. Available at: http://www3.ivl.se/rapporter/pdf/B1692.pdf (accessed
January 2015).
Tomasvewska, M., Mientka, A., 2009. Separation of HCL from HCL-H2SO4 solutions
by membrane distillation. Desalination 240 (1e3), 244e250.
Tomaszewska, M., Gryta, M., Morawski, A.W., 1995. Study on the concentration of
acids by membrane distillation. J. Membr. Sci. 102, 113e122.
Tomaszewska, M., Gryta, M., Morawski, A.W., 1998. The inuence of salt in solutions
on hydrochloric acid recovery by membrane distillation. Sep. Purif. Technol. 14,
183e188.
Tomaszewska, M., Gryta, M., Morawski, A.W., 2001. Recovery of hydrochloric acid
from metal pickling solutions by membrane distillation. Sep. Purif. Technol.
22e23, 591e600.
Tzanetakis, N., Taama, W.M., Scott, K., 2002. Salt splitting in a three compartment
200 membrane electrolysis cell. Filtr. Sep. 39, 31e38.
Tzoneva, D., 2008. New Sulphuric Acid Plant under Consideration. Available at:
http://mcgroup.co.uk/uc/leaet/report/Sulfuric%20Acid:%202015%20World%
20Market%20Outlook%20and%20Forecast%20up%20to%202019.pdf
(accessed
06.03.15.).
Vatavuk, 2002. Updating the CE plant cost index. Available at: http://www.
chemengonline.com/Assets/File/CEPCI_2002.pdf (accessed September 2015).
Venter, R., Boylett, M., 2009. The evaluation of various oxidants used in acid
leaching of uranium. In: Hydrometallurgy Conference, the Southern African
Institute of Mining and Metallurgy, 2009.

Y. Nleya et al. / Journal of Cleaner Production 113 (2016) 17e27


Wang, P., Chung, T.S., 2015. Recent advances in membrane distillation processes.
Membrane development, conguration design and application exploring.
J. Membr. Sci. 474, 39e56.
Wei, C., Li, X., Deng, Z., Fan, G., Li, M., Li, C., 2010. Recovery of H2SO4 from an acid
leach solution by diffusion dialysis. J. Hazard. Mater. 176, 226e230.
Xu, Z., Afacan, A., Chuang, K., 1999. Removal of acetic acid from water by catalytic
distillation. Part 1. Experimental studies. Can. J. Chem. Eng. 77, 676e681.
Yadav, S.K., 2010. Heavy metals toxicity in plants: an overview on the role of
glutathione and phytochelatins in heavy metal stress tolerance of plants. S Afr. J.
Bot. 76, 167e179.

27

Yu, L.X., Lin, T., Guo, Q., Hao, J.H., 2003. Relation between mass transfer and operation
parameters in the electrodialysis recovery of acetic acid. Desalination 154, 147.
Zhang, G.Q., Zhang, Q.X., Zhou, K.G., 1999. Acid recovery from waste sulphuric acid
by diffusion dialysis. J. Cen. South Univ. Technol. 6 (2), 103e106.
Zhao, Q., Liu, C., Shi, P., Zhang, B., Jiang, M., Zhang, Q., Saxen, H., Zevenhoven, R.,
2014. Sulfuric acid leaching of South African chromite. Part 1: study on leaching
behaviour. Int. J. Min. Process 130, 95e101.