Waste Management xxx (2015) xxx–xxx

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Review

A review of metal recovery from spent petroleum catalysts and ash

Ata Akcil a,⇑, Francesco Vegliò b, Francesco Ferella b, Mediha Demet Okudan a, Aysenur Tuncuk a
a
Mineral-Metal Recovery and Recycling Research Group, Mineral Processing Division, Department of Mining Engineering, Suleyman Demirel University, TR32260 Isparta, Turkey
b
Department of Industrial Engineering, Information and Economics (DIIIE), University of L’Aquila, Via G. Gronchi 18, 67100 L’Aquila, Italy

a r t i c l e i n f o a b s t r a c t

Article history: With the increase in environmental awareness, the disposal of any form of hazardous waste has become a
Received 6 May 2015 great concern for the industrial sector. Spent catalysts contribute to a significant amount of the solid
Revised 30 June 2015 waste generated by the petrochemical and petroleum refining industry. Hydro-cracking and hydrodesul-
Accepted 3 July 2015
furization (HDS) catalysts are extensively used in the petroleum refining and petrochemical industries.
Available online xxxx
The catalysts used in the refining processes lose their effectiveness over time. When the activity of cat-
alysts decline below the acceptable level, they are usually regenerated and reused but regeneration is not
Keywords:
possible every time. Recycling of some industrial waste containing base metals (such as V, Ni, Co, Mo) is
Recycling
Catalyst
estimated as an economical opportunity in the exploitation of these wastes. Alkali roasted catalysts can
Ash be leached in water to get the Mo and V in solution (in which temperature plays an important role during
Vanadium leaching). Several techniques are possible to separate the different metals, among those selective precip-
Molybdenum itation and solvent extraction are the most used. Pyrometallurgical treatment and bio-hydrometallurgical
Nickel leaching were also proposed in the scientific literature but up to now they did not have any industrial
Cobalt application. An overview on patented and commercial processes was also presented.
Ó 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
1.1. HDS catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
1.2. Fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
1.3. FCC catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Metal recovery techniques from petrochemical wastes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1. Hydrometallurgical, pyrometallurgical and biohydrometallurgical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1.1. Hydrometallurgical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1.2. Pyrometallurgical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1.3. Biohydrometallurgical methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Industrial processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction belong to heterogeneous catalysis, which involves acid, metal,

sulfur, and bifunctional catalysts and, to a lesser degree, oxide
Catalysis undoubtedly played a very important part during the phases (other than supports) (Marcilly, 2003). Catalysts are indis-
second half of the 20th century in the development of refining and pensable in the conventional production of gasoline, diesel fuel,
petrochemical industries. The main categories of catalysts mostly jet fuel, heavy hydrocarbons, petrochemicals and plastics in the
petroleum distillation and petrochemicals industry.
⇑ Corresponding author. Because the technology for the regeneration and reactivation of
E-mail address: [email protected] (A. Akcil). the catalysts that are deactivated by metal fouling is not available

http://dx.doi.org/10.1016/j.wasman.2015.07.007
0956-053X/Ó 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Akcil, A., et al. A review of metal recovery from spent petroleum catalysts and ash. Waste Management (2015), http://
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2 A. Akcil et al. / Waste Management xxx (2015) xxx–xxx

to refiners, the spent catalysts are discarded as solid waste (Marafi Catalytic cracking is similar to thermal cracking, except that cata-
and Stanislaus, 2008a,b; Macaskie et al., 2010). Although spent lysts ease the transformation of heavy molecules into lighter prod-
refinery catalysts correspond to about 4 wt.% of the overall refinery ucts. Use of catalytic cracking increases the quality product yield
waste (Liu et al., 2004), they are classified as one of the most haz- under easier conditions compared to thermal cracking. Typical
ardous wastes generated in petroleum refineries. Spent catalysts temperatures range between 454 and 482 °C at 0.7–1.4 atm.
are managed through the following approaches: (1) chemical or Catalysts used in catalytic cracking are generally in solid form (zeo-
microbial treatment for recovery of valuable metals for different lite, aluminum, hydro silicate, processed bentonite clay, bauxite,
applications, (2) regeneration and reuse and (3) landfilling. silica-alumina) and are shaped like dust, marble, particle or other
Beside the serious environmental threat, hydroprocessing catalyst various shapes (Gupta, 2003).
is also identified as one of the important potential sources of base Production of renewable fuels and waste disposal are two of the
and critical metals such as Ni, Co, Mo, W, V, Cr, Cu and Zn. major concerns facing the world today, because both environmen-
Considering all these facts, the treatment of spent refinery catalysts tal concerns and energy derived from petroleum-based fuels will
for metal recovery is becoming potentially viable (Marafi and define the future economic potential (Jopert et al., 2015).
Stanislaus, 2008a,b; Santhiya and Ting, 2006). Throughout the world, much research is being conducted on the
Recently, an increasing demand for clean chemical process use of waste materials (Van Jaarsveld et al., 1998) in order to either
technologies in engineering can be observed, especially for removal avert an increasing toxic threat to the environment or to stream-
of pollutants. It is very well known that the sulfur and nitrogen line present waste disposal techniques by making them more
impurities present in fuels are an important source of air pollution, affordable. It, therefore, follows logically that an economically
acid rain and they also affect pollution control devices. In order to viable solution to this problem should include utilization of waste
decrease pollution, new specifications for sulfur in diesel have been materials in new products for other applications rather than dis-
established in many countries (Zepeda et al., 2012; Liu et al., 2012; posal in a landfill.
Baeza et al., 2012). Conventional hydrotreating (HDT) methods are When the precious metal content is considered, petrochemical
effective for removing many sulfur and nitrogen compounds. wastes can be considered as significant secondary resources.
However, they are less competent for removing heterocyclic sulfur These solid wastes contain a high amount of metal oxide/sulfur.
or nitrogen compounds such as dibenzothiophenes and quinolines, The oxides and sulfur, which can easily be oxidized, react with
which are abundant especially in diesel (Song and Ma, 2003; Liu the environment by self-leaching when it comes in contact
et al., 2008; Guimarães et al., 2008). Other processes have been with the external atmosphere, and pollutes the environment
studied in order to remove refractory HDS compounds. (Furimsky, 1996). For this reason, storing petroleum catalyst waste
The largest petrochemical industries are located in the USA and is never an appropriate option. The only option is to determine
Western Europe; however, major growth in new production capac- metal recovery methods that are environmentally friendly and
ity is in the Middle East and Asia (Cefic, 2011). Currently, there are economical.
few companies with the ability to perform this process within the Hydroprocessed catalyst wastes require a strict adherence to
economical and environmentally acceptable boundaries. Energy environmental regulations due to their hazardous structure and
savings and environmental benefits are also important in these toxic chemical content. The importance of the amount of
recycling processes. Refineries are facing a difficult challenge to hydroprocessed catalyst waste has increased due to the following
reduce the sulfur content in their products, because of low quality reasons (Marafi and Stanislaus, 2008a,b):
petroleum with high sulfur content. Technically, it is possible to
remove sulfur from products during separation, but in terms of  Increase in distilled hydroprocess capacity to meet the demand
the main process modifications, the economic impact can be signif- for fuels with ultra-low sulfur content,
icant. As waste disposal is no longer considered to be the best  decreased recovery time in diesel hydroprocessing’s heavier
choice, disposing catalyst waste has become a significant environ- processes,
mental issue. In many cases, spent catalysts are considered to be  constant increase in heavy raw materials with high sulfur and
hazardous wastes and are subject to strict legislations. The amount metal content (heavy crude oil even from non-conventional
of hydro-processed catalyst wastes that are considered as solid resources like tight and shale oil).
wastes in the petrochemical industry has increased to meet
demand for low-sulfur fuels that have rapidly increased in terms The volume of installed capacity of hydroprocessing catalyst is
of hydroprocessing capacity (Marafi and Stanislaus, 2007). increasing in order to cope with the increasing demand for the
Raw petroleums are complex mixtures that have the texture development of nearly sulfur free clean fuels and the need for dee-
between water and tar. A typical raw petroleum is comprised of per heavy ends conversion. Similarly, low refining margins are driv-
84% carbon, 14% hydrogen, 1–3% sulfur and >1% nitrogen, oxygen, ing industry to cost optimization, while environmental regulations
metals and salts. Raw petroleum can be classified as paraffinic, are getting tougher. In addition to the growing fresh hydroprocess-
naphthenic or aromatic, based on the dominant ratio of hydrocar- ing catalyst market (hydrodesulfurization, hydrocracking), regener-
bons. Metals like nickel, iron and vanadium are found in low ated catalyst usage is also increasing with an estimated worldwide
amounts in petroleum and are removed during the separation pro- consumption of roughly 30,000 t/y. This additional tonnage of
cesses. Trace amounts of arsenic, vanadium and nickel can poison regenerated catalysts is extremely useful for refineries hoping to
and clog the porous structure of catalysts and this affects the cat- reduce their procurement expenses as well as to limit their gener-
alytic activity negatively. Catalytic hydroprocessing is a hydro- ation of chemical waste. Unfortunately, the ratio between the
genation process that is used to remove 90% of pollutants such regenerated and the fresh catalyst market in distillates hydropro-
as nitrogen, sulfur, oxygen and metals in petroleum fractions. If cessing is below 50%, meaning that not all spent catalysts are regen-
these pollutants are not removed from petroleum fractions, they erated at least once. This low reuse rate can certainly be increased
will move along the processing units and negatively affect the by a careful evaluation of the spent catalyst (Saha et al., 2012).
downstream equipment, catalysts and the quality of finished prod- Spent hydroprocessing catalysts have been classified by the U.S.
ucts. Generally, hydroprocessing is applied before processes such Environment Protection Agency (EPA) as hazardous wastes. EPA has
as catalytic regeneration to prevent pollution of catalysts by the added hydroprocessing catalyst (K171) and hydro-separation cata-
raw products. Hydroprocessing is also used to decrease the sulfur lyst (K172) in August 1998 due to their self-heating property and
content before cracking and to increase the product yield. the toxic chemical content (Federal Register, August 6, 1998).

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 A. Akcil et al. / Waste Management xxx (2015) xxx–xxx 3

Hydrocarbon catalyst waste has been also added to the list in 1999 (Shaikh and Supit, 2015; Bentz et al., 2015). Coal fly ash discharged
(Rapaport, 2000; USEPA, 2003). Metals such as Co, Ni and V that are from power plants can also be utilized as a by-product, and its use
present in spent hydroprocessing catalysts are included in the list of in recycling materials for agriculture and engineering is also being
potentially hazardous wastes published by the Environment studied (Ram and Masto, 2014; Basu et al., 2009; Iyer and Scott,
Canada. These metals can be leached by water after disposal and 2001; Kikuchi, 1999).
pollute the environment (Marafi and Stanislaus, 2007).
Many innovations took place in catalyst performance in distilla-
1.3. FCC catalysts
tion and waste oil hydroprocessing units (Stanislaus and
Absi-Halabi, 2002; Eijsbouts et al., 2003; Remans, 2003; Fujikawa
Fluid catalytic cracking (FCC), still one of the major downstream
et al., 2006; Furimsky, 2007). By developing new hydroprocessing
refining operations, is responsible for the conversion of heavy feed-
catalysts, the nature of active parts, structures, characteristics, and
stocks (gasoils from vacuum distillation towers or residues from
pore size have been improved (Delmon, 1990, 1993; Topsoe et al.,
atmospheric distillation towers) into lighter, more valuable prod-
1990, 1996; Hensen et al., 2001, 2002; Breysse et al., 2003;
ucts such as liquefied petroleum gases (LPG) and cracked naphtha,
Thomazeau et al., 2007).
the major constituent of the gasoline pool (Cerqueira et al., 2008).
Since the 1980s, a new type of secondary raw materials has
Fluid catalytic cracking units without any doubt belong to the
gained importance, i.e., residues of mineral oil processing. It is
most important refinery technologies. This process converts heavy
known that raw petroleum contains vanadium ranging from
atmospheric residues and vacuum distillates into fractions of motor
10 ppm (Middle East) to 1400 ppm (Central America). It was
fuels, mainly gasoline. The cracking of long-chain hydrocarbons is
observed that up to 40% vanadium is contained in waste and fly
the most important petroleum-refining process; the method of
ashes that remains after combustion in refining processes in petro-
cracking long-chain hydrocarbons has evolved over the years,
chemical facilities. This amount is more than enough to meet the
though the end goal always remained the same (Hudec, 2011).
current vanadium consumption worldwide (Ullmann’s, 2007).
The typical FCC catalyst consists of a mixture of an inert matrix
(kaolin), an active matrix (alumina), a binder (silica or
1.1. HDS catalysts
silica-alumina) and a rare earth exchanged Y-zeolite. The zeolites
typically applied as FCC catalysts are type X, type Y and ZSM-5. Y
Hydrodesulfurization (HDS) is commonly used to eliminate sul-
zeolites are synthesized by ion-exchange with rare earth elements
fur from a variety of organic compounds present in different frac-
like lanthanum and cerium. During the FCC process, a significant
tions of petroleum (Eijsbouts et al., 2003). The HDS process is
portion of the feedstock is converted into coke. This coke temporar-
commonly performed at high temperature and pressure, in a
ily deactivates the active sites of the catalyst by poisoning, pore
hydrogen atmosphere and in the presence of a heterogeneous cat-
blockage or both (Magnoux et al., 1987; Froment, 1991; Forzatti
alyst. Traditionally, bimetallic catalysts based on Mo/W, promoted
and Lietti, 1999) and (Cerqueira et al., 2000) resulting in an impor-
by Ni/Co and supported on c-Al2O3 are used in the HDS process.
tant activity loss. In order to recover the activity, the FCC catalyst
These catalysts exhibit high activity in removing sulfur from thio-
continuously circulates between the riser (FCC reactor) and the
phene and benzothiophene compounds, and some non-refractory
regenerator vessel. In the regenerator, coke is converted into CO,
dibenzothiophenes. However, their activity is very low in removing
CO2, H2O, SOx and NOx compounds which are causing a series of
sulfur from dibenzothiophenes with alkyl groups in positions 4 and
environmental issues, such as acid rain, photochemical smog,
6 of the molecule (positions close to the sulfur atom) (Ho, 2004;
ozone destruction and ultrafine particles pollution. It is widely
Srivastava, 2012). This leads to the production of diesel fuel, which
known that the main sources of nitrogen that cause NOx formation
after hydrotreatment still contains about 500–1000 ppm of sulfur
are the N-containing compounds in the FCC feedstock (fuel NOx).
due to the presence of unreacted refractory dibenzothiophene
NOx concentrations in the tail-gas of FCC regenerator can vary
compounds.
between 50 and 500 ppm depending on some parameters, e.g.
the feed oil component, operating conditions of the regenerator
1.2. Fly ash
and whether a CO combustion promoter was added (Peters et al.,
1998). Recently, FCC units tend to process heavier feed oils with
Coal fly ash, a by-product of coal combustion in thermal power
more N-containing compounds, which causes an increase of NOx
plants, is one of the most complex and abundant of anthropogenic
concentration in the FCC regenerator (Babich et al., 2005). This
materials. It accounts for 5–20 wt.% of feed coal and is typically
has increased environmental and safety concerns.
found in the form of coarse bottom ash and fine fly ash, which rep-
Various conventional solutions are being offered in order to
resent 70–85 and 15–30 wt.% of the total ash generated, respec-
recover metals from petrochemical wastes. In this study, the
tively. The generation of coal fly ash is anticipated to increase for
hydrometallurgical, biohydrometallurgical, and pyrometallurgical
many more years, as a result of the world’s increasing reliance
methods for metal recovery from petrochemical wastes have been
on coal-fired power generation. A more up-to-date estimate of
addressed in detail.
annual worldwide generation of fly ash is 750 million tonnes
(Blissett and Rowson, 2012). Internationally, millions of tons of
fly ash are generated each year by coal-fired power stations 2. Metal recovery techniques from petrochemical wastes
(Scheetz and Earle, 1998) as well as the petrochemical industry,
if it is based on coal instead of crude oil. Recycling coal fly ash Toxic fumes emerge when spent hydroprocessing catalysts
can be a good alternative to disposal, and could achieve significant come in contact with water. In previous studies by Furimsky
economic and environmental benefits as well (Yao et al., 2014). (1996), Trimm (1990) and Clifford (1997), disposal of used separa-
Mining, processing, and metallurgical activities associated with tion catalysts and areas of use were studied. There are various
the mixed sulfides industry generate large volumes of hazardous methods that include:
solid wastes and acidic leachates that may cause adverse impacts
to the quality of soils, surface water, and groundwater; fly ash  lower the used catalyst waste production;
has a potential in permeable reactive barriers for the decontamina-  make use of new catalysts and other beneficial substances;
tion of groundwater (Komnitsas et al., 2006). The cement industry  render the materials reusable;
might use it as a raw material for the production of concrete  dispose of catalyst wastes safely.

Please cite this article in press as: Akcil, A., et al. A review of metal recovery from spent petroleum catalysts and ash. Waste Management (2015), http://
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4 A. Akcil et al. / Waste Management xxx (2015) xxx–xxx

Table 1
Metal recovery by different leaching and roasting methods (Marafi and Stanislaus, 2008a,b).

Metal present in spent catalyst Reagent Metals recovered (wt.%)

Mo V Ni Co
V, Mo, Ni, Co, Al Na2CO3 + H2O2 99 85 – –
Mo, Ni, Al, C, S Na2CO3 + H2O2 85 – 65 –
V, Ni, Mo, Al NaOH (10%), pH 8.8 91.8 88.5 20 –
V, Ni, Mo, Al NaOH (10%), pH 8.4 98.8 92.7 10 –
V, Ni, Mo NaOH (atmospheric & pressure leaching in two steps) 97 92 – –
V, Ni, Mo, Al Aqueous NH3 Solution (17 M) – 98.8 – –
Ni, Mo, Al NaOH (1st stage) & H2SO4 (2nd stage) 84 – 98 –
Ni, Co, Mo, Al NaOH (1st stage) & H2SO4 (2nd stage) 97 – 92 92
V, Mo, Co, Ni, Al Na2CO3 (roasting + leaching with H2O) 90–95 90–95 – –
Co, Mo, Al NaOH roasting (1st stage) 90 – – 90
H2SO4 leaching (2nd stage)
V, Mo, Ni, Co, Al NaOH roasting (1st stage) 98.9 95.8 98.2 98.5
H2SO4 leaching (2nd stage)
Mo, Ni, Al2O3 NaCl roasting + water extraction 90 – – –
Mo, Ni, Co, Al KHSO4 fusion + water extraction 96 – 90 90
V, Mo, Ni, Co Aqueous NH3 + NH4CO3 + H2O2 93 88 80 78
Mo, V, Ni Citric acid 94 94 85 –
V, Mo, Ni, Al Oxalic acid + H2O 90 94 65 –

Vanadium and nickel have wide range of industrial use. Al-Mansi and Abdel Monem (2002) investigated the possibility
Ashes from power stations contain high amount of vanadium of recovering nickel from the spent catalyst (NiO/Al2O3) resulting
and nickel, they have high economic potential. In order to from the steam reforming process to produce water gas (H2/H2O)
recover vanadium and nickel, various hydrometallurgical and in many industries. In the extraction process, nickel is recovered
pyro-hydrometallurgical processes are applied. The most com- as sulfate using sulfuric acid as a solvent. Nickel was to be directly
monly applied among these are direct acid leaching, direct alkali recovered as a sulfate salt by direct crystallization method. The
leaching, acid leaching after roasting, alkali leaching after roasting conversion was 99% at 50% sulfuric acid concentration, solid: liquid
and water leaching after roasting (Mefos, 2006). Alkali leaching is ratio (1:12) by weight, particle size less than 500 lm for more than
known to be an effective method in selective separation of vana- 5 h and 800 rpm at 100 °C.
dium from iron, but it causes dissolution of some silica. In terms Direct H2SO4 processing of Egyptian boiler ash to produce sul-
of chemical reactants, it is a highly costly process. Sulfuric acid fate of vanadium and nickel is achieved by leaching under oxygen
does not dissolve silica, it is still an effective method in recovering pressure. The optimum conditions of pressure leaching process
nickel and vanadium together, but the selectivity is weaker than are; temperature 200 °C, partial oxygen pressure 15 bar, sulfuric
alkali leaching (Ho et al., 1994). acid concentration 60 g/L leaching period 15 min (Amer, 2002).
Navarro et al. (2007) studied the selective recovery of vanadium To recover molybdenum and vanadium from spent HDS cata-
from oil fly ash from power plants. Two-step procedure consisting lysts, the waste sample was roasted with NaCl3–H2/H2O at 850 °C
of an alkaline leaching using sodium hydroxide and a precipitation and leached with water at boiling point to make molybdenum
procedure was investigated. The sequential precipitation of alu- and vanadium soluble. After using liquid–liquid separation
minum at pH 8 followed by the addition of ammonium chloride (D2EHPA and TOA) to recover vanadium as NH4VO3, the metal
and precipitation obtained a quantitative recovery of vanadium was extracted from the organic phase and the end result was
in the form of an ammonium vanadate. Alkaline leaching was pre- 77% Mo and 75.5% V recovery (Biswas et al., 1985).
ferred to acidic leaching since it avoids the leaching of metals such Zhang et al. (1989) proved a new extraction method by using PC
as Fe and Ni that interfere in the precipitation process. 88 A for an effective separation and recovery of metals such as Mo,
Several methods such as chlorination, acid leaching, alkali V, Al, Co, Ni from sulfuric acid solutions leached from HDS.
leaching, bioleaching, roasting with soda salts have been studied Zeng et al. (2006) studied the removal of vanadium from
for the recovery of Mo, Ni, Co and V from the spent catalysts. ammonium molybdate solution by ion exchange. Over 99.84% of
Metal recovery efficiencies for different methods are compared in the vanadium was removed using a chelating resin D418 (function
Table 1 (Marafi, 2008). group: –NHCH2PO3Na2) at pH 7.2 for a contact time of 30 min.
In a study conducted by Tsai and Tsai (1998), three different The extraction properties of metallic elements from the spent
leaching reactants were tested on porous unburnt carbon, vana- refinery processing catalyst were examined under citric acid leach-
dium, nickel oxide and oil-fired fly ash samples. Sulfuric acid, ing conditions. The process consists of pre-washing and citric acid
sodium hydroxide, water with ammonia were investigated in extraction. Different temperatures were tested for the extraction
leaching of fly ash: 65% of vanadium, 60% of nickel, 42% of iron experiments and 80 °C was found to be most effective for metal
were recovered by 0.5 N sulfuric acid solution. In experiments extraction from the spent refinery processing catalyst. The acid
done with 2 N sodium hydroxide solution, 80% of vanadium was simultaneously reacted with all the metal in the catalyst solid
recovered, while recovery of iron was insignificant. When leaching under citric acid treatment condition but preferentially reacted
was done with ammonia and water, it was observed that the with Mo at room condition. The maximum metal extraction per-
increase in ammonia concentration increased the nickel recovery. centages were obtained at 5 h, and longer citric acid treatment
In a 4 N ammonia–water solution, nickel recovery was 60%, and conversely reduced the extraction effect (Shen et al., 2012).
vanadium extraction was much lower than that of sulfuric acid A Polish patent reported a process involving fusing the spent
or sodium hydroxide leaching. Fly ash electrostatically precipitated catalyst with concentrated sulfuric acid in 100–200 °C followed
in power plants was leached with 0.25 N ammonia–water solution by water leaching (Grzechowiak et al., 1987).
and 2 N ammonium sulfate solution, a selective recovery for nickel Medvedev and Malochkina (2007) presented a method of subli-
60% and 8% vanadium was obtained. mation, which was performed in a muffle electrical resistance

Please cite this article in press as: Akcil, A., et al. A review of metal recovery from spent petroleum catalysts and ash. Waste Management (2015), http://
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dx.doi.org/10.1016/j.wasman.2015.07.007
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Table 2
Summary of experimental studies carried out on spent hydrotreating catalysts for metal recovery (modified from Marafi and Stanislaus, 2008a,b; Ferella et al., 2011).

Catalyst Leaching reagent Mo recovery V recovery Ni recovery Co recovery Al recovery References

(%) (%) (%) (%) (%)
Mo, V, Ni, Co, Al2O3 H2SO4 99.7 92.5 – – – Inoue and Zhang (1993) and Inoue et al.
(1995)
Inoue and Zhang (1993)
Mo, Ni, Al2O3 H2SO4 93 – 98 – 96 Siemens et al. (1986)
Co, Mo SO2(aq) 100 – – 100 – Raisoni and Dixit (1988)
Co, Mo H2SO4 + HNO3 (3:1) 96 – – 96 – Raisoni and Dixit (1988)
Co, Mo H2SO4 + Al2(SO4)3 or (NH4)2SO4 92 – – 97 – Rastas et al. (1984)
Mo, Co, Ni, H2SO4 + H2S – – – – – Hyatt (1987)
Mo, V, Co, Ni H2SO4 >90 – – >90 – Jocker (1993)
Mo, V, Ni, Al Oxalic acid + H2O2 90 94 65 – 33 Mulak et al. (2006)

A. Akcil et al. / Waste Management xxx (2015) xxx–xxx

Mo, V, Ni Tartaric acid 93 94 83 – – Marafi and Furimsky (2005)
Mo, V, Ni Citric acid 94 94 85 – – Marafi and Furimsky (2005)
Mo, V, Co, Ni, Al H2SO4 – – – – – Toyabe et al. (1995)
Co–Mo Leaching by H2SO4 9 mol L1, 90 °C, 2 h 99 98 98 Valverde et al. (2008)
Co–Mo/Ni–Mo Fusion with KHSO4 (350–600 °C, 0.5–7 h) 87–90 96–99 91–94 Busnardo et al. (2007)
Spent HDS catalyst Na2CO3 (40 g L1) + H2O2 (6 vol%) – 99.4 MoO3 Not Park et al. (2006a,b)
(NiMo/b-Al2O3) Carbon adsorption measured
Desorption (NH4OH)
Roasting (450 °C)
Spent HDS catalyst Na2CO3 (30 g L1) 93 – 98 90 – Park et al. (2007)
(Co/Ni/Mo/Al2O3) H2SO4 (6 mol L1)
Solvent extraction of Al (Cyanex 272)
Spent hydro-refining 600 °C air roasting + Na2CO3 (12 wt.%) for 30 min Not measured – 92 Na2MoO4 Not – Kar et al. (2004)
catalyst Water leaching (90 °C) measured
Chemical treatment
Adsorption/desorption method
Spent hydro-refining 900 °C air roasting + NaCl (20 wt.%) Not measured – 90 Na2MoO4 Not – Kar et al. (2005)
catalyst Water leaching (90 °C) measured
Chemical treatment
Co–Mo Two steps alkali-acid procedure 80 – 97 80 – Angelidis et al. (1995)
Ni–Mo (1) Alkaline leaching ? dissolution of Mo (10 g L1; NaOH; 80 °C;
1/20 S/L)
(2) Acidic leaching ? dissolution of Co/Ni (10 g L1; H2SO4; 80 °C;
1/20 S/L)
Spent HDS catalyst Acidic leaching, 70 °C (HNO3/H2SO4/HCl = 2:1:1) – – 90 99 – Lai et al. (2008)
Electrolysis
Spent HDS catalyst Acidic leaching, 50 °C – – 90 65 – Mulak et al. (2006)
0.5 mol L1 H2C2O4 + 3 mol L1 H2O2
Spent HDS catalyst Acidic leaching, 80 °C (H2SO4 + H2O2) 81 – 72 Not – Ognyanova et al. (2008)
Alkaline leaching, 80 °C (NaOH + H2O2) + Al precipitation at pH 8 measured
Ammonia leaching Water leaching (90 °C, 15 min, 50% S/L) – – 91 – – Chen et al. (2006)
Residue

5
6 A. Akcil et al. / Waste Management xxx (2015) xxx–xxx

Resources
2.1. Hydrometallurgical, pyrometallurgical and biohydrometallurgical
methods

Dissolution Residue for 2.1.1. Hydrometallurgical methods

disposal/recycle
Hydrometallurgical processes have been in use for many years.
Hydrometallurgy has some benefits such as low cost requirements,
possible recovery of leachants and decrease of air pollution as
there are no particles produced (Salgado et al., 2003; Karakaya
Leach solution
et al., 2007).
Purification The tendency for the hydrometallurgical processes comes from
the fact that the industry can destroy the impurities in ores having
low grade hazardous chemicals by wet-chemical methods. During
recovery, some metal compounds cause process problems and
increase the metal contents above the desired limit. In this case
the hydrometallurgical methods can be applied more safely and
Recovery
Effluent for more efficiently. The basic units in hydrometallurgical processes
disposal/recycle are given in Fig. 1.
Catalysts are widely used in petroleum distillation processes
and in chemical industries. They are important in terms of having
economic value and being abundant as secondary resources, and it
is crucial that they are disposed for environmental reasons. Spent
Product hydrodesulfurization catalysts usually consist of molybdenum sul-
(metals) fide mixed with sulfides of vanadium, cobalt and nickel on an alu-
mina carrier. A wide variety of metallurgical processes are used to
Fig. 1. Basic unit process in hydrometallurgy. treat these catalysts (Furimsky and Massoth, 1999; Zeng and
Cheng, 2009a,b). Spent HDS catalysts generally consist of 10–30%
molybdenum, 1–12% vanadium, 0.5–6% nickel, 1–6% cobalt, 8–
furnace at 1200 °C to recover Mo directly as MoO3 from spent cat- 12% sulfur, 10–12% carbon and the balance is alumina, which
alysts. With the optimization of operating parameters, the extrac- makes it economically viable for recovery of valuable metals
tion of molybdenum into sublimate of no less than 80% can be (Biswas et al., 1986).
obtained in one stage of sublimation. In the patented process developed by Hyatt (1987), the spent
Standard beneficiation technologies were also investigated in CoMo/Al2O3 catalyst was treated with sulfuric acid in the presence
order to concentrate metals coming from spent HDS catalysts. of H2S under pressure (7.5–15 atm) in an autoclave at 100–200 °C.
Grain size separation, attrition and flotation were tested on spent The presence of H2S resulted in the precipitation of Mo and Co as
Ni–Mo–Co–V catalyst: the results showed that it was not possible sulfides while the Al2O3 was converted to soluble Al2(SO4)3. The
to achieve any concentration of those metals before the leaching metal sulfides were separated from the Al2(SO4)3 solution and sub-
stage (Ferella et al., 2011). jected to oxidation under pressure in an autoclave to convert MoS2
Vitolo et al. (2000) developed a three-stage process to recover to solid molybdic acid and the CoS to CoSO4. The molybdic acid was
vanadium from Orimulsion fly ash and heavy petroleum fly ash. separated by filtration from the CoSO4 solution. The cobalt was
This process is made up of acid leaching, oxidation and sedimenta- recovered by ion exchange. The extraction and recovery of valuable
tion of vanadium pentoxide. A different technique was used to metals, such as Mo and Co together with the alumina as Al2(SO4)3,
wash the salt recovered from the organic phase in order to remove could be achieved in this process. Recovery of V is not reported in
impurities like Cu, Co, Na, K, S and P and make the product ready this acid leaching study (Marafi et al., 2010).
for Fe–V alloy production. The heavy petroleum ash sample was In a process developed by the Hall Chemical Co (Ohio),
leached with 1 M H2SO4 solution with a liquid/solid ratio of hydrochloric acid was used for leaching of metals from spent
3 mL/g, whereas the Orimulsion fly ash sample was leached with hydrotreating catalysts (Parkinson, 1987). The spent catalyst was
2 M and 3 M H2SO4 solutions with liquid/solid ratios of 4 mL/g dissolved completely in HCl and then molybdenum was precipi-
and 3 mL/g, respectively. The leach product was filtered from the tated first, as a sulfide, by adding H2S. Next, vanadium was taken
carbonated waste, and afterward, in order to recover the remaining out by solvent extraction, reclaimed by adding caustic soda, and
waste, the filtrate was washed with water (150 mL/step) for 3 precipitated as vanadium pentoxide. Nickel was removed by sol-
stages. As a result of oxidative sedimentation, the sediment was vent extraction, and then recovered as a sulfate by adding sulfuric
separated by filtration, and was washed with a H2SO4 with a pH acid. Cobalt was salvaged in a similar manner as nickel (Marafi
of 2 (liquid/solid = 10 mL/g) in a 3-steps procedure. The impurity et al., 2010).
control was maintained after washing and V recoveries up to 85% Toida et al. (1979) invented a process for recovering molybde-
were obtained. After washing, acceptable loss of V (6.6%) was num from spent HDS catalysts by hot water alkaline leaching of
observed. roasted used catalysts. However, a disadvantage of this process
There are three main companies that are concerned with that it needs an organic solvent which is difficult to recover and
renewed catalyst production: Porocel (previously CRI), Eurecat unsuitable for commercial practice from the view point of environ-
and Tricat (Chang, 1998; Dufresne, 2007). Each of these companies mental pollution.
works with different rejuvenation techniques. Porocel (CRI) uses a Roasting and sulfuric acid leaching that comes after are consid-
moving band with a fluidized bed (Blashka, 1999), Eurecat uses a ered to be the best methods as they dissolve all precious metals.
rotating furnace (Dufresne, 2007) and Tricatusesa uses fluidized However, sub methods are quite complicated in obtaining separate
beds in rejuvenation processes (Neuman, 1995). products in high purity. Na2CO3 roasting and further leaching with
A summary of the experimental studies on recovery of metals water is the sole method applied in industry for HDS catalysts since
from hydrotreating catalyst is reported in Table 2. V and Mo are easily separated from Ni and Co (Kar et al., 2004).

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dx.doi.org/10.1016/j.wasman.2015.07.007
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Table 3
Comparison of some characteristics of hydro- and pyrometallurgical processes (Gupta and Mukherjee, 1990).

Terms of Reference Hydrometallurgy Pyrometallurgy

Treatment of high grade ores Less economical More economical
Treatment of low grade ores Suitable provided a selective leachant can be used Unsuitable because large amounts of energy is required to melt associated gangues
Treatment of complex ores Possesses the flexibility for treatment of complex ores and for production of a variety Unsuitable because separation is difficult
of by-products
Process economics Can be used for small-scale operations; it has a lower capital investment sensitivity to Best suited for large-scale operations requiring a large capital investment
plant size in lower plant capacity ranges
Treatment of secondary resources Suitable Unsuitable in most cases

A. Akcil et al. / Waste Management xxx (2015) xxx–xxx

Separation of chemically similar metals Possible Not possible
Treatment of sulfide ores Can be treated without generating sulfur dioxide; the need to make and market Sulfur dioxide is generated which in high concentrations must be converted to sulfuric
sulfuric acid is eliminated; possibility exists to recover sulfur in elemental form acid and in low concentrations must be disposed of in other ways. For the former, a
market has to be found and for the latter, methods are available but are expensive
Reaction rate Generally slow as all operations are carried out at relatively low temps Rapid as high temperatures are involved
Throughput Small throughput for production unit Very high unit throughput
Materials handling Solutions and slurries can be transferred in closed pipe lines Handling of molten metals, slags, mattes, etc. appears problematical
Environmental pollution No atmospheric pollution problems Problems of waste gas and noise; many processes emit large amounts of dusts which
must be recovered to abate pollution or because the dust itself contains valuable
metals
Solid residues Most solid residues are in finely divided states: in their dried conditions create dust Many residues, such as slags, are coarse and harmless, so that they can be stored in
problems, in their wet conditions release metal ions in solutions; this may contaminate exposed piles without danger of dissolution; piles may be unsightly and esthetically
the environment unacceptable
Toxic gases Many processes do not generate gasses, and if they do, reactors can be made gas-tight Many processes generate toxic gasses, expensive systems are required to combat their
easily nonrelease to the atmosphere
Process feed Sensitivity to major variations instead; the process feed, in general, has to be more Suitability for inhomogeneous feed
uniform and more attention to composition and mineralogy is required
Operational feature In general more sophisticated control schemes are required to maintain satisfactory Represents uniquely metallurgical plant features; engineering is not consider complex
operation; plants operate more like chemical plants with control philosophy
associated with chemical plants; plant engineering is more complex

7
8 A. Akcil et al. / Waste Management xxx (2015) xxx–xxx

Welsh et al. (1981), in one of the first process, claimed a chlori- treatment of metal containing wastes and by-products (Lee and
nation process where spent catalysts are leached by a mixture of Pandey, 2012). Over the last 40 years many researchers have inves-
gaseous chlorine, HCl and water. Vanadium and molybdenum vola- tigated the application of biotechnology in mining. To date, several
tilize as oxychloride, whereas aluminum volatilizes as chloride. biotechnologies have been exploited commercially in well mecha-
The three elements are adsorbed in an aqueous media containing nized, engineered systems that can be categorized under the term
HCl. Aluminum precipitates as hexahydrated chloride, whereas biohydrometallurgy (Mishra et al., 2007). Bioleaching approach is
nickel and cobalt remain in the solid residue. based on the ability of microorganisms, bacteria or fungi, to pro-
In the process of Sebenik et al. (1985) the spent catalysts are duce leaching agents (Beolchini et al., 2012). This technique allows
mixed with sodium carbonate and leached at 200–350 °C and metal recycling by processes similar to that in the natural biogeo-
800–2500 psig. Molybdenum is precipitated as MoS2 by H2S, recov- chemical cycles, and is therefore environmentally friendly, with
ered and roasted. Vanadium is precipitated by using NaClO3 as oxi- low cost and low energy requirement (Brierley, 2008a; Cui and
dant and NaOH to adjust the pH at the right value. In an alternative Zhang, 2008). Bacterial leaching is a scientifically proven econom-
process vanadium is extracted from the pregnant solution by a ical method in recovery of metals from low grade ores. 2000 years
quaternary ammine and recovered by washing with H2SO3. Also ago, bacterial leaching of copper sulfide from sulfide ores and
molybdenum is recovered by solvent extraction by using a sec- recovery of metallic copper by sedimentation was applied in
ondary ammine and stripped with ammonium hydroxide. Europe and China (Rossi, 1990). Being cheaper compared to other
Marcantonio (2007) patented a process where catalysts are treated methods and applicable to waste and low grade ores, interest in
in autoclave with water and ammonia: ammonium molybdate and bacterial leaching will remain strong. In these processes, bacteria
nickel ammonium sulfate are soluble and remain in solution, serve as catalysts (Habashi, 2002). For this reason, leaching with
whereas ammonium metavanadate precipitates. The latter is bacteria is easier than chemical processes that take place at room
recovered, dried and calcined. Nickel is separated in a solvent temperature and atmospheric pressure. The following four
extraction process by LIX 84 in kerosene and extracted from the species have been assessed in terms of their own potential or use
organic phase by sulfuric acid. The aqueous phase is treated to in bioleaching: Acidithiobacilli spp. (autotroph bacteria),
remove arsenic and phosphor, than ammonia and an acid are Pseudomonas spp. (heterotroph bacteria), Aspergillums spp. and
added to give ammonium polymolybdate which is crystallized Penicillium spp. (heterotroph fungi) (Brierley, 2008b).
and recovered. Bacteria from the genus Acidithiobacillus are the most important
In a patented process, Gutnikov (1971) used ammonium car- microorganisms applied to metal solubilization, particularly
bonate solution for leaching of metals from spent catalysts and because they are autotrophic and tolerate high concentrations of
recovered more than 90% of Mo and V, and 60–70% of Ni. heavy metals. Cells derive the energy required for their metabo-
Millsap and Reisler (1978) reported that spent Ni–Mo/Al2O3 lism from the catalysis of the aerobic oxidation of reduced sulfur
catalyst was first roasted and then leached with a solution of compounds including sulfides, elemental sulfur and thiosulfate.
ammonium hydroxide and ammonium carbonate to extract Mo Furthermore, Acidithiobacillus ferrooxidans can use Fe(II) as an
and Ni leaving Al2O3 as a residue. Ni was precipitated as carbonate energy source (Rohwerder et al., 2003). The usefulness of these
from the leach solution. Molybdenum was recovered by solvent microorganisms in metal solubilization – not only from ores and
extractions and precipitated as calcium molybdate. concentrates but also from solid wastes – is mainly related to their
Hydrometallurgy offers a number of significant advantages. ability to generate acidic media (sulfuric acid is the last product
There are also some disadvantages associated with hydrometallur- during the oxidation of sulfur compounds) and oxidizing media
gical operations. Comparison of some characteristics of hydro and [Fe(III) is produced during the growth of A. ferrooxidans on Fe(II)]
pyrometallurgical processes is given in Table 3 (Gupta and (Bosio et al., 2008). A. ferrooxidans are commonly used species in
Mukherjee, 1990). obtaining precious metals from the sulfur matrix in bioleaching
(Beolchini et al., 2009). This acidophilic has a great ability to oxi-
2.1.2. Pyrometallurgical methods dize iron and elementary sulfur to ferric iron and sulfuric acid.
Pyrometallurgy employs the thermal treatment to bring about These metabolites react with the species and dissolve metal sul-
physical and chemical transformations in the materials to enable fides and oxides during bioleaching. Microorganisms have been
recovery of valuable metals. Many techniques in pyrometallurgical shown to possess an ability to survive by adaptation or mutation
methods involve direct melting, calcination and melting, chlorina- to high concentrations of toxic heavy metals Some researchers
tion and roasting (Parkinson and Ishio, 1987; Howard and Barnes, had approaches for using Penicillium funiculosum, Aspergillus foeti-
1991; Gaballah and Djona, 1994; Kar et al., 2005; Busnardo et al., dus and Penicillium simplicissimum to bioleach nickel red ores to
2007; Jadhav and Hocheng, 2012). This process is fast because obtain heavy metals (Liu et al., 2008; Santhiya and Ting, 2006; Le
the physical form of the scrap is not as important as that required et al., 2006; Tang et al., 2006; Valix and Loon, 2003). Thiobacillus
in chemical treatments. However, pyrometallurgical processes ferrooxidans is also used in industrial mineral processing and have
require a high amount of energy and cause emission of SO2 gas the ability to oxidize both sulfur and iron, strains can be made
which is a severe environmental pollutant (Ojeda et al., 2009; adaptable by successive subculturing to a variety of metals such
Havlik et al., 2010). When using pyrometallurgical and hydromet- as Co, U, Cr and As. Metals recovered through this bioleaching pro-
allurgical methods together, spent catalysts are roasted before cess include Cu, U, Au, etc. (Komnitsas and Pooley, 1989, 1991).
chemical leaching (Lee et al., 1992; Park et al., 2007). Direct leach- In recent years, Mishra et al. (2004) worked on sulfur-oxidizing
ing of spent catalyst takes place at high pressures (Siemens et al., acidophilic bacteria to recover base metals such as Ni, V, and Mo.
1986). Nevertheless, a significant amount of chemicals used in Leaching of spent petroleum catalyst waste were is carried out in
chemical leaching are not environmentally friendly. Due to these one or two steps by using sulfur-oxidizing bacteria. Two-step
issues, biotechnological leaching methods have been developed leaching showed a greater yield in overall recovery. A
as alternative methods. biotechnological environmentally friendly strategy involving
bioleaching abilities of Fe/S oxidizing bacteria (A. ferrooxidans,
2.1.3. Biohydrometallurgical methods Acidithiobacillus thiooxidans and Leptospirillum ferrooxidans) was
For sustainable development, biological processes are often rec- tested on spent HDS catalysts containing naphtha. Ferrous iron
ommended which are poised to play a significant role not only in resulted to be essential for metal extraction: nickel and vanadium
the future metallurgical and chemical sector, but also for the extraction yields were 83% and 90%, respectively, while about 50%

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 A. Akcil et al. / Waste Management xxx (2015) xxx–xxx 9

Table 4
The advantages and disadvantages of bioleaching in comparison with the chemical leaching, thermal treatment, and other traditional processes for metal extraction (Asghari
et al., 2013).

Process Advantages Disadvantages

Chemical Leaching, Thermal Treatment, Other Shortest process time  Requires complex process plant
traditional processes for metal extraction and maintenance cost
 Requires large amount of acid
 Requires large amount of alkali
 High-energy requirement
 High operational cost
 Liability of hazardous chemical
usage during the treatment
 Requires sufficient (high) con-
centration of elements in ores
 Not applicable for highly con-
taminated materials
 Hazardous Emissions
Bioleaching (Bacterial and Fungal leaching)  Environmentally friendly (green technology)  Longer period of operation com-
 Low cost pared to chemical leaching
 Low-energy requirement  Dependency on several atmo-
 Simpler and cheaper to operate and maintain than traditional spheric conditions
processes
 Conditions of operation at ambient pressure and non-excessive tem-
peratures close to ambient
 Most efficient method in terms of heavy metal solubilization
 Higher removal efficiency for heavy metals
 Without strict requirements of raw material composition
 Intensively applied at industrial scale for low grade ores (containing
heavy metals at a concentration less than 0.5 wt.%)
 Applicable for highly contaminated materials
 Safety Emissions

with no iron. Molybdenum extraction yields were not as high as Ni of secondary raw metals. Vanadium was recovered from
and V ones around 30–40% (Beolchini et al., 2010). vanadium-phosphorous catalyst waste by using A. thiooxidans.
Microbial metal solution methods are generally more econom- The most common bacteria used in dissolving metal are
ical and environmentally friendly compared to physical chemical A. ferrooxidans and A. thiooxidans. These bacteria use S0 and Fe+2
methods (Rawlings, 2004; Akcil, 2004; Akcil and Deveci, 2010; as metabolite for their own growth and sulfuric acid production.
Gahan et al., 2013; Srichandan et al., 2013). Aspergillus niger, is one of the most common fungi used in
They do not use a great deal of energy compared with roasting bioleaching, since it has the ability to grow in strong alkaline med-
and melting, and they do not produce sulfur dioxide or other harm- ium Fungi are also used in production of organic acids such as citric
ful gases (Mishra et al., 2004). Microbial technology is an alterna- acid (Legisa and Gradisnik-Grapulin, 1995; Grewal and Kalra,
tive in the mining industry when high grade resources are 1995), oxalic acid (Strasser et al., 1994) and gluconic acid
dwindling (Rawlings, 2004). (Dronawat et al., 1995).
Molybdenite is highly resistant to bacterial attacks (Kelley, Microbial leaching techniques are used in recovering copper,
1986; Beolchini et al., 2009). A successful molybdenite bioleaching gold, uranium, and zinc from low grade ores or secondary
requires Mo-resistant organisms or a leach solution that decreases resources (Brombacher et al., 1997). Three groups of microorgan-
the toxicity of Mo. The general reaction of molybdenite’s biooxida- isms are used in leaching: autotrophic bacteria, heterotrophic bac-
tion is summarized below (Reaction (1)): teria and fungi. Using autotrophic thiobacilli is beneficial as they
do not require any organic carbon source for growth. On the other
MoS2 þ 4:5O2 þ 3H2 O ! H2 MoO4 þ 2H2 SO4 : ð1Þ
hand, heterotrophic bacteria and fungi can be used in high pH solu-
Currently bioleaching has an important role in present tions (i.e. alkali, acid consuming substances) (Schinner and
hydrometallurgical methods. In developing countries a wide range Burgstaller, 1989).
of bioleaching activity is present. The simplicity of bioleaching and It is noted that bio-hydrometallurgical approaches provide a
its low cost make it appropriate for developing countries with min- good potential for recovering precious metals from used petroleum
ing resources (Acevedo, 2002). Two bacterial mechanisms were catalysts (Aung and Ting, 2005; Santhiya and Ting, 2005).
suggested: (1) direct bacterial attack on the mineral surface and Metals such as Ni, V and Mo, commonly found in catalyst
oxidation by enzymatic reactions and (2) an indirect mechanism waste, have stable dissolving ions at 25 °C, pH < 2.0 and
where mineral oxidation takes place with thiosulfate or polysulfide Eh > 500 mV (Pourbaix, 1974). These parameters are compatible
with the oxidation of Fe+2 to Fe+3 (Schippers and Sand, 1999; with the Actinobacillus species that are chemo-autotrophic,
Tributsch, 2001). acidophilic and sulfur-oxidizing. In such conditions, sulfuric acid
Bioleaching is also used to recover precious metals in various that is produced as a result of the biooxidation of sulfur and/or
solid waste processes: biosolution of metals from fly ash, used bat- reduced sulfur compounds by acidophiles is the effective leaching
teries and electronic wastes. For example, Blaustein et al. (1993) agent.
used A. ferrooxidans to extract Mo from coal liquefying catalyst Acidithiobacillus produces some intermediate sulfur products
waste. Metals such as Al, Ni, Mo, V, and Sb are extracted by while growing on elementary sulfur (Reaction (2)) (Staley et al.,
liquid cracking catalysts. These catalysts are mainly used in 1989).
production of primary metabolites such as citric, gluconic, and
S þ O2 þ H2 O ! SO2 þ
3 þ 2H : ð2Þ
oxalic acid and thus this waste material is an important resource

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10 A. Akcil et al. / Waste Management xxx (2015) xxx–xxx

Fig. 2. Process diagram of the Gulf Chemical Corporation treatment (Gulf Chemical and Metallurgical Corporation, 2014).

For this reason sulfide ions that emerge can be oxidized by oxy- in a fixed mass ratio. The aim is to burn out sulfur, hydrocarbons
gen and catalyzed by bacteria. These bacteria develop at low pH and carbon, as well as to favor reaction of vanadium and molybde-
and can tolerate extreme conditions in concentrated metal solu- num. The furnace is characterized by different zones where differ-
tions. It was reported that A. thiooxidans and A. ferrooxidans reduce ent oxygen concentrations and temperatures are applied. Once
vanadium (V) to vanadium (IV) in the presence of elementary sul- cooled, catalysts are ground and thus leached with water: in this
fur (Bredberg et al., 2004; Briand et al., 1996). manner sodium molybdate and vanadate, being water-soluble,
The advantages and disadvantages of bioleaching in comparison are separated from the alumina, nickel and cobalt residue. The
with the chemical leaching, thermal treatment, and other tradi- pregnant solution is purified removing arsenic and phosphor by
tional processes for metal extraction are listed in Table 4. addition of magnesium and ammonium salts at basic pH. After fil-
tration, another ammonium salt is added and ammonium vanadate
3. Industrial processes precipitates around pH 9. The pH is acidified and molybdenum pre-
cipitates as ammonium molybdate at pH around 1. The two salts
Several companies around the world collect, recycle, regenerate are roasted at 400–500 °C to obtain the corresponding oxides
or recover spent HDT catalysts. Gulf Chemical and Metallurgical (V2O5 and MoO3). The solid residue from leaching is treated at a
Corporation of the Eramet Group runs a plant in Freeport, Texas, temperature above the melting point of alumina in an electric
where 30,000–40,000 t/y of spent catalysts are processed. The arc furnace. Calcium aluminate is recovered as slag and used as
company only recovers molybdenum and vanadium, whereas the inert material for the production of refractory and ceramics
Ni–Co alloy is sent to plants specialized in separation of Ni from whereas nickel, cobalt and the remaining part of molybdenum
Co. The process diagram is shown in Fig. 2. This industrial plant and vanadium form an alloy which is sold.
is based on the process described by Llanos et al. (1997). Spent cat- Valdi (www.eramet.com) recycles metals from batteries and
alysts are roasted in a multiple hearth furnace with a sodium salt accumulators, spent catalysts from the petrochemicals industry

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 A. Akcil et al. / Waste Management xxx (2015) xxx–xxx 11

Fig. 3. Nickelhütte’s recycling processes (www.nickelhuette-aue.de).

and waste resulting from the metallurgy of stainless steel. The HDS thermally treated in a fluidized-bed kiln, and/or rotating tubular
catalysts are treated in a roasting furnace to eliminate sulfur and kiln, depending on the type of material. Flue-gas is primarily
coke, and then smelted in an immersed electrode furnace, they cleaned in a cyclone and dust collecting filter, and the sulfur oxide
are transformed into ferroalloys, ultimately to be used by stainless compounds of the flue gas are treated with magnesium hydroxide,
steel manufacturers. in a series of scrubbing towers, and converted to magnesium sul-
Treibacher Industrie AG (www.treibacher.com/en) recycles cat- fate, which is refined to a quality suitable for use as an agricultural
alysts and residues that contain vanadium, molybdenum and fertilizer product. The intermediate metal products will be worked
nickel in cutting-edge recycling plants that meet the highest envi- up through a new well-developed hydrometallurgical process into
ronmental standards. In particular, it treats used catalysts from the pure metal oxide and concentrates. Finished products are molyb-
chemical, petrochemical, pharmaceuticals and foodstuffs indus- denum oxides, molybdenum concentrates, vanadates, cobalt oxi-
tries, boiler or gasification residues from oil combustion or gasifi- des and nickel products. Moreover, the plant produces other
cation operations and galvanic nickel residues. Some examples finished products such as high grade ferro/molybdenum, ferro/-
are represented by fluid cracking catalysts (FCC) for oil crackers, vanadium and ferro/nickel alloys in different shapes and forms
production of adipic, maleic, nitric and sulfuric acid, butadiene (fines, granules, and blocks).
rubber and styrene, ethylene-propylene-diene rubber, phthalic Others minor companies are GS EcoMetal Co., Ltd., operating as
anhydride and anthraquinone. a subsidiary of GS Caltex Corp. (South Korea), Eurecat (France),
Nickelhütte Aue GmbH (www.nickelhuette-aue.de) recycles Aura Metallurgic (Germany), Taiyo Koko Co. (Japan), Spent
catalysts containing nickel, vanadium, molybdenum, copper, zinc Catalyst Recycling (Germany), Taiyo Mining and Industrial Co.
and tungsten coming from chemical and petrochemical industries, (Japan), Full Yield Industries (Taiwan), Metallurgy Vanadium
refineries, cosmetic and fertilizer industries, as well as from phar- (USA), Metal-Tech, Nippon Catalyst Cycle Co. (Japan), and
maceutical processes. A flow-sheet of the process including the dif- Quanzhou Jing-Tai Industry Co. (China) (Marafi and Stanislaus,
ferent materials recycled and the resulting products is shown in 2008b).
Fig. 3.
Sadaci N.V. (www.sadaci.be) recycles spent hydroprocessing 4. Summary
catalysts from oil-refineries, through thermal and hydrometallur-
gical treatments. The plant is located in Belgium where HDS are The last years, recovery of metals from oil-refining waste and
recycled with the recovery of molybdenum only, sold as residues such as fly ash, spent petroleum catalysts have gained
technical-grade oxide and ferro–molybdenum (FeMo 65%) alloy. importance. The petrochemical industry is an industry branch that
Moxba-Metrex (www.moxba.com) is a Dutch company which produces organic intermediate products such as refinery products,
treats Ni–V–Mo–Co HDT spent catalysts. Spent catalysts are natural gas, plastic, rubber, fiber raw materials.
subjected to mechanical processes such as separation, sieving, Petrochemical waste cause an environmental risk due to their
breaking, in order to facilitate the downstream thermal and hazardous content. At the same time, they also represent
hydrometallurgical treatments. Subsequently the material is important secondary resources. Physical, hydrometallurgical and

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Please cite this article in press as: Akcil, A., et al. A review of metal recovery from spent petroleum catalysts and ash. Waste Management (2015), http://
dx.doi.org/10.1016/j.wasman.2015.07.007