sustainability

Article
Spent FCC E-Cat: Towards a Circular Approach in the
Oil Refining Industry
Francesco Ferella, Idiano D’Adamo * , Simona Leone, Valentina Innocenzi, Ida De Michelis
and Francesco Vegliò
Department of Industrial Engineering, Information and Economics, University of L’Aquila, Via G. Gronchi 18,
67100 L’Aquila, Italy; francesco.ferella@univaq.it (F.F.); simona.leone@graduate.univaq.it (S.L.);
valentina.innocenzi1@univaq.it (V.I.); ida.demichelis@univaq.it (I.D.M.); francesco.veglio@univaq.it (F.V.)
* Correspondence: idianodadamo@hotmail.it




Received: 29 November 2018; Accepted: 21 December 2018; Published: 26 December 2018


Abstract: Every year the oil refining industry consumes thousand tons of fluid catalytic cracking
zeolite from the E-cat generated in the fluid catalytic cracking (FCC) unit. In the present paper, a new
process for recycling of fluid catalytic cracking catalysts (FCCCs) is presented. The process, previously
tested at laboratory scale, was simulated by SuperPro Designer catalysts (FCCCs, also known as
equilibrium catalysts, E-cat), which are mainly landfilled. Their intrinsic value is quite low and the
content of rare earth elements (REEs), as lanthanum and cerium oxides, is around 3%wt. Moreover,
their reuse in other industrial processes as raw material is very scarce. For each metric ton of
spent FCCC treated for recovery of REEs, nearly the same amount of waste is generated from the
process, the majority of which is represented by the solid residue resulting from the leaching stage.
The manuscript presents a technological study and an economic analysis for the recovery of REEs,
as well as the production of synthetic © software package. The plant was designed for a capacity of
4000 metric tons per year. The discounted cash flow (DCF) method was applied and Net Present
Value (NPV) equal to about two-million € and Discounted Payback Time (DPBT) equal to two years
defined the profitability of the process for recycling of FCCCs. This result depends on the selling price
of zeolite. Consequently, a break-even point (BEP) analysis was conducted on this critical variable
and the condition of economic feasibility was verified with a price of 1070 €/ton. This study tried to
implement recycling strategies towards circular economy models.

Keywords: catalyst; circular economy; E-cat; FCC; rare earths; zeolite

1. Introduction
In the last half century, the use of catalysts for refinery processes, such as catalytic reforming (CR),
fluid catalytic cracking (FCC), hydrodesulphurization (HDS), alkylation, isomerization, and others
increased enormously [1]. Once exhaust, some of them can be regenerated by thermal treatments,
but after a certain number of regenerations they need to be replaced as their catalytic activity becomes
too low. Other catalysts, such as FCCCs, are poisoned by heavy metals and they cannot be regenerated;
periodically, they are replaced with fresh catalyst [2]. Rare earths (REs) are used in the structure
of FCC catalysts in order to improve the activity and obtain hydrothermally stable products with
enhanced yield [3]. Rare earth oxides (REOs) are able to enhance the catalytic activity and prevent
loss of acid sites. As the need for increased amounts of gasoline grew over time, refiners tended
to increase the level of rare earths in their catalyst formulation to meet their profitability targets [4].
REOs concentration gradually increased over the years, and their average is nowadays between 1 and
3%wt, depending on the producer and the feedstock to treat. REs extraction and refining from primary
ores are concentrated in few countries; the majority of mines are located in China [5,6], hence the

Sustainability 2019, 11, 113; doi:10.3390/su11010113 www.mdpi.com/journal/sustainability

Sustainability 2019, 11, 113 2 of 19

recovery of such elements from industrial waste will be crucial for countries, like the European ones,
which do not own primary mines [4]. It is difficult to quantify the total amount of FCCCs produced
every year in the world, as well as their price. The main manufacturers (Grace Davison, Columbia
(MD), USA; Johnson Matthey, London, UK; Albemarle, Charlotte (NC), USA; Basf, Ludwigshafen am
Rhein, Germany; Sinopec, Beijing, China) do not release this data freely and some available reports are
very expensive [7]. Moreover, the amount of spent FCCCs disposed of annually can be confidential or
even unknown. Nevertheless, some reliable estimations were done in recent years and a production of
840,000 ton per year was estimated [8,9].
There are several groups that focused their researches on direct reuse of spent E-cat, for instance,
as additive for partial replacement of sand in cement or mortar powder mixtures [10–13]. Nevertheless,
the amount of FCCC powder than can be used does not exceed 20%wt, in order not to negatively affect
the chemical and mechanical properties of cements and mortars. Thus, nowadays, the fraction of spent
E-cat reused is still low if compared to the huge amount disposed of annually. Nevertheless, no updated
global official data currently exists about the recycling rate of E-cat as cement and mortar additive,
refractory material, production of mineral wool, and ladle covering powder in steelmaking industry.
Regarding regeneration and rejuvenation of FCCC, additional research is required to find reliable
methods, since no effective techniques are currently available in the industrial scale. Direct reuse as
catalyst in other industrial processes has very limited applications, and in lab- or pilot-scale only;
for instance, spent E-cat was used as catalysts for plastic and biomass pyrolysis/gasification or for
the production of synthetic fuels [14,15]. Nonetheless, such processes were not widely developed in
industrial scale. Disposal in landfill or the use for concrete blend are still the main choices for handling
of spent catalysts, despite the content of rare earths elements and sometimes other minor metals in
terms of concentration, like vanadium and nickel, which could be recovered as well [7].
There are several works that studied the extraction of the two rare earth elements (REEs) contained
in FCCCs or waste slag from their production, i.e., lanthanum (La) and cerium (Ce), although no
industrial processes were developed in industrial scale. This is caused by the unprofitability of the
recovery of La and Ce. Some authors recovered La and Ce from FCC waste slag by leaching with
HCl and selective precipitation of the REs as NaRE(SO4 )2 ·xH2 O [16,17]. Furthermore, aluminum
is converted into soluble NaAlO2 that can be used as secondary raw material. Besides selective
precipitation [18], the most used technique for extraction and the further refining of REs from leach
liquors is solvent extraction [18–20]. Ion-exchange is another hydrometallurgical technique that was
used to extract REEs from leach liquors [21–24]. Bioleaching was also investigated to obtain an
environmentally friendly process [25].
Some works were focused on synthesis of zeolites from spent FCCC and the recovery of La and Ce
was not considered [26–28]. Thermal treatment can be carried out by fusion with NaOH or NaHCO3 .
For instance, some authors tested alkaline fusion with several FCCC to Na2 CO3 ratios at 800 ◦ C for
2 h, followed by hydrothermal crystallization with 4 mol/L NaOH solution at 80 ◦ C and dissolved
NaAlO2 [27].
REEs are included in the list of 27 critical materials released by the European Union (EU) in
2017 and their recycling and reuse is a fundamental step for the sustainable development in the
next years [29]. As a last option, since E-cat is sometimes classified as hazardous waste, a thermal
treatment at high temperature with a plasma arc furnace is able to convert spent E-cat into an inert
waste. The vitrification that occurs in the temperature range of 1400–1600 ◦ C avoids any possible
release of metals caused by rainfall water leaching when such waste is put in landfill. Nevertheless,
this high temperature process determines an increase of the disposal cost. Such treatment was tested,
for instance, by Tetronics (Swindon, UK).
The present paper is focused on the profitability analysis for a new recycling process developed
at the laboratories of Chemical Engineering of the University of L’Aquila. This process extracts Ce and
La and reuses the leaching residue for the production of a synthetic Na-A zeolite (also known as LTA,
Linde Type A). Such zeolite is widely used in several industrial and environmental processes, like the
Sustainability 2019, 11, 113 3 of 19

adsorption of metals and organics from wastewater and spent solutions, ion-exchange, catalysis,
formulation of phosphorus free detergents as water softener and for alkane/alkene separation [30,31].
According to the Ellen MacArthur Foundation, a circular economy is an economic system where
products and services are traded in closed loops, which is regenerative by design, with the aim to
retain as much value as possible of products and materials. Hence, the aim is to create a system that
allows for the long life, optimal reuse, refurbishment, remanufacturing, and recycling of products and
materials. This is the aim of the process presented in this paper, that was applied to a plant with a
realistic capacity of 4000 metric tons per year; the total amount of E-cat annually stockpiled or disposed
of in Italy is indeed in the range 10,000–12,000 tons.
The methodology used is based on DCF and multiple indexes, such as NPV, DPBT, and Internal
Rate of Return (IRR) are proposed. At the same time, other indexes, such as Gross Margin Ratio
(GMR) and Return on Investment (ROI), are useful to describe the economic performance of the project
according to the metric used in the balance sheet. The analysis is conducted in a baseline scenario and
varying the critical variables (selling price of zeolite, cost of sodium hydroxide, cost of sulfuric acid,
treatment/disposal cost for solid waste, treatment/disposal of aqueous liquid, and cost opportunity of
capital) alternative scenarios are investigated.

2. Materials and Methods

The first sub-section presents the entire recycling process as simulated by the software.
The following Section 2.2 lists the different techniques that are used for the characterization of solid
samples and liquid solutions. Sections 2.3 and 2.4 explain how the leaching tests were carried out
and how the two REEs were recovered from the leach liquor. The detailed experimental procedure
for the synthesis of zeolite is shown in Section 2.5. Finally, Section 2.6 presents the economic model
developed, and all input data and assumptions are described in Section 2.7.

2.1. The Description of the Process

Spent E-cat does not require any mechanical treatment like grinding or even roasting, as it is
already composed of fine oxidized particles (D50 = 80 µm). Hence, the process is characterized by a
direct leaching of the catalyst in sulfuric acid solution. After that, the unreacted material is filtered by
a plate and frame (P&F) filter. The solid residue undergoes synthesis of zeolite, whereas the pregnant
solution is heated and stirred for 1 h, while 50%wt NaOH solution is slowly added to increase the
pH at around 2 and cause the precipitation of RE double sulphate salts. Such salt is thus filtered by a
P&F filter or a two-phase centrifuge, washed, and dried for final storage in bags. The spent solution,
still containing an interesting amount of sulfuric acid, undergoes nanofiltration (NF) in a membrane
module in order to recover around 85% of the solution in the permeate with approximately the same
molarity of the feed solution; salts and other rejected compounds are recovered in the retentate stream,
a concentrated solution that is routed to the wastewater treatment. This recovery stage was already
tested by our research group for spent sulfuric acid solutions coming from the production of optical
quartz: in this way, the operating costs are strongly reduced as a small make-up of fresh acid is
required only.
The synthesis of the zeolite is carried out according to the procedure that is explained in Section 2.4.
Sodium carbonate is thoroughly mixed with the solid residue that acts as base silicoaluminate.
The mixture is put into a rotary kiln for roasting, and after cooling the hydrothermal treatment
with NaOH solution takes place. Afterwards, the solution is filtered by a two-phase decanter and the
solution, together with the water used for zeolite washing, is routed to the wastewater treatment.
The zeolite is dried in a rotary or belt kiln, thus cooled down, mildly milled, and stored in a dried
environment prior to final packaging. The flow-sheet of the process is shown in Figure 1. Nearly 85%
of the total water consumed is recycled back to the process after its treatment. This is very important,
since the process is water-intensive, as several washings are required (leaching cake and zeolite), thus
the recycling of water is necessary in the perspective of a circular economy approach. After the first
Sustainability 2019, 11, 113 4 of 19

treatment, part of the water has to be discharged into the industrial sewage network to avoid the
overconcentration of salts and any other compound in the recycled water.

Figure 1. Flow-sheet of the recycling process.

2.2. Characterization of the Samples

The characterization of the spent FCCC sample, products, and solutions was carried out at the
laboratories of Chemical Engineering at the University of L’Aquila, Italy. The spent E-cat catalyst
sample was provided by Orim SpA, Macerata, Italy. The catalysts and the zeolites synthesized during
the experimental campaign were characterized by X-ray fluorescence (XRF) (Spectro, Xepos, Kleve,
Germany) and Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES, 5110 Agilent
Technologies, Santa Clara (CA), USA), X-ray diffraction (XRD, PANalytical X’Pert PRO, Malvern
PANalytical, Malvern, UK), particle size distribution (PSD, Mastersizer 2000, Malvern PANalytical,
Malvern, UK), Brunauer-Emmet-Teller (BET) specific surface area (SSA, NOVA 1200e, Quantachrome
porosimeter, Boynton Beach (FL), USA), and scanning electron microscopy (SEM, 20 kV Philips XL30
CP microscope, Amsterdam, The Netherlands).

2.3. Leaching Stage

Several leaching tests were carried out with different acids [32]. Sulfuric acid was selected as the
most promising leachant. The leaching stage was carried out in a 2 L glass jacketed stirred reactor
equipped with a mechanical stirrer, with 1 L of 1.5 mol/L H2 SO4 solution, and solid to liquid ratio
Sustainability 2019, 11, 113 5 of 19

(S/L) equal to 200 g/L at 80 ◦ C. The reaction time was set at 3 h. These optimized conditions are based
on the results that were obtained in a previous research [18]. After the reaction time, the remaining
E-cat was filtered by a 142 mm air pressure filter (Millipore, cut off 0.45 µm, Burlington (MA), USA) in
order to separate the solid from the leach liquor. The solid was washed by distilled water and dried at
105 ◦ C for 24 h. The leaching trials were repeated twice, in the same conditions, to have an estimation
of the reproducibility of the results. The concentration of Ce, La, Al, and Si in the leach liquors was
measured by ICP-OES. Al and Si were determined as are the most concentrated elements that can
affect the final grade of the REs precipitate. The extraction yield was calculated, as indicated in [33].

2.4. Recovery of REEs

La and Ce were recovered from the leach liquor by a direct precipitation with 50%wt NaOH
solution. A soon as the pH reached 1.5, a white precipitate appeared in the flask. The precipitation
was carried out in a beaker on a heated plate, under mild magnetic stirring at 50 ◦ C. Further NaOH
solution was added to achieve a pH equal to 2, thus the reaction was stopped after 1 h. The solution
was filtered by the pressure filter and the precipitate washed with distilled water and then dried in
oven at 105 ◦ C for 24 h. The RE precipitate was characterized by ICP and XRD analyses.

2.5. Synthesis and Characterization of Zeolite

The solid residue from the leaching stage was used as raw silicoaluminate for the production of
synthetic zeolite. Unlike the hydrothermal synthesis that is described in [32], the roasting stage was
carried out with Na2 CO3 , which is a cheaper reagent. The E-cat residue from the leaching stage was
mixed with Na2 CO3 in a 50%wt ratio and roasted at 600 ◦ C for 2 h in a muffle oven (MF 100, Galli).
Hence, once cooled down, the material was ground by a ball mill (PM 100, Retsch). The hydrothermal
treatment was conducted in a 500 mL flask at 80 ◦ C under stirring in a water bath (Dubnoff, ISCO) and
S/L ratio of 15% wt/vol for 24 h. A concentration of NaOH in the range 1–1.5 mol/L was used.
After that, the material was filtered by pressure filter and washed with distilled water until the
wash water reached a pH value between 7 and 8. The synthetic zeolite, hence, was dried at 105 ◦ C for
24 h, ground manually, and stored in a closed flask in order to avoid moistening. The characterization
of physico-chemical properties was done by BET, XRD, and XRF analyses.

2.6. The Description of Economic Model

DCF is a well-known economic assessment method estimating the attractiveness of a project.
It tries to work out the value of an asset today, based on projections of all the cash flows that it
could make available to investors in the future. Several economic indexes can be chosen to assess the
profitability [34]:

• NPV is defined as the sum of present values of individual cash flows.

• DPBT represents the number of years needed to balance cumulative discounted cash flows and
initial investment.
• IRR identifies the discount rate at which the present value of all future cash flows will balance the
initial investment.
n
NPV = ∑ ( I t − Ot ) / ( 1 + r ) t (1)
t=0
DPBT
∑ ( I t − Ot ) / ( 1 + r ) t = 0 (2)
t=0
n
∑ (It − Ot )/(1 + IRR)t = 0 (3)
t=0

in which It = discounted cash inflows; Ot = discounted cash outflows; r = cost opportunity of

capital, t = time period; and, n = lifetime of investment.
Sustainability 2019, 11, 113 6 of 19

Other useful indicators are typically used in the balance sheet. For this purpose, their use
characterizes all firms. A combination with previous indexes can be useful, according to the existing
literature [35,36]:

• GMR is calculated by dividing the gross profit by sales.

• ROI measures the amount of return on a particular investment, relevant to the investment’s cost.

GMR = Gross margin/Revenues (4)

ROI = Net Profit/Investment Cost (5)

2.7. Input Data

The simulation of the entire process was carried out by the software package SuperPro Designer© ,
Intelligen Inc. (Cambridge (MA), USA). The process is divided into two main sections: the first
hydrometallurgical section in which La and Ce are extracted and recovered and the second one in
which the synthesis of the zeolite is performed. There is an additional section in which all spent
solutions and wastewaters are treated.
Spent FCC catalyst is usually classified as non-hazardous waste, but some samples are classified
as hazardous, because of the content and the particular speciation of metals, like nickel and
vanadium; for instance, V5+ (V2 O5 ) is considered to be very toxic to living organisms [7]. Nevertheless,
the concentration of such two metals is usually quite low (0.5–1.5% wt as oxides), depending on quality
of the feedstock and the operating time before the unloading of the column’s bed. After the leaching
stage, the solid residue is very stable as all the metals are mostly leached by a strong acid solution, so
the toxicity is eliminated. The toxicity characteristic leaching procedure (TCLP) test demonstrated that
such material is inert (results are not reported here). The testing methodology is used to determine
whether a waste has to be classified as hazardous, i.e. belongs to list according to the United States
(U.S.) Environmental Protection Agency (EPA).
Spent FCCC is usually collected by specialized companies that dispose it of responsibly in
appropriate landfills, and for such service refineries pay a fee that in Europe varies from 200 €/ton to
300 €/ton. This amount represents additional revenue for the recycling process. The plant works in
a continuous operating mode for a total of 7920 h/year (330 working days), considering the normal
maintenance periods. The total capacity of the plant is 4000 tons/year, with an hourly flow-rate of
around 505 kg/h. This capacity was chosen as case study for a country like Italy, where the annual
amount of spent E-cat is estimated to be between 10,000 and 12,000 tons. The project lifetime is set at
15 years, with a depreciation period of 10 years.
The raw materials that were used in the process are concentrated sulfuric acid 96%wt solution,
water, sodium hydroxide, and sodium carbonate. Utilities include electrical energy and natural gas,
burnt in a boiler to heat the jacketed stirred reactors. Natural gas is also used to heat the kiln up in order
to roast the mixture FCCC-Na2 CO3 , as well as to dry the final zeolite before packaging and storage.
The unit revenues of the plant and the cost of raw materials and utilities that are used in the
simulation are indicated in Table 1. Table 2 presents the list of the main equipment required to
develop the plant. The total purchase cost is 2450 k€; there are additional devices and machinery
not included in the list, such as conveyor belts, hoppers, pumps, compressor, weighting system,
and other minor auxiliary facilities, but whose purchasing cost was taken into account. The total
plant direct cost amounts to 3370 k€: the latter includes the equipment purchase cost, installation,
piping, instrumentation and control system, insulation, electrical, yard improvement, and buildings.
Engineering and construction costs plus contingency give the final direct fixed capital cost that amounts
to 3710 k€.
Operative costs regard several items as raw materials (Ca hydroxide, Na2 CO3 , NaOH, Sodium
Hydroxide, Sulfuric Acid, Water), labor-dependent (nine workers distributed on three shifts),
facility-dependent (the staff is completed by an office worker and the technical director of the plant),
Sustainability 2019, 11, 113 7 of 19

laboratory, consumables, waste treatment/disposal (solid waste, aqueous liquid), utilities (natural
gas, electric energy and compressed air), transportation, miscellaneous, running royalties, and failed
product disposal.

Table 1. Economic unit input.

Unit revenues Value

E-cat collection (disposal fee) 250 €/ton
RE oxides 2000 €/ton
Zeolite 1150 €/ton
Unit costs Value
H2 SO4 96%wt 120 €/ton
H2 SO4 96%wt considering recycling 100 €/ton
NaOH 300 €/ton
NaOH 50% sol. 150 €/ton
Na2 CO3 140 €/ton
Water 2 €/ton
Steam 12 €/ton
Electrical energy 0.18 €/kWh
Solid waste disposal 130 €/ton
Liquid waste disposal 120 €/ton

Table 2. List of the main equipment.

Item Capacity Service

Reactor 5 m3 Leaching
P&F filter 30 m2 Leaching solid filtration
Reactor 6 m3 RE precipitation
2-phase decanter 5 ton/h RE sulphate filtration
Belt dryer 50 kg/h RE sulphate drying
Reactor 10 m3 Wastewater treatment
P&F filter 25 m2 Waste sludge filtration
NF membrane module 5 m3 /h H2 SO4 solution recovery
Horizontal shaft mixer 1000 kg/h E-cat/NaOH mixing
Rotary kiln 1000 kg/h E-cat /NaOH roasting
Rod mill 1000 kg/h Grinding of E-cat/NaOH
Reactor (2) 50 + 50 m3 Hydrothermal treatment
2-phase decanter 4 ton/h Zeolite filtration
Rotary dryer 900 kg/h Zeolite drying
H2SO4 96% tank 30 m3 Storage of fresh H2 SO4
H2SO4 tank 20 m3 Storage of recovered H2 SO4
Water tank 50 m3 Fresh water storage
Water tank 50 m3 Recovered water storage
Waste tank 10 m3 Storage of waste acid solution
Stirred tank 4 m3 Preparation of 50% NaOH
Stirred tank 4 m3 Preparation of Ca(OH)2
Silos 12 m3 Storage of Na2 CO3
Boiler 100 kWth Hot water leaching
Packaging machine 500 kg/h Packaging of zeolite
1000
Scrubber Flue gas treatment
Nm3 /h
Tank (4) 5–10 m3 Intermediate storage

Concentrated sulfuric acid is one of the greatest costs among raw materials; for this reason,
the spent acid from the NF membrane module is recycled back and, taking into account such saved
amount, the equivalent cost of the fresh acid would be 100 €/ton instead of the market price of
120 €/ton. The cost of sodium hydroxide is equal to 300 €/ton; in this process, such chemical is used
Sustainability 2019, 11, 113 8 of 19

as aqueous solution in the REEs precipitation stage and in the hydrothermal treatment of the leaching
residue. The solutions are freshly prepared with water in two stirred tanks. Consequently, the price
per ton remains fixed but the amount of NaOH that is requested by the processes halved. According to
this assumption, it is possible to declare that the cost of NaOH 50% sol. is equal to 150 €/ton.
Finally, three items characterize the revenues: (i) E-cat collection (disposal fee), (ii) selling of RE
oxides, and (iii) selling of zeolite. The first item is derived from the treatment of a product that is
potentially dangerous and it is paid by oil industry. The other two items are linked to the materials
recovered by the process.

3. Results
In this section, a quick overview on the main results achieved during the experimental campaign
is given. After the results from the characterization of the spent FCCC (Section 3.1), the extraction
yields for La, Ce, Al, and Si are reported in Section 3.2, whereas in Section 3.3, the zeolite obtained
from the synthesis procedure is fully characterized. Several economic indexes (NPV, DPBT, IRR,
GMR, and ROI) are proposed in Section 3.4 regarding the baseline scenario. In addition, Section 3.5
investigates the variation of these indexes in function of critical variables.

3.1. Characterization of Spent FCCC

The concentration of the main elements is shown in Table 3. It underlines that the total
concentration of REs is rather low.

Table 3. X-ray fluorescence (XRF) and inductively coupled plasma (ICP) analyses of the spent E-cat.

Concentration (%wt)
Na Al Si P Ti V Fe Ni La Ce
XRF - 15.60 12.30 0.13 0.47 0.05 0.25 0.03 2.30 0.16
ICP-OES - 31.75 19.46 - - - - - 1.57 0.19

The XRD analysis showed that the most probable compounds are dealuminated zeolite Na-Y,
that is the main crystalline phase, followed by other minor phases, like zeolite ZSM-5 and alumina.
Regarding the BET analysis, the SSA was around 112 m2 /g, a bit lower than the area of a fresh FCCC,
which is usually in the range 120–180 m2 /g. The PSD was a Gaussian curve centered at 80.4 µm, with
a Sauter’s diameter D [2,3] equal to 73.6 µm.

3.2. Extraction and Recovery of REEs

The extraction yields of the main elements as a function of reaction time are listed in Table 4;
such yields are reported as medium values and standard deviation.

Table 4. Extraction yield for the main elements (ICP-OES).

Extraction Yield (%)

Sample
Ce La Si Al
H2 SO4 1 h 63.7 ± 1.1 73.1 ± 2.2 1.4 ± 0.1 16.7 ± 1.8
H2 SO4 2 h 77.8 ± 1.9 81.9 ± 1.8 1.4 ± 0.2 20.2 ± 2.5
H2 SO4 3 h 80.5 ± 2.7 88.1 ± 2.4 1.5 ± 0.2 22.9 ± 2.3

Hence, the best extraction yields for La and Ce were obtained after 3 h. The extraction of Si
was lower than 2%, but such element is present as colloidal silica that, once the solution cools down,
makes the filtration difficult. For this reason, the following filtration and precipitation shall be carried
out with warm solution. The extraction of Al was low as well, but the concentration in leach liquor
was not negligible. The initial pH of solution was 0.45 and NaOH was added to increase the pH to
 Sustainability 2019, 11, 113 9 of 19

Sustainability 2018, 10, x FOR PEER REVIEW 9 of 18

2. The precipitation occurred slowly as soon as the NaOH solution was added. The precipitation of
Thisinsoluble
precipitation
NaRE(SOmechanism as double
4 )3 ·H2 O is expressed, sulfate
as follows [37]:salt is also caused by the addition of Na2SO4
instead of NaOH [17]. The solubility of NaRE(SO 4)2·H2O in water (in particular, for Ce, La, Pr, Nd,
La2 (SO4 )3 + 2 Na+ + SO4 2- + 2 H2 O → 2 NaLa(SO4 )2 ·H2 O (6)
Pm, Sm, Eu, Sc) is very low and it decreases with the increase of temperature [18]. After cooling
down, the white salt was filtered, Ce2 (SO4 )3washed
+ 2 Na+ +with
SO4 2-distilled
+2 H2 O → water and dried
2 NaCe(SO 4 ) 2 · H2 Oat 105 °C for 24 h,(7)and thus
used for theThisanalysis. The results of ICP-OES showed the following element concentration: La
precipitation mechanism as double sulfate salt is also caused by the addition of Na2 SO4
36.54%, Ce 2.87%,
instead Na 2.88%,
of NaOH [17]. The Alsolubility
6.14%, and Si 0.7%4 )by
of NaRE(SO weight. The rest is mainly water, oxygen, and
2 ·H2 O in water (in particular, for Ce, La, Pr, Nd,
sulphur.Pm, Sm, Eu, Sc) is very low and it decreases with the increase of temperature [18]. After cooling down,
Thethe
XRDwhite salt was indicated
analysis filtered, washedthatwith
the distilled water andwas
RE precipitate at 105 ◦ Ccomposed
driedmainly for 24 h, andof
thus used for4)2·xH2O
NaLa(SO
the analysis. The results of ICP-OES showed the following element concentration: La 36.54%, Ce 2.87%,
and NaCe(SO4)2·xH2O, but Al2SO4 and small amount of Al(OH)3 cannot be excluded. The XRD
Na 2.88%, Al 6.14%, and Si 0.7% by weight. The rest is mainly water, oxygen, and sulphur.
spectrum of The
the XRD
RE salt was indeed not crystalline and characterized by large and not well-defined
analysis indicated that the RE precipitate was mainly composed of NaLa(SO4 )2 ·xH2 O
peaks. This
andRE concentrate
NaCe(SO shall be leached again and La be separated from Ce by solvent extraction.
4 )2 ·xH2 O, but Al2 SO4 and small amount of Al(OH)3 cannot be excluded. The XRD
Hence, the precipitated
spectrum of the REsalt can indeed
salt was be sold notto companies
crystalline with expertise
and characterized by large in separation and refining of
and not well-defined
peaks. This RE concentrate shall be leached again
REEs like Rhodia (France), Umicore (Belgium) or Solvay (Belgium). and La be separated from Ce by solvent extraction.
Hence, the precipitated salt can be sold to companies with expertise in separation and refining of REEs
like Rhodia (France), Umicore (Belgium) or Solvay (Belgium).
3.3. Characterization of the Synthesized Zeolite
3.3. Characterization of the Synthesized Zeolite
After the synthesis procedure that is described in Section 2.5, the zeolite from the acid leaching
After the synthesis
was fully characterized. procedure that
In particular, theisSSAdescribed
was in Section
83.2 m2/g, 2.5,whereas
the zeolite from
the thecumulative
BJH acid leaching average
was fully characterized. In particular, the SSA was 83.2 m2 /g, whereas the BJH cumulative average
pore volume was 0.062 cm3/g with an average pore size of 3 nm. Spent E-cat and synthetic zeolite
pore volume was 0.062 cm3 /g with an average pore size of 3 nm. Spent E-cat and synthetic zeolite
obtainedobtained
from the hydrothermal procedure are shown in Figure 2. The XRD spectrum of the latter is
from the hydrothermal procedure are shown in Figure 2. The XRD spectrum of the latter is
shown inshown
Figure 3, whereas
in Figure Figure
3, whereas 4 proposes
Figure 4 proposesaa SEM picture
SEM picture of of
thethe
samesame zeolite.
zeolite. The zeolite
The zeolite is light is light
brown inbrown
color,inwhereas the spent
color, whereas E-cat
the spent E-catisisgrey.
grey.

Figure
Figure 2. 2. Spent
Spent fluid fluid catalytic
catalytic cracking(FCC)
cracking (FCC) catalyst
catalyst(left) andand
(left) synthetic zeolitezeolite
synthetic (right). (right).
Sustainability 2019, 11, 113 10 of 19
Figure 2. Spent fluid catalytic cracking (FCC) catalyst (left) and synthetic zeolite (right).

Sustainability 2018, 10, x FOR PEER

Figure 3. REVIEW
X-ray diffraction (XRD) spectrum of the synthetic zeolite. 10 of 18
Figure 3. X-ray diffraction (XRD) spectrum of the synthetic zeolite.

Figure
Figure 4.
4. Scanning
Scanning electron
electron microscopy
microscopy (SEM) picture of the synthetic zeolite.

main phase
The main phasedetected
detectedininthethe zeolite
zeolite was was
Na-A, Na-A, withwith formula
formula Na1212SiAl
Na12Al 12O Si·27H
1248 12 O48 ·27H
2O. 2 O.
Small
Small percentages
percentages of dehydrated
of dehydrated zeolite
zeolite Na-X(Na
Na-X (Na9292
AlAl
92Si Si100
92100 O)384and
O384 ) andCl-free
Cl-free sodalite
sodalite (Na (Na88Al
Al66Si
Si66O24 ),
24),

another aluminosilicate mineral, were also present: this

another aluminosilicate mineral, were also present: this means that means that the conversion
conversion to phase-A was
not complete.
complete. The
Thezeolite
zeoliteNa-A
Na-Apresents
presentsa cubic
a cubiccrystalline
crystallinesystem withwith
system the lattice parameters
the lattice a=b
parameters
= c = 24.61 ÅÅand = β = γ = 90The◦ . The presence of high crystallinity was demonstrated by the
a=b=c=24.61 andα α=β=γ=90°. presence of high crystallinity was demonstrated by the high
intensity of
ofthe
thepeaks. Na-A
peaks. is the
Na-A is major constituent
the major phase (around
constituent 91%wt) and
phase (around spheroidal
91%wt) aggregates
and spheroidal
of remaining
aggregates ofsodalite andsodalite
remaining Na-X phase. Table phase.
and Na-X 5 showsTable the composition
5 shows theofcomposition
the main elements of the of the
main
zeolite that
elements of was obtained
the zeolite from
that wasthe residuefrom
obtained of the
thesulfuric
residueacid leaching.
of the sulfuric acid leaching.

Table 5.
Table Element concentration
5. Element concentration of
of zeolite
zeolite from
from H SO44 leaching
H2SO leaching measured
measured by
by XRF.
XRF.

Concentration
Concentration (%wt)
(%wt)
Na
Na Al
Al Si Si P P Ti
Ti V V Fe Fe Ni Ni La La Ce Ce
Zeo-H 2SOSO
Zeo-H 2
4
4
7.98
7.98 11.59 11.74
11.59 11.74 - - 0.45 0.005
0.45 0.005 0.190.19 0.030.03 0.330.33 0.03 0.03

Although this analysis is not as accurate as ICP, especially for light elements, like Na and Al, it
gives an indication about the Si/Al ratio: hence, from the XRF analysis, it can be inferred that this is a
low silica synthetic zeolite.

3.4. Economic Evaluation Report—Baseline Scenario

The description of the technical aspects was already elaborated and in this phase of the work,
the economic analysis is developed. There is a clear relationship between two perspectives. The
Sustainability 2019, 11, 113 11 of 19

Although this analysis is not as accurate as ICP, especially for light elements, like Na and Al,
it gives an indication about the Si/Al ratio: hence, from the XRF analysis, it can be inferred that this is
a low silica synthetic zeolite.

3.4. Economic Evaluation Report—Baseline Scenario

The description of the technical aspects was already elaborated and in this phase of the work,
the economic analysis is developed. There is a clear relationship between two perspectives. The
simulation software quantifies the several amounts of resources that were employed in the process and
some economic results (GMR, ROI) are obtained directly by this software, while other results (NPV,
DPBT, IRR) are elaborated through Excel programme—Table 6.

Table 6. Economic executive summary (baseline scenario).

Acronym Item Value Measure

A Total investment 4293 k€
B Zeolite 4890 k€/year
C Other revenues 1416 k€/year
d=b+c Revenues 6305 k€/year
E Raw Materials 1685 k€/year
F Waste Treatment/Disposal 1490 k€/year
g=e+f Operative costs 5306 k€/year
h=d−g Gross profit 999 k€/year
I Depreciation (10 years) 352 k€/year
j=h−i Taxable income (1–10 years) 647 k€/year
k=h Taxable income (11–15 years) 999 k€/year
L Tax percentage 40 %
m = f (j,l) Taxes 259 k€/year
n = f (k,l) Taxes 399 k€/year
o=h−m Net Profit (1–10 years) 740 k€/year
p=h−n Net Profit (11–15 years) 599 k€/year
q = h/d Gross margin ratio 15.8 %
r = o/a Return on investment 22.2 %
S Lifetime of investment 15 years
T Cost opportunity of capital 5 %
u = f (a,d,g,m,n,s, t) Net Present Value 2170 k€
v = f (a,d,g,m,n,s, t) Discounted Payback Time 2 years
z = f (a,d,g,m,n,s, t) Internal Rate of Return 56.7 %

The project is profitable in the baseline scenario and the results contribute to developing models
of circular economy. In fact, the evaluation of this typology of investment firstly considers the
environmental advantages derived from the recovery of these wastes and at the same time the
achievement of environmental goals set by the European Union (COM (2017) 490 final). The following
step is represented by the economic study. NPV quantifies the amount of potential profits when
considering the lifetime of the project. The value obtained is extremely relevant: it is equal to 2170
k€. NPV is a realistic metric for decision makers because the DCF method is based on two relevant
aspects: (i) the time value of the money and (ii) the lifetime of the project.
The distribution of cash flows permits to understand this result. From the revenues side,
the recovery of zeolite plays a key role. Its weight is equal to about three quarters (77%). The price
of RE oxides is greater than that of zeolite, but the amount of materials recovered in this waste is
extremely lower (about 5%). It is opportune to underline as the REO concentrate represents the lowest
value among the three revenues of the plant. This confirms that the recovery of REEs from spent E-cat
is unprofitable, even if they would be separated and recovered with 99.9% grade. The use of raw
materials (29%) and the phases linked to the waste treatment and/or disposal (26%) are the main items
of costs. Instead, the share of investment costs is not relevant (8%). The main item of the materials cost
is due to NaOH, used in solution for precipitation of La and Ce, as well as for hydrothermal treatment,
Sustainability 2019, 11, 113 12 of 19

with nearly 837 k€/year. The use of Na2 CO3 (around 277 k€/year) in the roasting stage results in
significant savings with respect to the use of sodium hydroxide. Despite the recycling of sulfuric acid
solution, the cost for such reagent is equal to 506 k€/year (cost of fresh acid only). Industrial water is
another raw material, but around 85% is reused after the wastewater treatment. The disposal cost of
solid and liquid waste is almost high, but the process produces a great amount of sludge and waste
Sustainability 2018, 10, x FOR PEER REVIEW 12 of 18
solution containing metals. This cost is equal to 644 k€ and 851 k€, respectively—Figure 5.

Revenues

77%

16%
7%

E-cat collection (disposal fee) RE oxides Zeolite

Costs

29%
26%

13% 15%
7% 8%
2%

Other Labor Investment Utilities Facility Waste Raw materials

dependent dependent treatment

Figure 5. The distribution of discounted cash flows (baseline scenario).

DPBT is coherent with the result of NPV. A cut-off period is not fixed in this work but certainly
the result is positive, since those cash flows allow the re-entering from the investment already at the
end of the second year. This depends on three elements: (i) the positive value of gross profit, (ii) the
application ofof third-party
third-partyfundsfundsthatthatdistribute
distributethe theinvestment
investment cost
costover thethe
over years of loan,
years andand
of loan, (iii) (iii)
the
share of investment
the share of investment costscosts
is lower thanthan
is lower the operative
the operative ones.ones.
Finally, also IRR defines the profitability of this project. A possible concern for users of the IRR
method is when the discount rate of a project is unknown, but in this case, it is significantly greater
than the cost opportunity of capital. The The analysis
analysis of cash flows underlines the presence of a single
change of sign (it is negative during the year zero and it is positive in the following years due to the
gross profit). For this reason, the possible issue issue ofof multiple
multiple values
values of of IRR
IRR is
is not
not verified.
verified.
NPV, DPBT,
NPV, DPBT, and and IRR
IRR measure
measure the the profitability
profitability of a project, while other two indexes (GMR, ROI)
are referred
referredonly
only to to
a single year year
a single of activity. It is linear
of activity. It iswith the role
linear withofthebalance
role sheet that characterizes
of balance sheet that
the world of firms.
characterizes Usefulof
the world indications
firms. Usefulare provided,
indications but are
theseprovided,
indexes are butmore appropriate
these indexes are for more
other
scopes as: (i)for
appropriate a comparison
other scopes with
as: the
(i) avalue of benchmarking
comparison of theofsector;
with the value (ii) a comparison
benchmarking with other
of the sector; (ii) a
firms employed
comparison within other
the same sector;
firms (iii) a monitoring
employed in the same to measure the performance
sector; (iii) a monitoring of to
a company
measureover the
time; and, (iv)offor
performance the purposes
a company overoftime;
the regulatory
and, (iv) for rules.
the purposes of the regulatory rules.
Gross profit is the difference between the annual revenues and the annual annual operating
operating costs.
costs.
Gross margin is is the
the direct
directpercentage
percentageofofprofitprofitininthethesale
saleprice.
price.ItsIts
positive
positivevalue is determined
value is determined by
the revenues that are greater than the operative costs (6305 k€ against 5306 €). When this value
becomes negative, not only it does not produce wealth, but it even generates economic losses.
Net Profit also considers the profit tax and the depreciation in comparison to the gross profit.
ROI determines how a purchase is profitable. Its positive value is determined by the positive value
of net profit. ROI and GMR are two metrics that give different information. For example, if money is
invested in a project, ROI measures the result of the added investment. Instead, GMR indicates
Sustainability 2019, 11, 113 13 of 19

by the revenues that are greater than the operative costs (6305 k€ against 5306 €). When this value
becomes negative, not only it does not produce wealth, but it even generates economic losses.
Net Profit also considers the profit tax and the depreciation in comparison to the gross profit.
ROI determines how a purchase is profitable. Its positive value is determined by the positive value
of net profit. ROI and GMR are two metrics that give different information. For example, if money
is invested in a project, ROI measures the result of the added investment. Instead, GMR indicates
whether revenues are going up faster than costs.

3.5. Economic Analysis—Alternative Scenarios

The aim of this sub-section is to give solidity to economic results obtained in the baseline scenario.
In fact, they are based on the assumption of a set of input parameters. Hence, a variance of the expected
results could occur. This issue can be overcome by implementing a sensitivity analysis on the critical
variables [38].
The choice of critical variables is linked to the results proposed in Figure 5 regarding the main
items that characterize the cash flows. A pessimistic and an optimistic scenario are evaluated for each
critical variable and a variation of ± 20% is applied.

• The zeolite has a weight equal to four-fifths of discounted cash inflows. Its price of reference
is equal to 1150 €/ton (see Table 1). The potential values of 920 €/ton and 1380 €/ton are
hypothesized in alternative scenarios.
• Raw materials have a weight equal to one-third of discounted cash outflows. In particular, the net
cost of NaOH (50% w/w) covers 35.7% of this cost, followed by the net cost of sulfuric acid with
the 30%. NaOH 50% sol. has a baseline value of 150 €/ton and alternative values of 120 €/ton
and 180 €/ton are proposed. Instead, 96%wt H2 SO4 when considering its recycling has a value of
reference of 100 €/ton and potential alternative values are 80 €/ton and 120 €/ton.
• Waste treatment/disposal have a weight slightly lower than raw materials (−3.5%). In particular,
liquid waste disposal covers 56.9% of this cost and the remaining share is linked to the solid one.
The difference is not significant and both variables are analysed. Solid waste has a baseline value
of 130 €/ton and alternative values of 104 €/ton and 156 €/ton are hypothesized. Regarding
liquid waste, instead, 120 €/ton is the baseline value and 96 €/ton and 144 €/ton are the
alternative values.
• A macro-variable of all cash flows is represented by the cost opportunity of capital. This variable
measures the return coming from an alternative project, which has the same risk level. It is
hypothesized to equal 5%. In this case, four scenarios are assessed with values varying from 3%
up to 7%.

The presentation of six critical variables has determined the elaboration of fourteen alternative
case studies. Several indexes change in function of both variables regarding revenues and
costs—Table 7—while cost opportunity of capital does not modify the value of balance sheet (GMR
and ROI) and at the same time the value of IRR is constant (baseline value equal to 56.7% is always
greater than values examined in this work)—Figure 6.
Sustainability 2019, 11, 113 14 of 19

Table 7. Economic results (alternative scenarios).

Index NPV IRR DPBT GMR ROI

Measure k€ % years % %
Baseline
2170 56.7 2 15.8 22.2
Price of zeolite
920 €/ton −4942 n.d. >15 0.4 8.5
1380 €/ton 8260 181.5 1 27.1 35.8
Net cost of NaOH (50% w/w)
150 €/ton 1423 40.9 3 13.9 20.5
120 €/ton 2917 72.2 2 17.7 23.8
Net cost of H2 SO4 96%wt
120 €/ton 1533 43.3 3 14.2 20.7
80 €/ton 2807 69.9 2 17.5 23.6
Costsolidwaste
156 €/ton 1367 39.8 3 13.8 20.4
104 €/ton 2973 73.3 2 17.9 24.0
Sustainability 2018, 10, x FOR PEER REVIEW 14 of 18
Costliquidwaste

144 €/ton 144 €/ton

1110 1110 34.1
34.1 4 13.1
4 19.8 13.1 19.8
96 €/ton 3230 78.6 2 18.5 24.5
96 €/ton 3230 78.6 2 18.5 24.5

NPV (k€) DPBT (years)

2559
2355 2 2 2 2 2
2170
2003
1853

3% 4% 5% 6% 7% 3% 4% 5% 6% 7%
Cost opportunity of capital Cost opportunity of capital

Figure 6. Sensitivity analysis—Cost opportunity of capital.

Results that
thatwere
wereobtained
obtained in in
these alternative
these casecase
alternative studies confirm
studies the profitability
confirm of the project.
the profitability of the
Economic losses are obtained in only one scenario (price of zeolite equal to 920 €/ton). In this
project. Economic losses are obtained in only one scenario (price of zeolite equal to 920 €/ton). In this situation,
it is opportune
situation, to elaboratetoaelaborate
it is opportune BEP analysis.
a BEPIt analysis.
defines the
It value ofthe
defines the value
price of
of zeolite from
the price of which
zeoliteafrom
null
value
whichof NPVvalue
a null is obtained—Figure 7.
of NPV is obtained—Figure 7.

NPV (k€)
8260

2170
0

-4942

920 €/ton 1070 €/ton 1150 €/ton 1380 €/ton

Price of zeolite
 Figure 6. Sensitivity analysis—Cost opportunity of capital.

Results that were obtained in these alternative case studies confirm the profitability of the
project. Economic losses are obtained in only one scenario (price of zeolite equal to 920 €/ton). In this
situation, it2019,
Sustainability is opportune
11, 113 to elaborate a BEP analysis. It defines the value of the price of zeolite15from
of 19
which a null value of NPV is obtained—Figure 7.

NPV (k€)
8260

2170
0

-4942

920 €/ton 1070 €/ton 1150 €/ton 1380 €/ton

Price of zeolite

Figure 7. Break even point analysis—Price of zeolite in presence of disposal fee.

BEP underlines that the profitability of this project is strictly linked to the price of zeolite. In the
baseline scenario,
scenario, aa consistent
consistentprofit
profitisisobtained
obtained(equal
(equaltoto2170 2170k€),
k€),but
butinina apessimistic
pessimistic scenario,
scenario, a
arelevant
relevanteconomic
economicloss lossisisreached
reached(equal
(equalto −4942k€).
to−4942 k€).From
Fromaamathematical
mathematicalpoint pointofofview,
view, the price
of zeolite that
that characterizes
characterizes NPV NPV== 00 isis contained
containedin inthe
therange
rangefrom
from920920€/ton
€/ton to 1150€/ton.
to 1150 €/ton. The high
level of accuracy of this analysis
analysis defines
defines the
the value
value of 1070 €/ton
of 1070 €/ton that is close to the baseline value and
it is lower than 7%.
other critical
The other criticalvariables,
variables,instead,
instead, dodo
notnot modify
modify the the profitability
profitability of project.
of the the project.
In fact,In NPV
fact,
NPV
presentspresents its value
its lower lower(equal
value to(equal to 1100
1100 k€) whenk€)thewhen
cost ofthe
thecost of waste
liquid the liquid
is 144waste this€/ton.
€/ton.isIn144 same
In this same
scenario, DPBTscenario,
is equalDPBT is equal
to four yearstothat
fouris,years that is,
however, a however,
reasonablea value
reasonable value forItinvestors.
for investors. remains
It remains
fixed equalfixed equal
to two to two
years when years
thewhen the cost opportunity
cost opportunity of capitalofiscapital is modified.
modified. NPV increased
NPV increased by 18%by if
18% if the cost opportunity of capital is equal to 3%, while it decreased by 15%
the cost opportunity of capital is equal to 3%, while it decreased by 15% when this variable is equal when this variable is
equal
to 7%.to 7%.
DPBT in other scenarios varies from two years to three years. There is a particular situation, situation,
only when the price of zeolite is modified. The investment is recovered already after one year if the
price of zeolite is fixed to 1380 €/ton, while the value >15 indicates that during the lifetime of the
project, the value of discounted cash inflows never will be match one of discounted cash outflows.
In this scenario, IRR cannot be calculated, since all cash flows are always negative (n.d. acronym
stands for “not definable”). In other scenarios, the minimum value is equal to 34.1%, which is
significantly greater than the cost opportunity of capital used in this analysis.
GMR proposes a comparison between revenues and operating costs. Such an index is positive,
even in the worst scenario (equal to 0.4%). In fact, the value of annual revenues is greater than the
operating costs, but, when also considering investment costs, the profitability is not accomplished.
This demonstrates as this index has a great limit. The value is significantly low, but it does not give
any information on relevant data of a project (as cost opportunity of capital and lifetime of the project).
The same is verified also for ROI.
The concept of circular economy requires not only to preserve the environmental value through
initiatives of recovery/recycling as those defined in this work, but also at the same time economic
opportunities must be developed. The sole recovery of REEs from spent E-cat is absolutely unprofitable,
so the production of zeolite plays a key-role. However, also the presence of a disposal fee is required to
make recycling of spent E-cat profitable. In this direction, another alternative scenario can be evaluated
considering the absence of a disposal fee. A BEP analysis is conducted on the price of zeolite—Figure 8.
initiatives of recovery/recycling as those defined in this work, but also at the same time economic
opportunities must be developed. The sole recovery of REEs from spent E-cat is absolutely
unprofitable, so the production of zeolite plays a key-role. However, also the presence of a disposal
fee is required to make recycling of spent E-cat profitable. In this direction, another alternative
scenario can
Sustainability be11,
2019, evaluated
113 considering the absence of a disposal fee. A BEP analysis is conducted
16 ofon
19
the price of zeolite—Figure 8.

NPV (k€)
2032
0

-5149
-8679

-15298

920 €/ton 1070 €/ton 1150 €/ton 1305 €/ton 1380 €/ton
Price of zeolite

Figure 8. Break even point analysis—Price of zeolite in absence of disposal fee.

Results highlight
highlight that
thatthe theprofitability
profitabilityofof baseline
baseline scenario
scenario with
with a price
a price of zeolite
of zeolite equalequal to
to 1150
€/ton €/ton
1150 is no longer
is no longer verified.verified.
In fact,In
NPV fact,isNPV is negative
negative and is equal −5149tok€−(a
and istoequal 5149 k€ (a difference
difference of about
of about 7319 k€—see Figure 7). At the same time, in the optimistic scenario
7319 k€—see Figure 7). At the same time, in the optimistic scenario in which the price of zeolite in which the price ofis
zeolite
increasedis increased
by 20%, NPV by 20%, NPV is(equal
is positive positive (equal
to 2032 to This
k€). 2032 economic
k€). This economic resultthan
result is lower is lower than
that from
that from the baseline
the baseline scenario scenario
(2170 k€), (2170 k€), despite
despite that thethatprice
the price of zeolite
of zeolite is is 230 €/ton.
increasedofof 230
increased €/ton.
Consequently, the zeolite has a key-role in the economic analysis, but in absence of disposal fee for
E-cat collection, the profitability is significantly lower. The profitability is achieved with a price of
the zeolite equal to 1305 €/ton without the
€/ton without the disposal
disposal fee. Majority
Majority ofof zeolites are manufactured using
alkaline and alkaline earth metals. The most common natural zeolites include analcime, analcime, chabazite,
chabazite,
clinoptilolite, erionite, ferrierite, heulandite, laumontite, mordenite, and and phillipsite.
phillipsite. Natural and
synthetic zeolites
zeolitesare most
are mostcommonly
commonly usedused
in various end-useend-use
in various industries, owing to owing
industries, varioustoproperties,
various
including
properties,unique adsorption,
including uniquemolecular
adsorption,sieve,molecular
superior catalytic, and ion-exchange
sieve, superior catalytic, properties. Natural
and ion-exchange
zeolites were
properties. the largest
Natural zeolitesproduct segment,
were the largestaccounting for overaccounting
product segment, 60% of thefor global
overmarket
60% of volume
the globalin
2014. Synthetic zeolites market demand has been tremendously increasing
market volume in 2014. Synthetic zeolites market demand has been tremendously increasing over over the past few years.
Most common
the past synthetic
few years. Mostzeolites
common include types
synthetic A, X, Y,
zeolites and ZMS-5.
include types The
A, X,segment accounted
Y, and ZMS-5. Thefor nearly
segment
40% in 2014for
accounted and share 40%
nearly is expected
in 2014toandincrease
shareby is the end of to
expected 2022. Growing
increase by utilization
the end of of theseGrowing
2022. zeolites
in the petroleum
utilization of theseindustry,
zeolites owing to its abilityindustry,
in the petroleum to purifyowing
gas streams, is expected
to its ability to be
to purify gasthe primary
streams, is
factor
expectedfor to
thebedemand growth
the primary overfor
factor thethe
forecast
demand period. The over
growth global
thezeolite market
forecast wasThe
period. valued
globalat around
zeolite
USD 3.50 billion in 2014 and it is expected to reach USD 4.50 billion in 2020 and over 2000 ktons of
zeolites produced worldwide, both natural and synthetic [39].

4. Conclusions
In this paper, a novel recycling process was developed for the full recycling of spent E-cat,
also known as FCC catalyst. Lanthanum and cerium were recovered by a leaching stage with sulfuric
acid solution, thus precipitated as RE sulphates with NaOH. The solid residue from the leaching
stage is used for the synthesis of zeolite. The analysis demonstrated that zeolite Na-A is the most
concentrated phase, and minor amounts of Na-X and sodalite are also present. Nevertheless, changing
the synthesis conditions (amount of Na2 CO3 , roasting, and hydrothermal stage temperature and time)
it could be possible to maximize the Na-A phase. This is the aim of the next experimental campaign.
Spent sulfuric acid solution is regenerated by nanofiltration, and also most of the water is recycled
back after treatment.
The economic analysis demonstrated that the process is profitable if the solid residue from the
leaching stage is used for production of zeolite; moreover, another important revenue of the plant is
the disposal fee for the E-cat. The current metal market prices do not make the recovery of La and Ce
profitable, as their concentration in spent E-cat is rather low. The baseline scenario is profitable and
Sustainability 2019, 11, 113 17 of 19

several alternative case studies present a positive sign of NPV. However, the profitability cannot be
verified in two case studies:

• The first concerns the price of zeolite, when such value is lower than 1070 €/ton in presence of
the disposal fee for E-cat collection.
• The second regards the price of zeolite when this value is lower than 1305 €/ton in the absence of
the disposal fee for E-cat collection.

The process and the relevant plant, thus, demonstrated a reliable and useful management of spent
E-cat; although part of such catalyst is already used for the partial replacement of cement and mortar
powders, powder in refractory materials and mineral woods, the majority of it is still landfilled. Hence,
it is crucial to find the market for such synthetic zeolites, which have many industrial uses and could
certainly reduce the consumption of natural zeolites that are mined worldwide and the amount of
spent E-cat landfilled every year.

Author Contributions: Conceptualization, F.F.; methodology, S.L. and I.D.M.; software, S.L.; validation, F.V.;
investigation, F.F. and V.I.; data curation, V.I.; writing—original draft preparation, F.F. and I.D.; writing—review
and editing, I.D.; visualization, I.D.M.; supervision, F.V.
Funding: This research did not receive any specific grant from funding agencies in the public, commercial, or
not-for-profit sector.
Acknowledgments: The authors would like to warmly thank Orim S.p.A., whose President Alfredo Mancini,
MEng., and R&D Manager Fabio Maggiore, MEng, have supplied the FCCC sample and other precious background
information. Moreover, our research group at the University of L’Aquila wants to dedicate such work to Orim’s
former CEO Andrea Mancini, who prematurely passed away in 2017. We all remember his efforts and diligence in
the recovery and recycling of industrial waste.
Conflicts of Interest: The authors declare no conflict of interest.

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