Catalysis Letters (2019) 149:272–282

https://doi.org/10.1007/s10562-018-2596-9

Manufacture Process Scale-Up and Industrial Testing of Novel

Catalysts for ­SOx-Emissions Control in FCC Units
R. Quintana‑Solórzano1 · A. A. Neri‑Gómez1 · H. Armendáriz‑Herrera1 · Jaime S. Valente1

Received: 11 September 2018 / Accepted: 11 October 2018 / Published online: 1 November 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Novel ­SOx-reducer ­(ReSOx) catalysts containing an Mg–Al–Fe anionic clay as precursor and primary constituent have been
scaled-up for commercial application in fluid catalytic cracking (FCC). The catalysts are manufactured, on a large scale,
through a facile, energy-wise, environment-friendly and economical procedure which, advantageously, does not require
external binding agents to produce fluidizable microspheroidal particles. Ce is added into the catalysts’ composition in
varying amounts to extend their flexibility for usage in partial or full combustion regenerators. When tested industrially in
a 40 MBPD (1000 barrels per day), 180 ton of catalyst inventory, partial combustion FCC unit, R ­ eSOx-catalysts exhibit a
notably high ­SOx reduction activity removing around 35 kg ­SO2 per kg of catalyst, without detecting upsets neither in the
base cracking performance nor in coke production in a continuous 48-days run.
Graphical Abstract

Keywords Catalytic cracking · FCC unit · SOx emissions · ReSOx-catalysts · Cracked products · Efficiency for ­SOx removal

Extended author information available on the last page of the article

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Manufacture Process Scale-Up and Industrial Testing of Novel Catalysts for ­SOx-Emissions…
1 Introduction
Sulfur oxides is the term used to denote ­SyOx-type com-
pounds, ­S O x referring specifically to S ­ O 2 and S­ O 3, the
most abundant species. The presence of S ­ Ox in atmosphere
is closely connected to primary and secondary industrial
activities, wherein sulfur-containing fossil fuels are burned
[1]. Besides reacting with ambient moisture to yield the
so-called acid rain, ­SOx adsorb onto fine particulate mat-
ter to form sulfate aerosols that harm to ozone layer. Also,
acid rain alters ecosystems’ equilibrium by modifying the
chemistry of forest soils and increasing the pH of water
bodies. Further, some human diseases of respiratory sys-
tem are related to S ­ Ox exposition [2]. Seeing that power
stations and other industrial facilities (e.g., oil refineries)
discharge around 90 wt% of total worldwide ­SOx emis-
sions, environmental awareness has encouraged state and
local authorities to establish stringent regulations to con-
trol ­SOx emission from fixed sources [3, 4].
Centering attention on the oil refining sector, the fluid
catalytic cracking (FCC) process, which is focused on
producing automotive fuels (gasoline and diesel) as well
as light olefins via the conversion of low-value sulfur-
containing heavy distillates termed gas oils, contributes
with near 90% of refinery’s and almost 7% of global ­SOx
discharges [5, 6]. Gas oils contain 0.1–4 wt% of sulfur
which, after cracking, distributes into the different reac-
tion products, i.e., 45–55 wt% to H ­ 2S, 35–45 wt% to liquid
fractions and 3–10 wt% to coke [7, 8]. ­SOx are specifically
produced in the regenerator of FCC units (FCCU), a sec-
tion wherein the coked catalyst is regenerated with air to
restore its cracking activity.
Varied strategies have been adopted in FCCU to control
­SOx emissions. Yet, purchasing low-sulfur content feeds
and hydrotreating (HDT) of gas oil streams represent very
effective routes, the former depends strongly on hydro-
carbons availability, while the latter implies large capital
and operating costs [9]. Using special S ­ Ox-reducer cata-
lysts (or additives) is recognized as an effective, practi-
cal, rapid response and economical option for reducing
in situ ­S O x emissions [10, 11]. Circumscribed to the
converter of FCCU, the catalytic cycle for S ­ O x abate-
ment by ­S O x-catalysts comprises four steps: (i) oxida-
tion of ­SO2–SO3 in the regenerator over a metallic oxide,
(ii) chemisorption of S ­ O3 to produce a moderately stable
metal sulfate in the regenerator, (iii) reduction of metal
sulfate to metal sulfide in the riser and, (iv) hydrolysis of
metal sulfide with stream in the stripper to release ­H2S and
restore pristine metallic oxide [4, 12, 13]. Seeing that par-
ticles of S
­ Ox-catalyst circulate together with those of main
cracking catalyst thorough the FCCU, they must possess
suitable mechanical properties, i.e., average bulk density
273
(ABD), attrition index (AI) and particle size distribution
(PSD). Aside, main cracking should remain unaltered with
the addition of ­SOx-catalysts into the FCCU to retain the
process’ profitability [14].
Taking into account the acid nature of ­SOx gases, basic
solids based on MgO, ­Al2O3, ­MgCO3, ­MgAl2O4 spinels,
CaO, ­CaCO3 and mixtures thereof, have been commonly
used to make catalysts for S­ Ox-emissions control in FCCU
[10, 15, 16], In recent publications [17, 18], basic mixed
oxides resulting from calcination of multimetallic anionic
clays (MACs) displayed enhanced properties for sorbing
­SOx. MACs are widely applied in catalytic heterogeneous
processes due to synergy of their metallic constituting ele-
ments, thermal stability, high surface area and mesoporos-
ity [19, 20]. Generally, MACs are prepared by co-precip-
itation, an intrinsically unfeasible synthesis method for
industrial-scale production of solids due to its high ener-
getic demand, excessive water consumption and inevita-
ble waste generation [21]. A simple, environment-friendly,
industrially scalable and economic novel synthetic proce-
dure that avoids most inconveniences of co-precipitation
route was disclosed lately [22–25]. When applied for pro-
ducing ­SOx-catalysts for FCC, an outstanding feature of
such a procedure is the fact that microspheroidal particles,
with proper mechanical properties to be used in circulating
FCC plants, can be made without needing external binding
agents [26].
Synthesized at our lab-scale facilities, R­ eSOx-catalysts
were reported to display a good performance when tested
at the pilot-scale using commercial resembling process
conditions [27]. However, considering the complexity
of the FCC process and the impact of scale differences
between pilot and industrial reactors, pilot plant results
should not be directly transferred into the industrial sce-
nario. The energy balance is, in fact, the most important
variance between industrial and pilot plants, leading to
changes in coke yields, catalyst-to-oil ratio and product
distribution. Therefore, an industrial testing would be
necessary to determine the real efficiency of the ReSOx
catalyst.
This work, hence, pertains to the manufacture procedure
scale-up and industrial-scale testing of novel ­SOx-catalysts
to remove in situ ­SOx emissions in the regenerator of FCCU.
The basic constituent of the catalysts is a Mg–Fe–Al con-
taining MAC which, with the addition of ceria in variable
amounts, gives a flexible material for use in partial or full
combustion regenerators. Microspheres of catalyst with suit-
able mechanical properties for fluidization are produced on
large scale, without requiring external binding agents, via a
simple, energy-wise, environment-friendly and economical
procedure. A R­ eSOx-catalyst is then tried out in continuous
in a 40 MBPD (1000 barrel per day) commercial FCCU,
which is equipped with a partial combustion regenerator.
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2 Experimental and Procedures
2.1 Catalyst Preparation
ReSO x -catalysts were prepared at the facilities of
INTERCAT-Johnson Matthey Co, in the U.S. Aimed at
generating ­SO x-removal industrial data in a continuous
testing of around 1 month and half length, for this end,
about 11 × 10 3 kg of catalyst were manufactured. The
­ReSOx-catalysts’ synthetic procedure corresponds essen-
tially to the one described elsewhere [26, 27], whereas
the required amount of the different reagents, i.e., MgO,
Fe(NO3)3, Ce(NO3)3, boehmite, C ­ H3COOH and water, has
to be adapted in terms of the target quantity of catalyst.
During catalysts’ production, the key synthesis parameters,
namely, temperature, stirring time and speed, aging time,
etc., were carefully supervised. Succinctly, such a proce-
dure comprised the following general steps.
(i) In a first container, ­CH3COOH (85 wt%) was dissolved
in water. Then, MgO (96.57 wt% purity) was gradu-
ally added into the acidic solution under continuous
stirring. The resulting mixture was cyclically passed
through an in-line high shear mixer for 3.6 ks to disag-
gregate and peptize uniformly the particles of MgO
yielding Mg(OH)2 with a brucite crystalline structure.
(ii) In a second container, Fe(NO3)3 (98.5 wt%) together
with Ce(NO3)3 was dissolved in water. Boehmite was
then added into the previous solution and, subsequently,
the resulting blend was vigorously stirred for a suffi-
cient time to produce a consistent, lump-free brownish
gel wherein both cerium and iron are highly dispersed.
(iii) The brownish gel containing Al, Fe and Ce made in the
second container was transferred into the first container
thus producing an admixture that was maintained at
373 K, which was later stirred at 500 rpm (revolutions
per minute) while passing through an in-line high shear
mixer for around 11 ks to form a slurry.
(iv) Corresponding to the “unshaped” catalyst precursor,
the slurry was then subjected to a spray-drying step
with hot air at 673 K and feed pressure of 3.9 kPa to
evaporate the aqueous phase and produce microspheres
of catalyst. No additional binding agents were added in
this step.
(v) The spray-dried microspheroidal particles of the as-
synthesized catalyst precursor were finally calcined at
1005 K for 14.4 ks for activation.
Note that in step (ii) Ce, which evidently is not part a
constituent part of MAC, was incorporated into the cata-
lyst composition to function as efficient oxidation pro-
moter [28]. The characterization results included further
13
R. Quintana‑Solórzano et al.
in Sect. 3.1, indicate that at the end of stage (iii) the
Mg–Fe–Al layered double hydroxide phase was formed
by an isomorphic substitution of Fe and Al into the brucite
crystalline structure. Notice that Ce, which has a relatively
large atomic radius, did not participate in such an isomor-
phic substitution. As will be also demonstrated below in
Sect. 3.1, the as-synthesized catalyst precursor produced in
stage (iv) actually consisted of mixture of two independent
crystalline phases, specifically, the Mg–Fe–Al containing
MAC, and ­CeO2. The latter is, in fact, the component of
the ­ReSOx-catalysts that increases the rate of the conver-
sion of ­SO2 into ­SO3, in accordance with the two chemi-
cal reactions represented by Eq. 1 and Eq. 2 below, an
essential starting step in the process of ­SO x removal as
pointed out above.
2CeO2 + SO2 → Ce2 O3 + SO3 (1)
Ce2 O3 + 12 O2 → 2CeO2 (2)
Also, recall that, in the regenerator of the FCCU, ­SO3
composing the combustion gases reacts with a metallic
oxide (MeO) composing ­ReSOx-catalysts to produce a metal
sulfate ­(MeSO4), a species that is stable in the regenerator
(Eq. 3) but reduces in the riser (Eq. 4, Eq. 5). Metal sulfides
(MeS) produced in the riser are hydrolyzed in the stripper
of the FCCU thus restoring the MeO (Eq. 6) and producing
­H2S.
MeO + SO3 → MeSO4 (3)
MeSO4 + 4H2 → MeO + H2 S + H2 O (4)
MeSO4 + 4H2 → MeS + 4H2 O (5)
MeS + H2 O → MeO + H2 S (6)
2.2 Characterization of ­ReSOx‑Catalysts
Catalysts were subjected to an X-ray fluorescence (XRF)
analysis to determine the content of the constituent metal-
lic oxides, to wit, MgO, A ­ l2O3, ­Fe2O3 and C­ eO2. This
analysis was done in a Siemens X-ray SRS 3000 Spectrom-
eter. It is worth commenting that MgO was also used as a
tracer compound to quantify indirectly the real amount of
­ReSOx-catalysts circulating in the FCCU inventory during
the course of the testing by analyzing samples of composite
flowing catalyst. Being uncommon and impractical, analyses
of independent ­ReSOx-catalyst samples during the course
of the testing were not performed as it is in admixture with
the main catalyst.
Specific surface area of catalysts was obtained out of
­N2 physisorption isotherms determined at 77 K in a Quan-
tachrome Autosorb-1C equipment, in agreement with
ASTM-D-3663 method. Prior to N ­ 2 adsorption, samples
Manufacture Process Scale-Up and Industrial Testing of Novel Catalysts for ­SOx-Emissions…
were outgassed overnight at 623 K. Surface specific area
values were ultimately estimated by means of BET equation.
X-ray diffraction (XRD) analyses of catalysts were car-
ried out at room temperature in a Siemens D-500 diffrac-
tometer that is equipped with a Cu-Kα radiation source
(1.5406 Å). It was operated at 35 kV and 25 mA, within the
2θ range 4°–70° using a step size of 0.03°. Average crys-
tal size (ACS) was calculated from indicated reflections in
agreement with the Debye-Scherer equation, L = K λ [B(θ)
cos(θ)]−1; L is the average crystal size, K the shape fac-
tor, λ the radiation wavelength, B(θ) the full width at half
maximum (FWHM) and θ the diffraction angle. For analysis
purposes, samples were formerly placed in a glass sample
holder with as dimensions 2.5 cm diameter × 0.5 mm depth.
Catalysts were subjected to a scanning electron micros-
copy (SEM) in a Phillips XL 30 environmental electron
microscope. The chemical composition and bidimensional
spatial distribution of elements was examined via X-ray
Mapping using an energy-dispersive X-ray spectrometer
(EDS) device attached to the microscope. Prior to the EDS
analysis, microspheres of catalyst were embedded in a car-
bon film.
Catalysts were also analyzed via a high-resolution trans-
mission electron microscopy (HRTEM). Micrographs were
obtained in a TITAN 80-300 equipped with a Schottky type
field emission gun operating at 300 kV. The resolution point
and information limit were better than 0.085 nm. HRTEM
digital images were obtained using a CCD camera and Digi-
tal Micrograph Software from GATAN. Elementary com-
position was determined by EDS equipped with an EDAX
spectrometer fitted to the TEM. Previous to the analysis, the
catalyst in the powder form was ultrasonically dispersed in
ethanol and then supported on holey carbon coated copper
grid.
ABD, which is related to the capacity of microspherical
bodies to fluidize, was obtained via the ISQ 941.02 method.
Associated to the resistance to a particle size decrease under
controlled turbulent motion, AI was determined using the
ASTM-D-5757 method. PSD, which was obtained via the
ASTM-D-4464 method, is an important indicator of the flu-
idization of microspheres as, for instance, a large number of
fine particles, i.e., below 40 μ, would result relatively high
catalyst losses even though this fraction fluidizes better.
2.3 Commercial Run of a ­ReSOx‑Catalyst
A 48-days industrial run was performed in a MW Kellogg
Orthoflow FCCU with a nominal processing capacity of 40
MBPD (~ 6400 m3/day, considering the value of specific
gravity of the feedstock included in Table 1) and a crack-
ing catalyst inventory of 180 × 103 kg. This industrial unit
is provided with a regenerator that is operated in the partial
combustion mode in which, a sub-stoichiometric amount
275
Table 1  Average properties of the feedstock processed in the FCCU
during the industrial testing of a ­ReSOx-catalyst
Property Value
Specific gravity 298/277 K(°API) 0.911 (23.32)
Boiling point distribution
IBP/FBP (K) 502/830
30/50/70 vol% (K) 687/721/753
Average boiling point (K) 830
Aniline temperature (K) 351
Conradson residual carbon (wt%) 0.29
Refraction index, 0/20 1.5261
K-UOP 11.91
Sulfur (wt%) 2.33
Total nitrogen (ppm) 1,349
of air (oxygen) related to what is required for burning off
the coke produced during cracking reactions is supplied.
Apart from working at oxygen deficient conditions, partial
combustion regenerators operate at a lower temperature
compared with full combustion counterparts indicating
that the rate of the combustion reactions taking place in
the former is lower. In other words, the oxidation rate of
­SO2–SO3, a key oxidation step in the cyclic operation of
­SOx-catalysts, is slower in partial combustion regenera-
tors. Increasing the amount of ceria (the oxidation pro-
moter compound) in the formulation of ­ReSOx-catalysts
is aimed at compensating the slower rate of S ­ O3 formation
in partial combustion regenerators, as was qualitatively
pointed out above in Sect. 2.1.
Average properties of the equilibrium cracking catalyst,
a rare earth ultra-stable Y zeolite based material, that circu-
lates through the FCCU were as follows: MAT activity = 76,
specific surface area = 166 m2/g, unit cell size = 24.29 nm,
pore volume = 0.40 cm3/g, ABD = 0.825 g/cm3, Ni = 221
­ppmw, V = 933 ­ppmw and Na = 5500 p­ pmw. Table 1 displays
values of the average properties of the feedstock processed
during the commercial run whilst, additionally, Table 2, in
turn, shows some relevant information related to mean val-
ues of the FCCU process conditions used in the run.
In the testing, 6000 kg of a R­ eSOx-catalyst was used in
the as-received form. During the 48-days continuous trial,
­SO2 concentration in the combustion gases emitted by the
regenerator of the FCCU was cautiously tracked. For this
end, a portable COSA Model 704 analyzer equipped with
electrochemical cells was utilized. Likewise, attention was
paid to the main cracking performance of the unit by evalu-
ating available information related to feedstock conversion,
products distribution and coke deposition.
Conveniently, the ­ReSOx-catalyst test has been divided in
five general consecutive stages, which are briefly explained
in the coming lines:
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276
Table 2  Mean values of representative operating conditions for the
industrial testing of a ­ReSOx-catalyst
Feedstock Value
Inlet flow rate, MBPD 36
Preheating temperature (K) 480
Riser
Catalyst-to-oil ratio (kg/kg) 9.2
Outlet temperature (K) 802
Regenerator
Temperature of the dense phase (K) 950
Oxygen content in the flue gas (mol%) 0.29
CO content in the flue gas (mol%) 0.41
CO2 content in the flue gas (mol%) 11.52
Inlet flow rate of air ­(m3/h) 110 × 103
Stage I—measurement of the baseline of uncontrolled
­SO2 emissions for 7 days: the flue gas was continuously
monitored for ­S O 2 concentration without loading any
­ReSOx-catalyst into the FCCU.
Stage II—addition of 1000 kg of R ­ eSOx-catalyst within a
period of 9 days: 200 kg of catalyst were added into the unit
distributed in three independent additions of 66.6 kg. In the
following 8 days, 800 kg more of catalyst were incorporated
into the FCCU adding 100 kg per day.
Stage III—addition of 2000 kg of ­ReSOx catalyst within a
period of 10 days: The catalyst was now loaded into the unit
at a rate of 200 kg/day delivering three individual catalyst
loadings per day.
Stage IV—addition of 3000 kg of ­ReSO x-catalyst
within a period of 10 days: the blending rate of catalyst
was further increased to 300 kg per day making three addi-
tions a day. Notice that at the end of this stage, 6000 kg of
­ReSOx-catalyst had been added into the FCCU.
Stage V—return to the value of uncontrolled ­SOx emis-
sions: from this point on, no more ­ReSOx-catalyst was
added into the unit. The ­SO2 concentration in the flue gas
was tracked in a continuous fashion the necessary time until
returning to the baseline uncontrolled ­SOx emissions (vide
Stage I).
2.4 Efficiency of the ­ReSOx‑Catalyst
In order to assess the capacity of the R­ eSOx-catalyst to
remove ­SOx, its efficiency (or pick-up factor) was deter-
mined in accordance with the expression represented by
Eqs. 4 and 5. It actually corresponds to the ratio between
­ O2 removed and mass of catalyst added. Typical
mass of S
values of efficiency in commercial FCCU range from 4 to
40 kg ­SO2/kg of catalyst. Even though values of efficiency
depend upon diverse factors, they are largely conditioned
by the amount of oxygen incorporated into the regenerator
13
R. Quintana‑Solórzano et al.
Table 3  Specific surface area and chemical composition of the
­ReSOx-catalysts after shaping into microspherical particles via spray-
drying and subsequent calcination at 1005 K
Specific surface area ­(m2/g) Composition (wt %)
MgO Al2O3 Fe2O3 CeO2
151 62 18 4 16
of the unit. It is known that efficiencies are noticeably larger
in units equipped with full combustion regenerators for the
technical reasons outlined above.
BLESO2 − CESO2
Efficiency = (7)
Wcat
BLESO2 corresponds to Base Line S ­ O2 Emissions on
mass basis, i.e., in the absence of any ­ReSOx-catalyst,
CESO2 is used for denoting the Controlled ­SO2 Emissions
also on mass basis, whereas ­Wcat is the accumulated mass
of ­ReSOx-catalyst incorporated into the FCCU.
3 Results and Discussion
3.1 Physico‑Chemical Properties
of the ­ReSOx‑Catalyst Tested Industrially
Table 3 summarizes infomation related to the specific sur-
face area and composition, the later specifically referred to
the correspoding metallic oxides. The constituent compo-
nents of the catalyst in decreasing order of amount are MgO,
­Al2O3, ­CeO2 and ­Fe2O3. Notice that more than 60 wt%. of
the catalyst corresponds to MgO, while amount of ceria,
the component that acts as oxidant promoter, is as high as
16 wt%.
The formation of crystalline phases was closely followed
during the synthesis procedure described in Sect. 2.1, via
XRD analyses. Essential was to detect the crystalline phases
associated to as-synthesized catalyst precursor after shaping
into microspheres via spray-drying in stage (iv) and subse-
quently to the ­ReSOx-catalysts resulting from stage (v) that
comprises microspherical particles subjected to calcination
at 1005 K. It is first observed in Fig. 1, which displays the
XRD spectrum of the as-synthesized catalyst precursor, that
no other crystalline phases than layered double hydroxide
and ­CeO2 are constituting the solid. Specifically, the pres-
ence of MAC phase is evidenced by sharp harmonic 001
reflections at low 2θ values, i.e., 11° and 23°, and weaker in-
plane reflections at higher angles. Diffraction peaks located
at 28°, 47° and 56° are associated to the C ­ eO2 in a cubic
fluorite structure.
Manufacture Process Scale-Up and Industrial Testing of Novel Catalysts for ­SOx-Emissions…
Fig. 1  X-ray diffraction spectra of the as-synthesized catalyst after
shaping into microspheres via spray-drying
­ReSOx-catalyst particles are included in Table 4. Notice
Fig. 2  X-ray diffraction spectra of the ­ReSOx-catalyst after shaping
into microspherical particles via spray-drying and subsequent calci-
nation at 1005 K
­ReSO x-catalyst is a characteristic to be highlighted as,
The XRD spectrum of the ­ReSOx-catalyst is, in turn,
presented in Fig. 2. First, diffraction peaks at 36.5°, 42.5°
and 62.4° denotes the formation of MgO in rock-salt
crystal structure. Clearly, as a result of the calcination
step, MAC phase transforms into a mixed metallic oxide.
Brucite, Mg(OH)2, and other crystalline phases such as
boehmite are no longer observed in the XRD pattern of
calcined sample resulting from stage (v). Aside, the fluo-
rite like cubic structure of cerium oxide, which consists
277
of a simple cubic oxygen sub-lattice with cerium ions
occupying alternate cube centers, is preserved after cal-
cination. The XRD spectrum in Fig. 2 also indicates that,
­ eO2 crystalline phase is preserved
after calcination, the C
albeit with a higher crystal size in comparison with what
is observed in the XRD of Fig. 1,
As the original MAC structure collapses during the cal-
cination step due to temperature, Fe and Al are expected
to be well dispersed inside the MgO crystalline structure.
Aside, as Ce is transformed into C ­ eO 2 concomitantly
with the formation of MAC crystalline structure, ceria is
highly dispersed within the catalysts particles. In our pre-
vious works [26, 27], the SEM/EDS analysis allowed to
prove that all the metallic components referred to above
were well dispersed within the R ­ eSOx-catalyst particle.
A uniform distribution of the metallic components has an
enhancing effect on the performance of S ­ Ox-reducing cata-
lysts. As cited formerly, the addition of iron into catalyst
formulation aims to modulate the overall solid’s basicity
and, at the same time, increasing the catalyst’s susceptibil-
ity to regeneration at the reducing conditions in the riser.
As no large clusters of ­Fe2O3 are detected, iron’s capacity
to catalyze unwanted dehydrogenation reactions is practi-
cally suppressed.
SEM micrographs of the ­ReSOx-catalyst displayed in
Fig. 3 confirms that it comprises microspheroidal parti-
cles with rather regular sizes of around 70 μ. The value
of a the most meaninfgul mechanical properties of the
that ABD is higher than 0.85 g/cm3 while the AI is lower
than 2.0. Aside, microspheres of the ­ReSOx-catalyst exhib-
its a mean size equal to 76 μ, with a 0–40 μ size fraction
lower than 7 wt%. All these mechanical properties are,
clearly, within the specifications for commercial cracking
catalysts, i.e., ABD of 0.73–1.0 g/cm3, APS of 60–80 μ,
0–40 μ fraction of 6–16 wt% and, therefore, the catalyst
particles are expected to fluidize properly, to exhibit a
high resistance to attrition due to motion and to display
relatively high retention indices reducing the formation of
sharp-edged and irregular particles.
The simplicity of the methodology for producing the
according with the synthesis steps outlined in Sect. 2.1,
the slurry produced in stage (iii) was directly spray-dried
without adding external binding agents to produce micro-
spherical particles in stage (iv) which were, at the end
subjected to a single calcination step at 1005 K in order to
produce the S ­ Ox-reducer catalysts in accordance with stage
(v). It is worth emphasizing that despite the relatively large
content of MgO displayed in Table 4, a metallic oxide
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278 R. Quintana‑Solórzano et al.

Fig. 3  SEM image at × 1000 showing microspheres of the R

­ eSOx-catalyst produced via spray-drying and subsequent calcination at 1005 K

Table 4  Mechanical properties of the R ­ eSOx-catalyst after shaping depicts the progress of the amount, on mass basis, of the
into microspherical particles via spray-drying and subsequent calci- ­SO2 produced in the regenerator of the FCCU throughout
nation at 1005 K
the course of the testing. Conveniently by using differ-
ABD (g/cm3) Attrition Particle size ent colors, the corresponding values of (i) the baseline of
­indexa uncontrolled ­SO2 emissions measured on-site (red mark-
APS (µm) 0–20 µm 0–40 µm
(wt%) (wt%) ers), (ii) the controlled S
­ O2 emissions measured on site
(green markers), and (iii) the projected reference values
0.88 1.65 76 1.0 6.1
of uncontrolled ­SOx emissions (blue markers) have been
a
Determined via the Grace Davison method number 163,070—high included in Fig. 4. The information accounted for in item
severity attrition index (postreatment: 24 slpm—standard litters per (iii) was required to determine formally the amount of S­ Ox
minute for 2 h at room temperature) removed from the FCCU due to the continuous additions
of ­ReSOx-catalyst. In other words, the S
­ Ox emissions with-
with poor physical and mechanical properties, in the cata- out having loaded any ­ReSOx-catalyst had to be predicted
lyst the ABD and AI are adequate, corresponding to an for Stages II–IV. For this end, the correlation between the
additional advantageously feature of the layered double sulfur in coke and the sulfur in slurry reported elsewhere
hydroxide-based catalyst for ­SOx abatement. [29] was applied. The amount of coke was calculated from
the whole mass and thermal balances. The sulfur content
3.2 Commercial Plant Performance in the slurry, in turn, was determined on a daily basis via
the method ASTM-D-4294.
3.2.1 SOx in the Flue Gas Having a look at the plot in Fig. 4, it is evident that
the FCCU responded quickly to the first ­ReSOx-catalyst
In the following lines, the most relevant results of the loading noticing a sudden decline in the S ­ Ox emissions
industrial run, taking into consideration the five stages emitted from the regenerator. Next, from day 8 to day 36,
comprising the testing protocol presented formerly in ­SOx emissions continued decreasing monotonically reach-
Sect. 2.4, are outlined and discussed. The graph in Fig. 4a ing a minimum as low as 530 ppm. Then, from day 37
displays the evolution of the regenerator flue gas ­SO2 con- on ­S O x emissions augmented continuously as no more
centration during the course of the testing as a function ­ReSOx-catalyst was loaded into the unit. By day 48, the
of time. Complementarily, Fig. 4b includes a plot which

13
Manufacture Process Scale-Up and Industrial Testing of Novel Catalysts for ­SOx-Emissions… 279

Fig. 4  Summary of the indus-

trial run of the ­ReSOx-catalyst:
a ­SO2 concentration in combus-
tion gases versus time and, b
­SO2 produced in the regenerator
versus time. Baseline uncon-
trolled ­SO2 emissions (filled
red diamond), Controlled ­SO2
emissions (filled green square),
Projected reference values of
uncontrolled ­SO2 emissions
(filled blue triangle)

Fig. 5  Summary of feed con-

version and yield of cracked
products in vol% versus time of
the industrial run of the ­ReSOx
catalyst: conversion (filled
green triangle), LPG (filled red
circle), and Gasoline (filled
blue diamond). The secondary
Y-axis denotes the real wt%
of ­ReSOx-catalyst in the unit
catalyst inventory

13
280 R. Quintana‑Solórzano et al.

unit returned to its value of baseline of uncontrolled ­SOx Ton of ­SO2. Taking into consideration that the quantity
emissions, ca. 1850 ppm. The most relevant results of the of ­ReSOx-catalysts employed in the complete testing was
industrial run are summarized in the coming lines: equal to 6.0 Ton, the global efficiency yielded 34.8 ­kgSO2
per kg catalyst. Likewise, bearing in mind that the cost of
Stage I the ­ReSOx-catalyst was 17,000 USD per Ton, the average
Regenerator flue gas average flow 96,326 kmol/day expenditure of the catalyst per Ton of trapped S­ Ox was as
rate high as 488 USD.
Average baseline of uncontrolled 1850 ppm
­SO2 emissions
3.2.2 Effect on Main Cracking
Amount of ­SO2 discharged to the 11.4 ton/day
atmosphere
Mass of ­ReSOx-catalyst in the FCCU 0.0 kg When testing an additive in the FCC process, it is important
inventory to verify whether its presence in the catalyst inventory alters
Stage II or not the so-called base cracking performance, namely, the
SO2 emitted to the atmosphere 9.3 ton/day feed conversion, products distribution and coke formation.
SO2 discharged to atmosphere with- 12.2 ton/day Admixing an additive with the main cracking catalyst may
out ­ReSOx-catalyst (i) dilute the activity of the later or/and (ii) induce undesired
Cumulated mass of ­ReSOx-catalyst 1000 kg catalytic effects due to the intrinsic composition of the for-
added into the FCCU​ mer. In the course of the ­ReSOx-catalyst industrial testing
Percentage of S ­ O2 emissions reduc- 25% the mass balances of the FCCU were computed on a daily
tion
basis in order to detect a possible upset in the base cracking
Efficiency 26 kg ­SO2/kg ­ReSOx-catalyst
performance of the unit.
ReSOx-catalyst cost per amount of 649 USD/ton S ­ O2
­SO2 removed Taking into consideration the first 40 days of the indus-
Stage III trial run encompassing Stages I–IV, Fig. 5 displays the pro-
SO2 emitted to the atmosphere 6.0 ton/day gress of the total feed conversion as well as the yield to LPG
SO2 discharged to the atmosphere 12.6 ton/day and gasoline as a function of time, while Fig. 6 shows the
without ­ReSOx-catalyst evolution of the yield to LCO, HCO and coke with time.
Cumulated mass of ­ReSOx-catalyst 3000 kg Notice that a secondary Y-axis is included in both Figs. 5
added into the FCCU​ and 6 for displaying the real concentration of ­ReSOx-catalyst
Percentage of S ­ O2 emissions reduc- 52% in the catalyst inventory of the unit. Such a concentration
tion
was indirectly quantified by determining the MgO content
Efficiency 33 kg ­SO2/kg ­ReSOx catalyst
of samples of composite catalysts taking into account that
ReSOx-catalyst cost per amount of
the pure R ­ eSOx-catalyst contains a known amount of Mg,
­SO2 removed: 516 USD/Ton ­SO2
vide Table 3. It is observed that the incorporation of the
Stage IV
­ReSOx-catalyst into the FCCU did not induce a negative
SO2 emitted to the atmosphere 4.3 ton/day
affect neither on total feed conversion nor on the yield of
SO2 discharged to atmosphere with- 12.4 ton/day
out ­ReSOx-catalyst valuable products such as LPG and gasoline. Also, the yield
Percentage of S ­ O2 emissions reduc- 65 vol% to the unconverted gas oil fractions, to wit, LCO an HCO
tion remained essentially unaffected by the presence of ­ReSOx
Mass of R ­ eSOx-catalyst in the FCCU 6000 kg catalyst in the catalyst inventory. Finally, it is also detected
inventory that the amount of coke, a by-product that has a very impor-
Efficiency 27 kg ­SO2/kg ­ReSOx-catalyst tant role in the thermal balance of the FCCU, did not vary
ReSOx-catalyst cost per mass of ­SO2 628 USD/ton S ­ O2 significantly in the course of the industrial run.
removed
Stage V
The average ­SO2 concentration in the combustion gas leaving the
regenerator was as high as 1354 ppm, while the reduction of S ­ O2
4 Conclusions
emissions amounted to around 36 Ton. After the last addition of
­ReSOx-catalyst into the FCCU at Stage IV, it took 10 days for A novel S ­ Ox-catalyst to remove the S­ Ox species contained
the ­SO2 emissions to return to the value of the so-called “base- in the flue gas of the FCCU has been successfully scaled-up
line uncontrolled S
­ O2 emissions” corresponding to the value
and produced at the large scale (tons) for usage in commer-
measured at Stage I
cial operation to help refineries’ to meet the prevailing envi-
A global analysis of results of the industrial testing ronmental regulations. Manufactured via a simple, energy-
indicates that the R
­ eSOx-catalyst was able to remove 208 wise, environment-friendly and economical procedure, the
­ReSOx-catalysts essentially comprises two crystalline phases

13
Manufacture Process Scale-Up and Industrial Testing of Novel Catalysts for ­SOx-Emissions…
Fig. 6  Summary of yield of
cracked products in vol%
or wt% versus time of the
industrial run of the ­ReSOx
catalyst: LCO (filled red circle),
vol%, HCO, vol% (filled blue
diamond) and coke, wt% (filled
green triangle). The secondary
Y-axis denotes the real wt% of
­ReSOx-catalyst in the FCCU
catalyst inventory
(i) MgO containing Fe and Al resulting from the transfor-
mation of the multimetallic anionic clay, and (ii) cerium
oxide, the latter corresponding to an oxidation promoter. The
usage of metals which are toxic for the main catalyst, e.g.,
vanadium, was avoided. The manufacture procedure has, as
additional feature that does not require the incorporation of
external binding agents to produce microspheres of catalyst
by spray drying the slurry containing the as synthesized
catalyst.
The ­ReSOx-catalysts displayed an outstanding perfor-
mance when tested at very demanding conditions, namely,
in an industrial FCCU equipped with a partial combustion
regenerator which operates at oxygen deficient conditions. In
a continuous 48-days testing, the catalyst was able to remove
35 kg ­SO2 per kg of catalyst without altering the base crack-
ing performance and coke production. The novel catalytic
system presented herein is a viable, low investment, flexible
and effective option for an in situ control of the S
­ Ox species
produced in the FCC process.
Acknowledgements Technical aid from the staff of the Area de Plantas
Piloto at IMP (Ing. Lázaro M. García). Administrative and technical
facilities from PEMEX-Refinación (Ing. Víctor García) and Refinería
of Salina Cruz, Oax. (Ings. Jorge Valdivieso and Alejandrino Toledo.)
Funding Mexican Institute of Petroleum by means of the Research
Project No. D.00355.
Compliance with Ethical Standards
Conflict of interest The authors declare that they have no conflict of
interest.
281
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* R. Quintana‑Solórzano
rquintana@imp.mx
* Jaime S. Valente
jsanchez@imp.mx
A. A. Neri‑Gómez
aneri@imp.mx
13
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H. Armendáriz‑Herrera
harmenda@imp.mx
1
Instituto Mexicano del Petróleo, Eje Central Lázaro
Cárdenas Norte 152, C. P. 07730 Ciudad de México, Mexico