Microporous and Mesoporous Materials 323 (2021) 111216

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Microporous and Mesoporous Materials

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Enhanced selectivity of benzene-toluene-ethyl benzene and xylene (BTEX)

in direct conversion of n-butanol to aromatics over Zn modified
HZSM5 catalysts
Tatinaidu Kella, Debaprasad Shee *
Department of Chemical Engineering, Indian Institute of Technology Hyderabad, Kandi, Sangareddy 502 285, Telangana, India

A R T I C L E I N F O A B S T R A C T

Keywords: The sustainable aromatics production from renewable source is indispensable to circumvallate the dependence
n-butanol on fossil fuel for commodity chemicals. Direct conversion of n-butanol to aromatics using xZn-HZSM5 (0–10 wt
Aromatics %, SiO2/Al2O3 = 23, 55 and 280) catalysts was proposed in the present investigation. Characterization studies
BTEX
revealed the formation of different Zn species depending on the Zn loading. Furthermore, XPS analysis confirmed
Zn-HZSM5
XPS
strong interaction of Zn species with the electronegative oxygen atom of zeolite framework. Zn deposition
Coke analysis enhanced the selectivities of aromatics and BTEX. The presence of Zn species suppressed the hydride transfer
reaction and promoted the dehydrogenation reaction resulting in higher selectivities of aromatics and BTEX. The
rising temperature and declining in WHSV enhanced the selectivities of aromatics and BTEX. The high pressure
had adverse effect on the selectivities of aromatics. The maximum selectivity of total aromatics (74.83%) and
BTEX (68.75%) were achieved at 723 K, 1 bar pressure and 0.75 h− 1 of WHSV. The coke analysis revealed the
formation of polynuclear aromatic coke at high pressure. The alkyl substitute aromatics and polynuclear aro­
matics were formed predominately on pure HZSM5 (55) than 5Zn-HZSM5 (55). A plausible reaction mechanism
was suggested considering the products distribution.

1. Introduction
Dependency on fossil fuels is increasing as the demands for organic
chemicals and fuels are rising continuously because of the improvement
of quality of life, which leads to faster depletion of fossil fuels and causes
harmful effect to the environment. Especially, the demand for the BTEX
(benzene, toluene, ethyl benzene and xylenes) has increased in recent
years [1,2]. BTEX in aromatics family are the most important feedstocks
to the petrochemical industry for the production of array of commodity
chemicals, which are the key ingredients for the manufacture of auto­
motive parts, building materials, perfumery, medicine, etc. [3]. For
example, toluene and xylenes by blending with gasoline are used as
octane enhancers [4]. Another important chemical p-xylene is used for
the production of terephthalic acid, which can be polymerized to pro­
duce polyester and polyethylene terephthalate (PETE) [5–8]. Conven­
tionally, these BTEX are produced via petroleum routes like naphtha
reforming and oil cracking, and non-petroleum routes like aromatiza­
tion of paraffins (methane, ethane, propane, butanes) derived from coal
and natural gas [9–12]. Depletion of fossil fuels and growing global
climate problems are the strong motivation behind the exploration of
alternate sustainable renewable resources to produce the aromatics,
especially BTEX. Renewable sources like solar, wind, thermal, tidal and
geothermal energies can be used to produce electricity and heat energy
but are incompetent to produce liquid fuels and organic chemicals.
Biomass is the only carbon-neutral renewable resource that can be used
to produce liquid transportation fuels and organic chemicals in sus­
tainable manner [13,14]. Biomass derived alcohols (methanol, ethanol,
propanol and butanol) are one such alternative for the production of
aromatics using solid acid catalysts such as zeolites (HZSM, SAPO, H-β,
Mordenite etc.), and metal incorporated zeolites [3,15–17]. It has been
reported in the published literature that the transformation of methanol
and ethanol to aromatics resulted in the formation of undesired higher
aromatics. Alcohols with higher carbon to oxygen ratio, produce hy­
drocarbon with higher theoretical yield [18]. From the structural point
of view, butylenes obtained from n-butanol dehydration are easily oli­
gomerized and aromatized compared to methanol and ethanol derived
olefins because of their lower activation energy [18]. The catalytic ac­
tivity for the production of liquid range hydrocarbons is higher for

* Corresponding author.
E-mail address: dshee@che.iith.ac.in (D. Shee).

https://doi.org/10.1016/j.micromeso.2021.111216
Received 3 February 2021; Received in revised form 6 May 2021; Accepted 31 May 2021
Available online 5 June 2021
1387-1811/© 2021 Elsevier Inc. All rights reserved.
T. Kella and D. Shee
n-butanol compared to methanol, ethanol and propanol [18]. n-butanol
is considered as a fuel, and potentially important diesel and gasoline
additive, to reduce the emissions and soot [19]. Moreover, n-butanol
also has been used as a solvent and feedstock for the production of useful
derivatives [20,21]. In recent years, butanol isomers have drawn
numerous attention to produce butylenes, gasoline range hydrocarbons
and aromatics [3,22–25]. n-butanol is being produced commercially by
propylene hydroformylation to aldehydes followed by hydrogenation
[26]. Traditionally, bio-butanol is being produced from biomass through
ABE (Acetone-Butanol-Ethanol) fermentation of sugars by using clos­
tridium microorganism [27].
Product distribution in the alcohol conversion to aromatics is
affected mostly by the nature of acidic sites and textural properties of the
catalyst. Hence, development of efficient catalysts and choosing the
appropriate process conditions are the key factors, which influence the
aromatic product distribution [22,25,28]. So far, numerous studies on
the conversion of alcohols to various range of hydrocarbons have been
carried out using different types of zeolites such as MFI zeolites, H-β,
faujasite, offretite, and mordenite zeolites [3,22,25,29,30]. Among the
MFI zeolites family, the HZSM5 catalyst has shown superior perfor­
mance in the conversion of different alcohols (methanol, ethanol,
propanol and butanol) to olefins, gasoline range hydrocarbons and ar­
omatics due to their excellent shape selectivity, tunable acidity
(Brønsted and Lewis) and pore size (0.55 nm) matching with kinetic
diameter of BTX [15,18,25,31]. However, the two major challenges
faced during alcohol aromatization were selectivity of BTEX and catalyst
deactivation. The conversion of n-butanol to hydrocarbons over HZSM5
catalyst achieved nearly 38% selectivity for aromatics (selectivity for
BTEX around 27%) along with the high proportion of light alkanes like
propane and butanes [22]. To improve the selectivity for BTEX, the
formation of light alkanes and higher aromatics is required to suppress.
Apart from the pore size, catalyst acidity and dehydrogenation activity
are two important factors to be considered for enhancing the aromati­
zation [3,22]. Brønsted acid sites within the zeolites are involved in the
oligomerization of olefins, which are then aromatized to form aromatic
hydrocarbons. Moreover, the strength and density of acid sites have
significant influence on the selectivity of total aromatics and BTEX [25].
On the other hand, the MFI zeolites supported metal or metal oxides are
effective for the enhancement of dehydrogenation activity, which results
increase in the selectivity of aromatics and BTEX. Numerous literatures
are available on the conversion of alcohols and light alkanes and alkenes
to aromatics over different metal (Zn, Ga, Re, Mo, Pt) modified zeolites
[3,17,32–38]. These metal or metal oxides enhance the dehydrogena­
tion and aromatization of alkanes. These metal cations limit the pref­
erential elimination of hydrogen by transferring to olefins (hydride
transfer) resulting in the formation of light alkanes. Recently, Lok et al.
reviewed the promotional effect of Ga and Zn on the production of
bio-aromatics during thermochemical conversion of biomass and waste
in the temperature range of 673–773 K and space velocity of 0.5–1.0 h− 1
[17]. It was reported that the extraframework Ga cations and close
proximity Brønsted acid sites were active for the aromatization, whereas
ZnOH+ species seem to be the active sites for the aromatization reaction
over Zn/HZSM catalyst. The aromatization of various alkanes and al­
kenes such as methane, ethane, ethylene, propane, butane, pentane, and
hexane has been reported over Zn/HZSM5 catalysts [33,34,37–43].
Wang et al. investigated methanol to aromatic (MTA) reaction in flu­
idized bed reactor over Zn/HZSM5 catalyst [36]. p-xylene was reported
as the primary product in MTA reaction. Other xylenes were formed by
isomerization of p-xylenes. Moreover, benzene, toluene and trimethyl
benzene were formed by dealkylation, alkylation or disproportionation
of xylene. The single step conversion of isobutyl alcohol to aromatic
hydrocarbons over different zeolites and metals modified zeolites was
reported by Yu et al. [3]. The Zn modified HZSM5 (Si/Al ratio 34.3)
produced highest aromatic yields (~60 wt%) among all the supported
metal species (Zn, Ga, Mo, La, Ni, Ag, and Pt) at 0.1 MPa, 723 K, WHSV
of 3.88 h− 1 [3]. Zn modified HZSM5 exhibited improvement in the
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Microporous and Mesoporous Materials 323 (2021) 111216
formation of toluene and xylene and also inhibited the formation of light
alkanes. From the above discussion, it is evident that metal incorporated
zeolites are effective for the production of aromatics from light alkanes
and alcohols. However, conversion of n-butanol to aromatics was not
studied over metal incorporated zeolite catalysts.
Based on the above discussion, it is also evident that incorporation of
suitable metal/metal oxide can improve the selectivity of aromatics and
BTEX. In the present investigation, Zn incorporated HZSM5 catalysts of
different Zn loading and silica alumina ratios (23, 55 and 280) were
studied for the direct conversion of n-butanol to aromatics (BTA). The
promotional effect on the selectivities of total aromatics and BTEX was
discussed. All the catalysts were well characterized by a number of
techniques such as BET, XRD, NH3-TPD, pyridine FTIR, UV–vis and XPS
and the physico-chemical properties of these catalysts were correlated
with the selectivity of different aromatics formed under wide range of
process conditions (temperature, pressure and WHSV). The alcohols to
aromatics reaction suffers from catalyst deactivation because of the
deposition of carbonaceous species. The spent Zn-HZSM5 catalysts were
well characterized by various characterizations to delineate character­
istics of coke deposited on the catalyst surface. A plausible reaction
mechanism was suggested based on the product distribution derived
under broad range of process conditions.
2. Experimental
2.1. Materials
The ammonium form of HZSM5 [SiO2/Al2O3 ratio = 23, 55 and 280]
was purchased from Zeolyst International, USA. n-butanol [C4H9OH,
Purity ≥ 99.0%] was purchased from Merck Life Science Pvt. Ltd. and
zinc nitrate hexahydrate [Zn(NO3)2.6H2O, Purity ≥ 98.0%] was pro­
cured from Sigma-Aldrich. HZSM5 zeolite was heat treated at 823 K for
6 h and all the other chemicals were used without further purification.
2.2. Catalyst preparation
Several zinc (Zn) incorporated HZSM5 catalysts of different Zn
loading were prepared by incipient wetness impregnation method. The
Zn precursor solution was prepared by adding a calculated amount of
zinc nitrate hexahydrate precursor corresponding to the particular Zn
loading to the incipient volume of millipore water. The required amount
of pretreated HZSM5 was added to the precursor solution and stirred for
1 h to ensure intimate mixing. The pretreatment of HZSM5 zeolite was
performed by adding incipient volume of millipore water followed by
heat treatment similar to catalyst preparation. The wet paste was kept in
a desiccator for drying at room temperature for overnight (about 12 h).
The room temperature dried material was dried further in a hot air oven
for 6 h at 383K. Finally, the dried material was calcined in the static air
at 823 K for 6 h using a heating rate of 1 K/min. The calcined catalysts
were denoted as xZn-HZSM5 (x = 0, 1, 3,5,7 and 10 wt%, SiO2/Al2O3 =
23, 55 and 280), where x represents wt% of Zn metal.
2.3. Catalyst characterization
The N2 adsorption-desorption studies were performed over xZn-
HZSM5 catalysts at 77 K using physisorption analyzer (Micromeritics
ASAP2020). Before the measurements, all the catalysts were heat
treated at 473 K for 5 h under vacuum (5 × 10− 5 mmHg) in order to
eliminate adsorbed moisture and residual impurities. The Brunauer-
Emmett-Teller (BET) equation and adsorption isotherm data in the
relative pressure (P/P0) range of 0.05–0.30 were used to determine the
surface area of the catalysts. The pore size distribution (PSD) was
determined by Barrett-Joyner-Halenda (BJH) method and average pore
volume was considered as the volume of liquid nitrogen adsorbed at P/
P0 = 1.0 ca. The micropore area and volume were determined by t-plot
method.
T. Kella and D. Shee
The powder X-ray diffraction (powder XRD) patterns of xZn-HZSM5
catalysts were acquired by using Rigaku Smart Lab X-ray Diffractometer
equipped with a Cu-Kα radiation (λ = 1.5418 Å) source and D/teX ultra
250 detector and operated at 45 kV and 30 mA. The XRD patterns were
acquired in the 2θ range of 10 to 90◦ with a scanning speed of 2◦ /min.
The relative crystallinity of the xZnHZSM5 catalysts was determined by
the integral areas of the peaks in the 2θ range of 22.0–25.0◦ with the
pure HZSM5 as reference [44]. The crystallize size of the HZSM5 was
determined using Scherrer equation.
FTIR spectra (Fourier Transform Infrared) under ambient condition
of the fresh and spent xZn-HZSM5 catalysts were recorded using a
Bruker TENSOR 37 FTIR spectrometer in transmission mode in the
wavenumber range of 400–4000 cm− 1 with a resolution of 4 cm− 1 and
256 no of scans. Prior to the analysis, all the catalyst samples were mixed
with spectroscopic grade KBr powder and transformed into a trans­
parent circular wafer. All the spectra were taken against the KBr back­
ground acquired separately under similar conditions.
The IR spectra of pyridine adsorbed xZn-HZSM5 catalysts were
recorded in the above mentioned spectrometer under similar conditions.
A few drops of pyridine were added to the powder catalyst sample and
then left at room temperature for 8 h. Then the pyridine soaked sample
was kept in hot air oven maintained at 383 K for 1 h to eliminate
physisorbed pyridine. A transparent circular wafer was made in similar
way as mentioned above for acquiring the IR spectra.
The temperature programmed NH3 desorption (NH3-TPD) studies of
xZn-HZSM5 catalysts were performed in Micromeritics Chemisorption
analyzer (Autochem 2920 II, Micromeritics, USA). Before the analysis,
all the catalysts were pretreated at 473 K in flowing of Ar for 1 h to
eliminate adsorbed moisture and any other residual impurities. On
completion of pretreatment, the catalyst temperature was lowered to
373 K in flowing of Ar and 10 vol%NH3/Ar gas mixture was fed at a flow
rate of 20 mL/min. The pretreated catalyst was exposed to NH3/Ar gas
mixture for 1 h and subsequently the gas flow was changed to pure Ar.
The Ar gas flow was maintained for another 1 h to remove physisorbed
NH3 from catalyst surface and entire flow path. The catalyst was heated
to 1073 K using a heating rate of 10 K/min. The desorbed NH3 was
monitored using a thermal conductivity detector (TCD).
UV–vis spectra of the xZn-HZSM5 (both fresh and spent) catalysts
were recorded by using UV–vis NIR PerkinElmer spectrophotometer
(Model No.: Lambda 1050) equipped with Harrick scientific diffuse
reflectance accessory (Praying Mantis, Model No.: DRK-4-P72). The
spectra of all the samples were collected in the wavelength region of
200–800 nm using BaSO4 as reference.
X-ray photoelectron spectroscopy (XPS) measurement of selected
xZn-HZSM5 catalysts was performed on Thermo Scientific™ K-Alpha™
XPS spectrometer (UK) using a micro focused monochromatized AlKα
radiation. The powder catalyst was dispersed on a sample holder using
double-sided tape before introducing into the treatment chamber. The
sample pretreatment compartment was maintained under high vacuum
(ca. 10− 8 Torr) before shifting to the analysis chamber. XPS survey scan
spectra were acquired using 200 eV analyzer electron pass, while the
high resolution XPS region scan spectra were obtained at 50 eV pass
energy within a short period of time to avoid or minimize the photo-
reduction. The binding energies calibration was performed using
adventitious carbon (C 1s) peak appeared at 284.6 eV [45].
The amount of carbonaceous species (coke) deposited on the spent
HZSM5 and 5Zn-HZSM5 catalysts was quantified using thermogravi­
metric analyzer (TGA, Perkin Elmer Pyris 1 TGA). About 6–10 mg of
spent catalyst sample was loaded in the platinum crucible and kept in­
side the furnace. The sample was then heated to 1073 K using a heating
rate of 10 K/min in flowing of nitrogen (30 ml/min) carrier gas and held
3
Microporous and Mesoporous Materials 323 (2021) 111216
at this temperature for 10 min. Then the carrier gas was switched over to
air (30 ml/min) and held at this temperature for 30 min to completely
burn the deposited coke on the catalyst. The amount of coke was
considered as the percentage loss in weight.
2.4. Reaction studies
The butanol to aromatics (BTA) reaction was performed in a high
pressure and temperature fixed bed reactor over xZn-HZSM5 catalysts
under different reaction conditions. The catalyst bed was made with the
physical mixture of measured amount of catalyst and quartz particles.
The catalyst bed supported by two layers of quartz wool was placed
inside a stainless steel reactor (1-inch ID × 8-inch length) and the reactor
loaded with catalyst was placed inside a vertically placed tubular
furnace. The catalyst bed temperature was measured and controlled by a
K type thermocouple placed immediately above the bed and PID tem­
perature controller. The catalyst was first pretreated at the reaction
temperature in flowing of nitrogen (40 mL/min) for 1 h. The mass
flowrate of nitrogen was maintained by a thermal mass flow controller
(Bronkhorst, EL-Flow). On completion of pretreatment, n-butanol was
pumped at a certain flowrate (0.1 mL/min) using HPLC pump (Lab
alliance, Series-I) into the reactor through a preheater maintained at
473 K. The vaporized butanol in preheater was carried by nitrogen into
the reactor. The product gas mixture releasing from the exit of the
reactor was routed through a vertical condenser, where low boiling
organic compounds were condensed. The condensed liquid products
were separated from non-condensable gas mixture in a high pressure
gas-liquid separator. The liquid products were collected at regular in­
terval of time and the non-condensable gaseous products were sent for
analysis to the online Gas chromatograph (GC). The permanent gases
(CH4, N2 and H2) were quantified using a micro GC (Agilent, Model no:
490C) equipped with thermal conductivity detector (TCD) connected to
PPU (pora plot U) and MSSA (CP-molsieve) columns. The gaseous hy­
drocarbons (C1–C5 alkanes and alkenes) were quantified by online GC
(Agilent series, Model no. 7890B) equipped with flame ionization de­
tector (FID) and GS-GasPro capillary column (Agilent J&W, 30 m × 0.32
mm). The liquid products were analyzed offline by Gas chromatograph
equipped with FID and DB-5HT column (Phenomenex, 30 m × 0.32 mm
× 0.10 μm). GC FID operating conditions for both gas and liquid anal­
ysis, the injector and detector temperatures were kept at 523 K, and oven
temperature varying from 313 K to 513 K. The phenanthrene was used
as the external standard for the quantification purpose. Methane was
considered as the tie component to determine complete gas phase
compositions. The conversion of n-butanol over all the tested catalysts
and reactions conditions was achieved 100% and results reported were
considered beyond 5 h TOS. Material and carbon balance was verified
for all the conducted experiments and the errors were in the range of
±5% for atmospheric pressure experimental runs. The carbon and ma­
terial balance for high-pressure reactions were nearly 76–93% as shown
in Table 2. All the liquid and gaseous products were identified using gas
chromatography mass spectroscopy (GC-MS, Shimazdu GC-MS QP2010
Ultra). The selectivity of the products and WHSV were calculated by the
following equations (1) and (2) [22].
Selectivity ​ of ​ Cn ​ hydrocarbon, ​ % = 100
×[
n × (moles ​ of ​ Cn ​ hydrocabon ​ produced)
] (1)
4 × (moles ​ of ​ butanol ​ reacted)
Where ‘n’ refers to the number of carbon atoms present in the particular
hydrocarbon.
T. Kella and D. Shee Microporous and Mesoporous Materials 323 (2021) 111216

Total ​ massflowrate ​ of ​ butanol ​ and ​ N2 ​ gas ​ (g/h)

Weight ​ hourly ​ space ​ velocity ​ (WHSV), ​ h− 1 = (2)
weight ​ of ​ the ​ catalyst ​ (g)

at low Zn loading (upto 3 wt%). At higher Zn loading, ZnO was also

3. Results and discussion
3.1. Catalyst characterization
The textural properties of the xZn-HZSM5 (x = 0 to 10 wt%; SiO2/
Al2O3 = 55) catalysts were determined by N2 adsorption/desorption
studies and the results were tabulated in Table 1. The BET surface area of
xZn-HZSM5 (55) decreases with increasing the Zn loading. However,
decrease of total pore volume was insignificant for these catalysts. The
micropore analysis of these catalysts was performed using t-plot method.
The micropore area (Am) was increased by about 35% on deposition of 1
wt% ZnO and remained constant on further increase in ZnO loading upto
3 wt%. The initial increase in micropore area might be because of the
transformation of relatively lower size mesopores to micropores by the
deposition of ZnO. Further increase in the Zn loading (at and above 5 wt
%) decreases the micropore area and cumulative decrease of micropores
was about 13% with the increase in ZnO loading from 1 to 10 wt%.
However, the external surface area (AE), which includes mesopores and
macropore/crystal void space is gradually decreased (loss of 48%) with
increase in Zn loading from 0 to 10 wt%. An insignificant variation of
micropore volume was noticed with the increase in Zn loading. Again,
the relative decrease of external surface was much low above 5 wt%.
Furthermore, an insignificant variation of micropore volume was
noticed with the increase in Zn loading. These results indicates that the
ZnO was preferentially deposited in the mesopores and or macro pores
deposited in micropores of xZn-HZSM5 (55) in addition to the meso­
pores and or macro pores. The decrease in surface area was because of
the increase in surface coverage and blockage of pores by deposited ZnO.
A slight increase in pore diameter for higher Zn loading catalyst in­
dicates the blockage of micropores.
The XRD patterns of xZn-HZSM5 (55) catalysts were depicted in
Fig. 1. All the catalysts showed the characteristic diffraction peaks at 2θ
of 8.01◦ 8.9◦ and 23.1◦ 23.9◦ 24.4◦ of MFI crystal structure. However,
the intensity of these peaks for Zn-HZSM5 (55) catalysts decreases as the
Zn loading increased in comparison to HZSM5 (55). The characteristics
diffraction peaks corresponding to ZnO were not noticed for any of these
xZn-HZSM5 (55) catalysts indicating the higher dispersion of ZnO.
However, the diffraction peak at 2θ of 23.1◦ shifted to lower angle in Zn-
HZSM5 catalysts. The shift of diffraction peak around this region is
attributed to the different Zn content and skeleton dealumination of
zeolite lattice [46]. The XRD patterns of 5Zn-HZSM5 of different
silica-alumina ratio (23, 55 and 280) were also shown in Fig. S4. Similar
features were noticed in the XRD patterns of 5Zn-HZSM5 of different
silica-alumina ratio. The intensity of peaks characteristics of HZSM5
zeolite (2θ = 8.01◦ , 8.9◦ ) was noticed to decrease with the increase in
ZnO loading and silica-alumina ratio for a particular ZnO loading
resulting in decrease in relative crystallinity of xZn-HZSM5 catalysts
(Table S2). However, the relative crystallinity was noticed to be affected
more with the increase silica-alumina ratio of HZSM (Table S2).
The FTIR spectra of xZn-HZSM5 (55) catalysts in the hydroxyl region
exhibit three distinct IR bands at 3660, 3611 and 3437 cm− 1 (Fig. 2).

Table 1
Textural properties of HZSM5 (55) and xZn-HZSM5 (55) catalysts.
Catalyst SABETa (m2/g) AEb (m2/g) VTc (cm3/g) Vmd (cm3/g) DAAe (nm) Amf (m2/g)

HZSM5 (55) 373 195 0.29 0.12 5.9 162

1Zn-HZSM5 (55) 360 141 0.29 0.11 5.86 219
3Zn- HZSM5 (55) 343 125 0.28 0.11 6.3 218
5Zn- HZSM5 (55) 309 109 0.24 0.10 6.15 200
7Zn- HZSM5 (55) 307 104 0.25 0.10 6.90 203
10Zn- HZSM5 (55) 291 101 0.25 0.10 7.74 190
a
BET surface area.

b
External surface area derived from t-Plot method.

c
Total pore volume derived from BJH method.

d
Micropore volume derived from t-Plot method.

e
BJH adsorption average pore diameter (4V/A).

f
Micropore surface area derived from t-Plot method.

Table 2
Product distribution over HZSM5 (55) and 5Zn-HZSM5 (55) catalysts for conversion of butanol to aromatics, Reaction conditions: Temperature = 723 K; WHSV = 0.75
h− 1.
C1–C2 C3–C4 C5–C12 Aromatics BTEX Other higher aromatics Carbon balance (% error)

5Zn-HZSM5_1 bar 8.18 17.68 0.15 74.08 68.21 5.87 2.88

5Zn-HZSM5_5 bar 7.78 26.01 0.48 65.72 57.45 8.27 2.43
5Zn-HZSM5_10 bar 7.13 27.74 0.77 64.36 54.36 10.00 4.16
5Zn-HZSM5_20 bar 7.57 26.05 0.98 65.40 52.51 12.89 14.28
5Zn-HZSM5_30 bar 8.64 22.97 0.74 67.65 52.92 14.74 24.40
HZSM5_20 bar 15.14 30.81 0.47 53.58 37.85 15.73 17.37

4
T. Kella and D. Shee Microporous and Mesoporous Materials 323 (2021) 111216

Fig. 1. XRD patterns of xZn-HZSM5 (55) (x = 0 to 10 wt%) catalysts.

Fig. 2. FTIR spectra of xZn-HZSM5 (55) (x = 0 to 10 wt%) catalysts in the hydroxyl region.

5
T. Kella and D. Shee Microporous and Mesoporous Materials 323 (2021) 111216

Fig. 3. UV–vis spectra of xZn-HZSM5 (55) (x = 0 to 10 wt%) catalysts.

Fig. 4. Pyridine FTIR spectra xZn-HZSM5 (55) (x = 0 to 10 wt%) catalysts.

The IR bands at 3660, 3611 and 3437 cm− 1 were assigned to the extra groups in hydroxyl nests, respectively [22,25,47,48]. After impregna­
framework alumina with Lewis acid character, bridged hydroxyl group tion of zinc into HZSM5 (55), the band intensity at 3610 cm− 1 (Brønsted
(Al–OH–Si) with Brønsted acid character and hydrogen bonded Si–OH acid groups) was decreased, which was attributed to the consumption of

6
T. Kella and D. Shee
protons by Zn species. It was also observed that the band intensities at
3660 and 3437 cm− 1 considerably changed after the introduction of Zn
species [40]. The UV–vis spectra of HZSM5 (55) and Zn-HZSM5 (55)
catalysts as shown in Fig. 3 reveal a weak band at ~365 nm for
Zn-HZSM5 (55) catalysts and was appeared because of the formation of
ZnO crystal on the surface of the catalyst [3].
Fig. 4 shows the pyridine FTIR spectra of the HZSM5 (55) and Zn-
HZSM5 (55) catalysts. The adsorption of pyridine molecule on Lewis
and Brønsted acid sites is resulted IR bands at 1450 cm− 1 and 1546
cm− 1, respectively. The synergistic effect between Lewis and Brønsted
acid sites during pyridine adsorption is characterized by the evolution of
IR band at 1490 cm− 1. The exchange of zeolite proton with the Zn2+
species generates ZnOH + species and reveal strong IR band at 1620
cm− 1 [16,49,50]. Moreover, the IR band intensity at 1620 cm− 1 in­
creases with the rise in Zn loading suggesting enhancement of the con­
centration of ZnOH + species. The IR band intensity at 1546 cm− 1
(Brønsted acid sites) decreases as the Zn loading increased suggesting
increase in exchange of zeolite protons with Zn2+ species (Fig. 4) [51].
In contrast, the amount of Lewis acid sites increases with increasing Zn
loading. The increase in Lewis acid sites suggests that a fraction of Zn
metals are present in cationic form [51].
The NH3-TPD profile of xZn-HZSM5 catalysts revealed desorption
peaks in three regions (273–473, 473–673 and above 673 K) corre­
sponding to weak, medium and strong acid sites (Figs. 5 and S5) [40,52].
The pure HZSM5 showed two NH3 desorption peaks corresponding to
the weak (446 K) and medium acid sites (625 K). The NH3 desorption
peaks corresponding to the weak acid site was gradually shifted to
higher temperature with the decrease in silica-alumina ratio suggesting
increase in strength of the acid sites (Fig. S5). A weak NH3 desorption
peak was also noticed at 768 K because of the occurrence of strong acid
sites. The incorporation of Zn species on HZSM5 affects greatly the
distribution and strength of acid sites. The NH3 desorption peak attrib­
uted to the strong acid sites (768 K) gradually shifted to the lower
temperature as the Zn loading increases. A few new strong acid sites
were appeared at around 790 K and above for higher Zn loading
Fig. 5. NH3-TPD profile of xZn-HZSM5 (55) catalysts (x = 0 to 10 wt%).
7
Microporous and Mesoporous Materials 323 (2021) 111216
catalysts. The presence of Zn species alters the amount and strength of
medium and weak acid sites. Depending on the Zn loading new acid sites
of weak and medium strength were also formed as shown in Fig. 5.
The XPS spectra of selected Zn-HZSM5 (55) catalysts such as 1Zn-
HZSM5 (55), 5Zn-HZSM5 (55) and 10Zn-HZSM5 (55) were acquired
to understand the distribution of different Zn species (Fig. 6). Pure ZnO
(2p1/2 and 2p3/2) showed peaks at BE of 1021.9 and 1045.0 eV [45,53].
The peak appeared at BE 1022.2 eV for the Zn-HZSM5 (55) catalysts are
ascribed to -O-Zn-OH species. This species prevails as a portion of zinc
oxide clusters integrated with the zeolite lattice. However, the size of
this zinc oxide cluster is not as large as the clusters of bulk zinc oxide
with BE of 1021.9 eV [53]. A high BE of 1023.0 (Zn 2p3/2) for
1Zn-HZSM5 (55) indicates presence of Zn species situated at the cation
exchanged sites of zeolite. The hypochromic shift of BE is because of the
higher electronegativity of the lattice oxygen than the O2− ligand in bulk
ZnO [53]. The XPS spectra of 5Zn-HZSM5 (55) and 10Zn-HZSM5 (55)
exhibit higher BE peaks at 1049.5 eV and 1026.5–1027.5eV corre­
sponding to ZnOH+ species (2p1/2 and 2p3/2). Again, the shift of peaks at
higher BE indicates strong interaction with the electronegative oxygen
in zeolite framework [45].
3.2. Conversion of butanol to aromatics
The conversion of butanol to aromatics (BTA) reactions were per­
formed under wide range of process parameters such as temperature
(573–723 K), WHSV (0.75–14.99 h− 1) and pressure (1–30 bar) over pure
HZSM5 (55) and xZn-HZSM5 (x = 1–10%, SiO2/Al2O3 = 55) of varying
Zn loading. The various products formed both in the gas and liquid
phases were identified by GC-MS and quantified by gas chromatography
as shown in Fig. S1. The hydrocarbon products identified in the liquid
phase were benzene, toluene, xylene isomers, ethyl benzene, propyl
benzene, trimethyl benzenes and higher aromatics (>C9+) and cyclic
paraffins (C6–C12), and in gas phase were hydrogen, methane, ethane,
ethylene, propane, propylene, butane isomers, butylene isomers,
pentane and pentene isomers. Further these hydrocarbons were
T. Kella and D. Shee
Fig. 6. XPS spectra of 1Zn-HZSM5 (55), 5Zn-HZSM5 (55) and 10Zn-HZSM5 (55) catalysts.
classified as C1–C2, C3–C4, C5–C12 and aromatics for ease of discussion.
The variation of selectivities of these products under wide range of
process parameters are discussed in the following sections.
3.3. Effect of zinc loading
The BTA reaction was performed over pure HZSM5 (55) and xZn-
HZSM5 (55) (x = 1 to 10 wt%) catalysts at 673 K, WHSV of 0.75 h− 1
and 1 atm pressure (Fig. 7). The selectivity of total aromatics and BTEX
was increased with the increase in Zn loading upto 5% and decreased
thereafter. The maximum selectivities of total aromatics and BTEX ob­
tained for 5Zn-HZSM5 (55) were 72% and 62%, respectively. This result
indicates enhancement of the aromatization of C3–C4 olefins as the
selectivity of C3–C4 olefins follows the reverse trend of aromatics
selectivity. The lower selectivity of total aromatics (~37.5%) over pure
HZSM5 (55) indicates that presence of Zn enhanced the aromatization
(cyclization followed by dehydrogenation) reaction of olefins leading to
the formation of higher amount of aromatics in Zn-HZSM5 (55). More­
over, the higher selectivity of C3–C4 hydrocarbons for pure HZSM5 (55)
confirms the enhance rate of aromatization reactions in presence of Zn.
The selectivity to propane and butane isomers over HZSM5 (55) was
nearly 32% and 20.5%, respectively, which were decreased to 5.25%
and 11.8%, respectively over 5Zn-HZSM5 (55) catalyst as shown in
Fig. S7. The formation of various aromatics may also proceed by hydride
transfer reaction of olefins and naphthene together with cyclization and
dehydrogenation reaction. In order to shed more light in this regard, a
8
Microporous and Mesoporous Materials 323 (2021) 111216
parameter H2/(H2+propane + butane) was calculated for pure HZSM5
(55) and Zn-HZSM5 (55) catalysts. It was observed that H2/
(H2+propane + butane) value was increased for Zn-HZSM5 (55) cata­
lysts (Fig. S8). This result clearly indicates that hydride transfer reaction
was prominent over pure HZSM5 (55) compare to Zn-HZSM5 (55) cat­
alysts under the studied reaction conditions. The hydride transfer re­
action decreases the amount of olefins, which are primary precursor for
the aromatics. The hydride transfer reaction was suppressed in presence
of Zn leading to increase in dehydrogenation of naphthene to produce
various aromatics. The higher yield of hydrogen in Zn-HZSM5 (55)
catalysts further support this statement. The nature and strength of acid
sites also influence the various reactions leading to the formation of
aromatics such as cyclization, oligomerization, hydride transfer reaction
and dehydrogenation of naphthene [25]. The Brønsted acid sites pro­
mote the cyclization, oligomerization, and hydride transfer reaction of
olefins, whereas dehydrogenation of naphthene occurs on Lewis acid
sites. The strong Brønsted acid sites result in the formation of higher
hydrocarbons through oligomerization reaction, whereas medium
strength Brønsted acid sites are appropriate for oligomerization reaction
to limits the formation of higher aromatic hydrocarbons. The L/B ratio
of Zn-HZSM5 (55) catalyst increases with the increasing Zn loading
suggesting the formation of additional Lewis acid sites and decreases the
Brønsted acid sites (specially higher strength) as discussed earlier. The
decline of hydride transfer reaction was because of the decrease in
strong Brønsted acid sites and increase in Lewis acid sites, which
enhance the dehydrogenation of naphthene to aromatics leading to the
T. Kella and D. Shee Microporous and Mesoporous Materials 323 (2021) 111216

Fig. 7. Effect of Zn loading over product distribution, Reaction conditions: Temperature = 673 K; WHSV = 0.75 h− 1; Pressure = 1 atm.

Fig. 8. Effect of Zn loading on individual aromatics selectivity, Reaction conditions: Temperature = 673 K; WHSV = 0.75 h− 1; Pressure = 1 atm.

formation of more hydrogen and less C3–C4 hydrocarbons. Therefore,
the decrease in selectivity of total aromatics above 5 wt% of ZnO loading
was because of the decrease in Brønsted acid sites, which were respon­
sible for the oligomerization reaction followed by cyclization of olefins
leading to the formation of napthene, a precursor for the aromatics.
In BTEX fraction, the benzene selectivity was virtually remained
constant with the increase in Zn loading, whereas selectivities of toluene
and C8 aromatics (Xylenes and ethyl benzene) were increased upto 5% of
Zn loading (Fig. 8). Further increase in Zn loading decreases the selec­
tivities of toluene and C8 aromatics resulting in decrease in BTEX se­
lectivities. The formation of C10 and higher aromatics was significantly
lower compare to the pure HZSM5 (55). However, selectivity to C9

9
T. Kella and D. Shee Microporous and Mesoporous Materials 323 (2021) 111216

Fig. 9. Effect of Zn loading on C8 aromatic hydrocarbons selectivity, Reaction conditions: Temperature = 673 K; WHSV = 0.75 h− 1; Pressure = 1 atm.

aromatics was increased with the increase in Zn loading (Fig. 8). The rise which confirms the enhancement of selectivity to C9 aromatics. Thus,
in selectivity to C9 aromatics might be because of the enhance alkylation the products stream comprised of different aromatics including C8 aro­
reaction of C8 aromatics over Lewis acid sites. As discussed earlier, the matics. These result indicate that self and cross oligomerization of
amount of Lewis acid sites enhances with the increase in Zn loading, various alkenes followed by cyclization and dehydrogenation reaction

Fig. 10. The variation of product distribution at different temperatures, Reaction conditions: WHSV = 0.75 h− 1; Pressure = 1 atm; 5Zn-HZSM5 (55) catalyst.

10
T. Kella and D. Shee Microporous and Mesoporous Materials 323 (2021) 111216

results in the formation of various aromatics. Formation of different multiple oligomerization and cracking of oligomeric intermediates
lower alkenes was attributed to the cracking reactions over Brønsted leading to the formation of unsaturated C6 oligomer, precursor of ben­
acid sites. Cracking reaction was more prominent over pure HZSM5 (55) zene. The unsaturated C6 oligomers further transform to benzene via
compared to Zn-HZSM5 (55) catalysts because of the higher Brønsted aromatization reaction. However, the selectivities of toluene and xy­
acidity of HZSM5 (55) as shown in Fig. 4. Total higher aromatics (C9+) lenes were varied with the Zn loading, which are well correlated with
selectivity was higher over HZSM5 than Zn-HZSM5 catalysts, and spe­ the published literature [3]. The toluene and xylenes selectivities over
cifically, C9 aromatics selectivity was increased on Zn-HZSM5 (55) HZSM5 (55) were about 12.6% and 8.75% and were increased to nearly
catalysts. The selectivity for C9+ hydrocarbons was higher over HZSM5 29% and 26.6%, respectively over 5Zn-HZSM5 (55). Further increase in
(55) because of the higher external surface area and pore volume. From Zn loading slightly decreases the selectivities of toluene and xylenes. The
BET analysis, external surface area, micropore area and pore volume of slight decrease in selectivities of toluene and xylenes might be because
the HZSM5 (55) were 195 m2/g, 162 m2/g and 0.26 cm3/g, respectively. of the decrease in Brønsted acid sites (Fig. S8) for higher Zn loading
External active sites promote the formation of higher hydrocarbons, catalyst.
whereas internal active sites favor the formation of light aromatics of
matching kinetic diameter with pores dimension. HZSM5 (55) has more
3.4. Effect of temperature
external active sites, which promote the formation of large molecular
size aromatics. In contrast, the external surface area, micropore area and
The influence of temperature on selectivity to various aromatics was
pore volume were decreased to 109 m2/g (29% reduction), 200 m2/g
investigated in the wide temperature range of 573–773 K and WHSV of
(15.6% reduction) and 0.24 cm3/g, respectively for the 5Zn-HZSM5 (55)
0.75 h− 1 using 5Zn-HZSM5 (55) catalyst under atmospheric pressure.
catalyst. The external surface area was affected more than the micropore
The selectivity of total aromatics was enhanced with the increasing
area. Hence, the 5Zn-HZSM5 (55) catalyst favors the formation of more
temperature from 573 K to 748 K, and was decreased on further increase
lighter aromatics (BTEX) [54,55]. The methane and ethane selectivities
in temperature to 773 K. The selectivities to C5–C12 range hydrocarbons
were increased over 5Zn-HZSM5 (55) than HZSM5 (55) catalyst because
and C3–C4 hydrocarbons were decreased as the temperature was
of the enhancement of the interconversion of the different aromatics by
increased in the studied temperature range. The selectivities to BTEX
hydrodealkylation/transalkylation and disproportionation reactions
and total aromatics were nearly 20.55% and 33.28%, respectively,
(Fig. S6) [56,57].
whereas the selectivity for C3–C4 and C5–C12 hydrocarbons at 573 K
The variation of selectivities of C8 aromatics fraction consisting of
were 50.70% and 15.27%, respectively. As the temperature increased to
ethylbenzene, p-xylene, o-xylene, and m-xylene with Zn loading is
773 K, the selectivities to C3–C4 and C5–C12 hydrocarbons were gradu­
shown in Fig. 9. The deposition of Zn and its amount have insignificant
ally decreased to 10% and 0%, respectively as shown in Fig. 10. The
influence on the selectivities of benzene and m-xylene. During BTA re­
maximum selectivities to BTEX (68.75%) and total aromatics (74.83%)
action, the benzene was formed through multiple oligomerizations of
were achieved at 723 K. The selectivity to higher aromatics was initially
olefins and cracking of oligomeric intermediates [3]. The multiple
increased to 17.48% at 598 K and then was gradually decreased to
oligomerization and cracking of oligomeric intermediates occur over
4.41% at 773 K because of the enhance cracking reaction at high tem­
strong Brønsted acid sites. Deposition of small quantity of ZnO reduces
perature (Fig. 11). The gradual increase in selectivities to C1–C2 hy­
the concentration of strong Brønsted acid sites, which suppress the
drocarbons indicates the increase of cracking of higher aromatics side

Fig. 11. The variation of aromatics product distribution at different temperatures, Reaction conditions: WHSV = 0.75 h− 1; Pressure = 1 atm; 5Zn-HZSM5
(55) catalyst.

11
T. Kella and D. Shee Microporous and Mesoporous Materials 323 (2021) 111216

Fig. 12. The influence of temperature on BTEX selectivity, Reaction conditions: WHSV = 0.75 h− 1; Pressure = 1 atm; 5Zn-HZSM5 (55) catalyst.

chain with the increasing temperature. The selectivity to C3–C4 hydro­ can be concluded that dehydrogenation of naphthene was the primary
carbons was declined with the increase in temperature. The decrease in reaction for the formation of aromatics at high temperature. However,
selectivity of C4 paraffins in C3–C4 fraction might be because of the the selectivity to propane was approximately remained constant over
decrease in hydride transfer reaction at high temperature (Fig. S9). It the studied temperature range.

Fig. 13. Effect of WHSV on the product distribution, Reaction conditions: Temperature = 723 K; Pressure = 1 atm; 5Zn-HZSM5 (55) catalyst.

12
T. Kella and D. Shee
The selectivities to xylenes were increased from 11.33% to nearly
26.63% as the temperature increased from 573 K to 673 K. Further in­
crease in the temperature, the xylenes selectivities were decreased to
17.07% at 773 K (Fig. 12). The decline in xylenes selectivities beyond
673 K was attributed to the hydrodealkylation of xylenes to toluene and
methane. Moreover, the benzene selectivity was gradually increased
with the increasing temperature because of the enhanced hydro­
dealkylation of toluene to benzene and methane (Fig. 12).
The toluene selectivity was increased from 6.8% to 32.67%, as the
temperature increased from 573 K to 723 K and thereafter the toluene
selectivity was decreased to 30.58% at 773 K. Above 723 K, the
hydrodealkylation reaction of toluene to benzene and methane was
dominated resulting in decrease in selectivity. Hence, the hydro­
dealkylation of xylenes and toluene increases the selectivity to benzene
as the temperature raised from 573 K to 773 K (Fig. 12). The selectivity
for BTEX and total aromatics remained nearly constant upto 773 K.
However, the variation of individual selectivity of benzene, toluene and
xylenes was attributed to the hydrodealkylation of toluene, xylenes to
form benzene and methane and the hydrodealkylation of C9 aromatics
(Ethyl toluene, trimethyl benzene) could be the another reason for in­
crease in selectivity of BTEX as shown in Fig. S10. For example, C9 ar­
omatics, ethyl toluene might have undergone hydrodealkylation
reaction to produce toluene and ethane at higher temperatures. Due to
these pronounced hydrodealkylation reactions various aromatics were
formed at higher temperatures leading to the increase in selectivities for
methane and ethane. From Fig. S11, the selectivities to methane and
ethane were increased to 8.62% and 8.83%, respectively at 773 K from
0.13% to 0.08%, respectively at 573 K. The sharp rise in selectivity of
methane and ethane above 673 K was attributed to severe hydro­
dealkylation reactions of various alkyl substituted aromatics. The
interconversion of various aromatics might also proceed by dispropor­
tionation and transalkylation reactions. However, the hydro­
dealkylation might be more pronounced than disproportionation and
transalkylation reactions over the 5Zn-HZSM5 (55) catalyst in the
studied temperature range [57–59].
Fig. 14. Effect of WHSV on the aromatics product distribution, Reaction conditions: Temperature = 723 K; Pressure = 1 atm; 5Zn-HZSM5 (55) catalyst.
13
Microporous and Mesoporous Materials 323 (2021) 111216
3.5. Effect of WHSV
Effect of WHSV on selectivities of BTEX and aromatics using 5Zn-
HZSM5 (55) catalyst was studied with different WHSV of 14.96 h− 1,
7.48 h− 1, 2.99 h− 1, 1.50 h− 1, 0.75 h− 1 and 0.50 h− 1 at 723 K and 1 atm
pressure. The selectivity to total aromatics was increased from 29.19%
to 74% as the WHSV decreased to 0.50 h− 1. Similarly, the selectivities to
BTEX was also increased from 25.88% to 66.83% within the WHSV
range of 14.96 h− 1 to 0.5 h− 1. The maximum BTEX selectivities of 68%
was achieved at WHSV of 0.75 h− 1 (Fig. 13). The C5–C12 and C3–C4
hydrocarbons selectivities were decreased from 12% and 54.25% to
0.14% and 17.12%, respectively. However, C1–C2 selectivity was
increased from 4.47% to 8.71% as the WHSV decreased from 14.96 h− 1
to 0.5 h− 1 as shown in Fig. 13. It was clearly evident that low WHSV
favors the formation of more aromatics and subsequently suppresses the
formation of C3–C4 and C5–C12 hydrocarbons. Prolong exposure (higher
contact time) of olefins to acid sites leads to successive oligomerization,
cyclization and dehydrogenation reactions resulting in the formation of
various aromatics. The other higher aromatics cumulative selectivity
was also increased from 3.32% to 7.18% with the decrease in WHSV
from 14.96 h− 1 to 0.5 h− 1 (Fig. 14). More specifically, all the individual
higher aromatics selectivities were enhanced with the decrease in
WHSV, which was attributed to the oligomerization of various olefins
followed by aromatization (Fig. S12). The selectivities for methane and
ethane at WHSV of 14.96 h− 1 were 0.45% and 0.15%, respectively and
were increased to 4.18% and 3.56%, respectively for the WHSV of 0.75
h− 1 as shown in Fig. S13. This result might be due to the hydro­
dealkylation of higher aromatics and interconversion of the light aro­
matics on the strong acid sites at higher contact time [58].
Formation of butylenes and propylene were observed to be signifi­
cant at high WHSV and declined with the decrease of WHSV [22]. The
propylene was formed by dehydroformylation of butanal, which was
formed by dehydrogenation of n-butanol. The dehydrogenation of
n-butanol and dehydroformylation of butanal were favorable route for
n-butanol transformation at lower temperature. However, these re­
actions may contribute significantly to n-butanol transformation at high
T. Kella and D. Shee Microporous and Mesoporous Materials 323 (2021) 111216

Fig. 15. Effect of WHSV on BTEX hydrocarbons selectivity, Reaction conditions: Temperature = 723 K; Pressure = 1 atm; 5Zn-HZSM5 (55) catalyst.

Fig. 16. Effect of pressure on the aromatic product distribution, Reaction conditions: Temperature = 723 K; WHSV = 0.75 h− 1; 5Zn-HZSM5 (55) catalyst.

temperature resulting in higher selectivity of propylene. The selectiv­ respectively at WHSV of 0.5 h− 1 (Fig. S14). In contrast, the selectivities
ities for propylene and butylenes at WHSV of 14.96 h− 1 were 18.31% of light aromatics, benzene, toluene and xylenes were increased from
and 29.72%, respectively and was decreased to nearly 1% and 1.36%, 2.19%, 11.93% and 11.20% to 12.4%, 30.36%, and 17.30%,

14
T. Kella and D. Shee
respectively as WHSV decrease from 14.96 h− 1 to 0.5 h− 1 (Fig. 15).
These results clearly indicates that the oligomerization of olefins and
aromatization reactions are favorable at relative low WHSV meaning
high contact time.
Another interesting observation was that the selectivity of propane
was increased with the decrease of WHSV (Fig. S14). This result in­
dicates that hydride transfer reaction favors at lower WHSV. The
decreasing trend of values of H2/(H2+C3+C4) further confirms the
increasing contribution of hydride transfer reaction as the WHSV is
decreased. Hence, the selectivity for butylenes isomers and propylene
was decreased and the aromatics selectivity was increased with the
decrease in WHSV (Fig. S15).
3.6. Effect of pressure
The influence of pressure on total aromatics and BTEX selectivities
were studied at different pressures (1, 5, 10, 20 and 30 bar), 723 K, and
WHSV of 0.75 h− 1. The selectivity for BTEX was decreased as the
pressure increased from 1 bar to 30 bar as shown in Fig. S16. In contrast,
the selectivity to total aromatics was decreased as the pressure increased
upto 10 bar and was marginally increased with the increasing pressure
beyond 10 bar. The marginal increase in the selectivity to total aro­
matics was due to the formation of higher aromatics. The selectivity for
higher aromatics at 1 bar was 5.87% and was increased to 14.74% at 30
bar pressure (Fig. 16).
These higher aromatics were primarily consisted of ethyl toluene,
trimethyl benzenes and naphthalenes (naphthalene, methyl, ethyl,
propyl - naphthalenes). The selectivity of these aromatics at 1 bar was
3.22%, 1.04% and 1.12%, respectively and was increased to 5.18%,
1.65% and 4.75%, respectively at 30 bar pressure (Fig. S17). These,
higher aromatics were formed on the external surface of the 5Zn-HZSM5
(55) catalyst. The formation of various carbonaceous deposits on cata­
lyst was explained by hydrocarbon pool model [60]. This model suggests
the involvement of organic active species and inorganic active sites (acid
sites and metal center) during the formation of hydrocarbon pool from
Fig. 17. Effect of pressure on BTEX hydrocarbons selectivity, Reaction conditions: Temperature = 723 K; WHSV = 0.75 h− 1; 5Zn-HZSM5 (55) catalyst.
15
Microporous and Mesoporous Materials 323 (2021) 111216
n-butanol. Depending on the reaction conditions (temperature, pressure
and WHSV) and strength of acid sites, the hydrocarbon species either
desorb from the catalyst surface or further converted to higher
substituted aromatics and polynuclear aromatics, which may deposit
inside the porous channel and or external surface of the catalyst. For
example, the low reaction temperature favors the formation of oligo­
mers and polymers as primary carbonaceous species. However, high
reaction temperature and pressure promotes the formation of poly­
aromatics (naphthalene) and highly substituted aromatics (trimethyl
benzene, ethyl toluene etc.). These higher aromatics were formed over
acid sites through various complex reactions, which include condensa­
tion, rearrangement, hydrogen transfer reaction and dehydrogenation
reactions. Thus, enhanced selectivities of these higher aromatics at
higher pressures were attributed to the condensation and rearrangement
reactions [56,60]. Furthermore, a comparison on formation of higher
aromatics (C9–C13) over HZSM5 (55) and 5Zn-HZSM (55) was made as
shown in Fig. S18. In case of 5Zn-HZSM5 (55), the selectivity of all the
aromatics increases with the increase in reaction pressure (Fig. S22). The
selectivity of C9 aromatics at 20 bar was higher for 5Zn-HZSM5 (55)
than the pure HZSM5 (55). However, the selectivities of C10–C13 were
higher for HZSM5 (55) than the 5Zn-HZSM5 (55). These results indicate
pure HZSM5 (55) favors the formation of higher aromatics. From
Fig. 17, The selectivity of light aromatics benzene, toluene and xylenes
were 11.93%, 32.26% and 23.59% at 1 bar pressure and was decreased
to 8.78%, 23.89% and 19.04%, respectively at 20 bar pressure. How­
ever, no significant change in selectivities of these aromatics was noticed
at 30 bar pressure.
The variation of selectivities of BTEX was monitored with time on
stream (TOS) at different pressure using 5Zn-HZSM5 (55) (Fig. 18). At
ambient pressure, the selectivities of BTEX were increased upto first 2 h
of TOS and remained constant at higher TOS. In contrary, the selectiv­
ities to BTEX were continued to decrease with the increase in TOS at 10
bar and above pressure. However, a small fluctuation in selectivities was
observed at relatively lower pressure of 5 bar. The high pressure favors
the formation of higher aromatics of large kinetic diameter, which were
T. Kella and D. Shee
Fig. 18. Effect of pressure on BTEX selectivity over 6 h TOS, Reaction conditions: Temperature = 723 K; WHSV = 0.75 h− 1; 5Zn-HZSM5 (55) catalyst.
deposited on the external surface of the HZSM5 (55) causing catalyst
deactivation by blockage of pores. The light aromatics, BTEX of smaller
kinetic diameters were selectively formed inside the porous channel of
HZSM5 (55). The gradual decrease in selectivities of BTEX (upto 20 bar)
further confirms the limited access of pores to light aromatics. The
decline in BTEX selectivities was more prominent at higher pressures,
particularly at 10 bar, 20 bar and 30 bar over 5Zn-HZSM5 (55) catalyst
after 1h of TOS.
The BTEX selectivities were 63.99%, 62.89% and 62.44% at 1 h
decreased to 54.35%, 50.56% and 48.05% after 6 h TOS, at 10 bar, 20
bar and 30 bar, respectively. The other higher aromatics (>C8) selec­
tivity after 1 h of TOS were 12.34%, 15.90% and 22.45% at 10 bar, 20
bar and 30 bar, respectively and were decreased to nearly 10%, 12.29%
and 13.79% respectively at 6 h TOS (Fig. S19). There were two impor­
tant findings clearly evident from here. First, the formation of higher
aromatics (>C8) at the beginning of the BTA reaction was higher due to
higher availability of active sites and later decreased gradually as the
reaction progressed. Second was the enhancement of the formation of
higher aromatics (>C8) at the beginning as the reaction pressure in­
creases. Thus, higher aromatics formed at the beginning might be
strongly adsorbed on the active sites for a longer time or trapped in the
catalyst pores resulting in catalyst deactivation and decrease in the
product selectivity. The carbon and material balance errors were
increased particularly at higher pressure reactions (Table 2) and was
attributed to the deposition of higher aromatics.
At higher pressure, the internal conversion of aromatics to heavy
aromatics could be possible as mentioned earlier [57]. The higher aro­
matics (>C8) selectivity over pure HZSM5 (55) after 1h of TOS (25.86%)
was much higher than over 5Zn-HZSM5 (55) (12.29%) at 20 bar pres­
sure because of the higher Brønsted acidity, external surface area in pure
HZSM5 (Figs. S20a and b). The higher aromatics of large kinetic diam­
eter were readily formed on the external surface [54,55,57,61]. How­
ever, the individual selectivities of BTEX and other aromatics were
decreased with the increasing TOS, due to the deposition of higher ar­
omatics. From Fig. S21, it was evident that the variation of selectivity of
16
Microporous and Mesoporous Materials 323 (2021) 111216
methane and ethane was insignificant with pressure indicating minor or
no effect on hydrodealkylation intermediate reaction. The propane
selectivity was found to be increased upto 10 bar pressure and was
decreased with the further increase in pressure. The hydride transfer
reaction for the formation of aromatics favors at high pressure over
dehydrogenation reactions leading to the formation of various aro­
matics. However, alkylation reactions dominates at high pressure
resulting in decrease of propane selectivity [57]. Butanes selectivity was
also decreased at higher pressure (Fig. S22). The selectivity for C3–C4
hydrocarbons was increased with the increase in pressure upto 10 bar
and decreased with a further increment in the pressure. In summary, the
maximum selectivities of total aromatics and BTEX achieved were
74.83% and 68.75% (B: 11.10%, T: 32.67%, E: 0.54%, X: 24.44) at 723
K, 1 bar and 0.75 h− 1 WHSV for 5Zn-HZSM5 (55) catalyst.
3.7. Effect of silica-alumina ratio
The BTA reaction studied over 5Zn-HZSM5 catalysts of different
silica-alumina ratio (23, 55 and 280) was studied under optimized re­
action conditions as mentioned above (Fig. S23). The highest selectivity
of total aromatics and BTEX was achieved for 5Zn-HZSM5 (55). The
lower selectivity total aromatics and BTEX over 5Zn-HZSM5 (23) was
because of the presence of strong acid sites (Fig. S5) which promotes
formation of higher hydrocarbons leading to deactivation of the catalyst
[25]. The HZSM5 (23) is associated with lower external surface area
than the other zeolites in the present investigation [25]. It was
demonstrated before that ZnO deposits preferencially on external sur­
face area. Thus, deposition of ZnO in micropores of HZSM5 (23) is
inevitable because of low external surface area, which may cause
blockage of pores. The pore blockage phenomena may also contribute
towards poor performance of 5Zn-HZSM5 (23) catalyst. The signifi­
cantly lower performance of 5Zn-HZSM5 (280) catalyst was due to the
insufficient concentration of Brønsted acid sites. In addition, the higher
crystallite size and poor crystallinity might be another reason for poor
performance of this catalyst (Table S2).
T. Kella and D. Shee Microporous and Mesoporous Materials 323 (2021) 111216

Fig. 19. TGA analysis of spent HZSM5 (55) and 5Zn-HZSM5 (55) catalysts, Reaction conditions: Temperature = 723 K; WHSV = 0.75 h− 1.

3.8. Coke analysis
The amount of carbonaceous species (coke) deposited in the spent
catalysts (5Zn-HZSM5 (55) and HZSM5 (55)) was determined by ther­
mogravimetric analysis (TGA) as shown in Fig. 19. From Fig. 19, the
total weight loss was increased with the increase in reaction pressure
from 1 bar to 30 bar for 5Zn-HZSM5 (55) catalysts. The total weight
losses observed were 7.19, 8.01, 8.07, 9.71 and 9.72 wt% at 1, 5, 10, 20
and 30 bar pressure, respectively. The total weight loss of 9.60 wt% was
obtained for spent HZSM5 (55) (20 bar), which was fairly close to the
weight loss obtained for spent 5Zn-HZSM5 (55) catalysts at 20 bar and
30 bar pressures. The thermogravimetry curve shows stage wise loss of
weight indicating deposition of different types of coke on the catalysts
(Fig. 19). The derivative thermogravimetry (DTG) curves of the spent
catalysts obtained at different reaction pressures were generated to
know the temperature for decomposition/removal of different types of
coke as shown in Fig. S24.
The weight losses occurred during TGA analysis were at four
different temperature region as reported in the literature: 293–438,
438–531, 531–673, and 673–873 K [60]. The first stage (<438 K) loss of
weight corresponds to the removal of moisture and any other physically
adsorbed species. The weight loss occurred in the moderate tempera­
tures (438–673 K) is because of the removal of volatile species named as
“soft coke”, whereas the weight loss occurred between 673 and 873 K is
because of the matured coke called “hard coke”. The soft cokes are
aliphatic in nature and soluble in organic solvents. Whereas hard coke

Fig. 20. Spent HZSM5 (55) and 5Zn-HZSM5 (55) catalysts, A) 5Zn-HZSM5 (55)_1 bar, B) 5Zn-HZSM5 (55)_5 bar, C) 5Zn-HZSM5 (55)_10 bar, D) 5Zn-HZSM5 (55)_20
bar, E) 5Zn-HZSM5 (55)_30 bar, and F) HZSM5 (55)_20 bar, Reaction conditions: Temperature = 723 K; WHSV = 0.75 h− 1.

17
T. Kella and D. Shee
Table 3
Textural properties of spent HZSM5 (55) and 5Zn-HZSM5 (55) catalysts.
Catalyst SABETa (m2/g) AEb (m2/g)
Fresh 5Zn-HZSM5 309 110
5Zn-HZSM5_1 bar 252 95
5Zn- HZSM5_5 bar 240 87
5Zn- HZSM5_10 bar 226 88
5Zn- HZSM5_20 bar 210 79
5Zn- HZSM5_30 bar 192 69
HZSM5_20 bar 223 53
HZSM5 (Fresh) 373 195
a
BET surface area.
b
External surface area derived from t-Plot method.
c
Total pore volume derived from BJH method.
d
Micropore volume derived from t-Plot method.
e
Micropore surface area derived from t-Plot method.
are primarily of polyaromatic in nature and insoluble in organic sol­
vents. The weight losses observed in different temperature ranges for
spent HZSM5 (55) catalyst (20 bar) follow the trend: 293–438 <
<438–673 < 673–873. In contrast, for 5Zn-HZSM5 (55) (20 bar) the
weight losses observed were more in the temperature range of 438–673
K and significantly less in the temperature region of 673–873 K. At
ambient pressure, both the soft and hard coke were formed over
5Zn-HZSM5 (55) catalyst. As the reaction pressure increased to 30 bar
(for 5Zn-HZSM5 (55)), the more weight loss in the medium temperature
range corresponding to soft coke was observed and the weight loss peak
corresponding to hard coke shifted from 673 K to 773 K. This result
indicates the formation of more polynuclear aromatic species as hard
coke at higher pressure. High external surface area and high Brønsted
acidity in case of HZSM5 (55), enhance the formation of more hard coke
at high pressure as mentioned earlier. These results indicate that HZSM5
(55) promotes the formation of hard coke, whereas 5Zn-HZSM5 pro­
motes the formation of soft coke (volatiles) at 20 bar reaction pressure,
723 K temperature and 0.75 h− 1 WHSV. The coke deposited on spent
HZSM5 (55) and 5Zn-HZSM5 (55) catalyst was extracted using the
procedure described by Zhang et al. [60]. The details of the coke
extraction procedure are available in the supplementary information. As
shown in Fig. 20, higher amount of hard coke was deposited on spent
HZSM5 as deep black color solution together with higher amount of
insoluble black residue was obtained compared to spent 5ZnHZSM5 (55)
catalyst. The CH2Cl2 organic solvent extracted phase was analyzed by
GC for both the HZSM5 (55) and 5Zn-HZSM5 (55) catalysts (Figs. S26a
and b). The alkyl-substituted aromatics and polynuclear aromatics
(naphthalene and alkyl naphthalenes) were formed on both the cata­
lysts. However, relative amount of alkyl substituted aromatics and
polynuclear aromatics were higher in spent HZSM5 (55) than
5Zn-HZSM5 (55).
Moreover, pore size and surface area measurement revealed a
decrease in the micropore volume and external surface area of spent
catalysts with an increase in reaction pressure (Table 3) suggesting
deposition of carbonaceous species. The drastic drop in the external
surface area was observed for spent HZSM5 (55) (20 bar), which was
because of the deposition of higher aromatics on the external surface
compared to Zn-HZSM5 (55) spent catalysts. The internal (inside pores)
and external (external surface) cokes were estimated based on the
method reported in the literature [62–64] and details are also available
as supplementary information. A small increase in amount of internal
coke than external coke at higher pressure attributed to the formation of
higher molecular aromatics on the surface of the catalyst as discussed
earlier. The high amount of external coke observed for spent HZSM5
(55) at 20 bar reaction pressure was because of the formation of heavy
18
Microporous and Mesoporous Materials 323 (2021) 111216
VTc (cm3/g) Vmd (cm.3/g) Ame (m2/g)
0.24 0.10 199
0.23 0.08 157
0.22 0.08 153
0.21 0.07 138
0.21 0.07 131
0.19 0.06 123
0.21 0.07 170
0.29 0.12 162
aromatics (Fig. S27). The ratio of internal to external coke over spent
5Zn-HZSM5 (55) at 1, 5, 10, 20, 30 bar and spent HZSM5 (55) at 20 bar
were 0.53, 0.45, 0.87, 0.61, 0.99 and 0.15 respectively.
In addition, the spent catalysts were characterized by FTIR and
UV–vis spectroscopy. The IR spectra in the wavenumber region of
1300–1700 cm− 1 and 2800-3100 cm− 1 are important to characterize the
coke in spent catalysts (Figs. S28a and b). In the first region, the IR band
appeared at 1390 cm− 1 is assigned to the terminal –CH3 groups, whereas
IR band at 1460 cm− 1 is attributed to the combination of aliphatics
(bending and scissoring) and alkyl aromatics [64]. Thus, the assignment
of the later IR band is not free from ambiguity. The IR bands appeared at
1620, 1515, 1400 and 1370 cm− 1 are assigned to the νC = C vibrations
of unsaturated hydrocarbons, νC-C, νC-C in ring aromatic vibration,
δaCH3 and δsCH3 of aliphatic hydrocarbon. In the second region, the IR
band at 2870 cm− 1 corresponds to CH3 groups, and the IR bands ~2900
and 2935 cm− 1 are assigned to – CH2 and –CH3 groups [65,66]. The IR
band appeared at 2960 cm− 1 is due to the –CH3 groups [64]. As observed
from the figures, the intensity of the IR band for aliphatic and alkyl
aromatics at 1460 cm− 1 is increased with the increase in reaction
pressure from 1 bar to 30 bar. So, it is clearly evident that at higher
pressures more aliphatic and alkyl aromatics hydrocarbons were
deposited on the 5Zn-HZSM5 (55) catalysts. The UV–vis spectra of spent
catalysts at different reaction pressure are shown in Fig. S30. All the
spent catalyst UV–vis spectra revealed broad band suggesting hetero­
geneity of the coke. The band appeared at 365–375 nm is attributed to
the conjugated double bond and poly condensed aromatics with multi­
ple aromatic rings [64]. The appearance of band at 560 and 700 nm
further confirms the formation of polycondensed aromatics. The in­
tensity of bands characteristics of polycondensed aromatics increases
with the increase in reaction pressure confirming the formation of pol­
ycondensed aromatics at higher reaction pressure.
3.9. Reaction mechanism
The BTA reactions was performed over xZn-HZSM5 catalysts under
wide range of process parameters. Various aliphatic hydrocarbons (C1 to
C12) and aromatic hydrocarbons (C6 to C12) were formed as products
under the studied reaction conditions. Water and hydrogen was also
formed. However, CO was not observed in the gaseous products mixture.
The absence of CO might be because of its rapid transformation to
methane, which was identified as gaseous product. Based on the product
distribution obtained under various reaction conditions, a plausible re­
action mechanism was proposed for the direct conversion of n-butanol
to various aromatics over xZn-HZSM5 catalysts as shown in Scheme 1.
The direct conversion of n-butanol to various aromatics was
T. Kella and D. Shee
Scheme 1. Reaction pathway for the aromatization of n-butanol to aromatics over Zn-HZSM5 catalysts.
proceeded via the formation of olefins (butylenes and propylene), which
were subsequently transformed to different aromatics following various
reactions as discussed below. n-butanol underwent direct dehydration
reaction and or via the formation of di-butyl ether to produce butylenes
over acid sites [22,25]. However, contribution of these dehydration
pathways was not discernible. Nonetheless, the di-butyl-ether was not
identified in the present investigation as this product is generally formed
at lower temperature (below 550 K). The butylenes including all of its
isomers were formed via isomerization reaction over acid sites. In
another route, the n-butanol was first transformed to butanal via
dehydrogenation reaction, which was then transformed to propylene
and propane via dehydroformylation and decarbonylation reaction,
respectively. The dehydrogenation of n-butanol proceeds over metallic
center of the Zn-HZSM5 catalysts and to some extent over extra frame­
work alumina of zeolites [22,25]. The various olefins formed were oli­
gomerized to form C5–C12 olefins over acidic sites. The ethylene was
formed because of the cracking of alkyl chains of the aromatics at high
reaction temperature. The self metathesis of 1-butylene or propylene
was another possibility for the formation of ethylene [22].
The hydrogenation of various olefins (C2–C12) led to the formation of
corresponding paraffins, C2–C12. The C6–C12 olefins transformed to cy­
clic paraffins (naphthene) via cyclization reaction and dehydrogenation
of these cyclic paraffins led to the formation of aromatics. Moreover, the
hydride transfer reaction of C3–C4 and cyclic paraffins (naphthene) was
another pathway for the formation of C3–C4 paraffins and aromatics.
The contribution of hydride transfer reaction was declined with the
19
Microporous and Mesoporous Materials 323 (2021) 111216
increase in Zn loading. In case of Zn-HZSM5 (55) catalysts, the dehy­
drogenation of naphthene was dominant reaction pathway for the for­
mation of aromatics. Thus, the suppression of hydride transfer reaction
and enhancement of dehydrogenation of naphthene in presence of Zn
were the key factors for the higher selectivity of BTEX. The distribution
of aromatics, specifically BTEX was also greatly influenced by various
reaction parameters. Isomerization, disproportionation, transakylation
and hydrodealkylation reactions were important for their inter trans­
formation as shown in Scheme 1.
4. Conclusions
The direct conversion of n-butanol to aromatics with enhanced
selectivity to BTEX was performed over Zn impregnated HZSM5 (SiO2/
Al2O3 = 23, 55 and 280) catalysts under different process parameters.
The incorporation of Zn in HZSM5 has a great influence on the textural
properties and, nature and strength of acidity of Zn-HZSM5 catalysts.
Deposition of Zn decreases the external surface area significantly than
the micropore area. The NH3-TPD studies revealed the generation of
medium strength acidity on deposition of Zn in HZSM5. The concen­
tration of Brønsted acid sites decreases, whereas Lewis acid sites in­
creases as the Zn loading increases. The incorporation of Zn in HZSM5
has strong influence on the selectivity of total aromatics and BTEX. The
selectivity of total aromatics and BTEX increases with the increase in Zn
loading till 5 wt% and slightly decreases thereafter. The presence of Zn
species suppresses the hydride transfer reaction and promotes the
T. Kella and D. Shee
dehydrogenation reaction of naphthene leading to the enhancement of
the selectivity of aromatics and BTEX. Moreover, the enhancement of
Lewis acidity increases the alkylation of C8 aromatics resulting in the
enhancement of C9 aromatic selectivity. Specifically, in BTEX fraction,
the variation of benzene and ethyl benzene selectivities were insignifi­
cant, whereas the selectivity of toluene and xylenes selectivities was
increased significantly upto 5 wt% of Zn loading. The higher selectivity
of C8 aromatics might be because of the enhanced alkylation of
respective lighter aromatics. The reaction parameters have also signifi­
cant effect on the aromatics product distribution. Low WHSV favors the
aromatization reaction resulting in higher selectivity of total aromatics
and BTEX. Moreover, low WHSV promotes hydride transfer reaction for
the production of aromatics. The selectivity of aromatics and BTEX in­
crease with the rise in temperature till 748K. Hydrodealkylation was
favorable reaction for the production of light aromatics at high tem­
perature. However, the reaction pressure has adverse effect. The selec­
tivities of total aromatics and BTEX decreases with the increase in
reaction pressure. The high reaction pressure results in the formation of
higher aromatics causing deactivation of the catalysts. The maximum
selectivities of total aromatics and BTEX achieved were 74.83% and
68.75% (B: 11.10%, T: 32.67%, E: 0.54%, X: 24.44) at 723 K, 1 bar and
o.75 h− 1 WHSV for 5Zn-HZSM5 (55) catalyst. Detail coke analysis
revealed that high reaction pressure led to the formation of coke of
polynuclear aromatic in nature. The alkyl substitute aromatics and
polynuclear aromatics were formed predominately on pure HZSM5 (55)
than 5Zn-HZSM5 (55). A plausible reaction mechanism was proposed
based on the product distribution obtained at different reaction
conditions.
CRediT authorship contribution statement
Tatinaidu Kella: Investigation, Formal analysis, Writing – original
draft, preparation. Debaprasad Shee: Supervision, Conceptualization,
Resources, Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2021.111216.
References
[1] P.S. Rezaei, H. Shafaghat, W.M.A.W. Daud, Production of green aromatics and
olefins by catalytic cracking of oxygenate compounds derived from biomass
pyrolysis: a review, Appl. Catal. A Gen. 469 (2014) 490–511, https://doi.org/
10.1016/j.apcata.2013.09.036.
[2] G. Fogassy, N. Thegarid, G. Toussaint, A.C. van Veen, Y. Schuurman, C. Mirodatos,
Biomass derived feedstock co-processing with vacuum gas oil for second-
generation fuel production in FCC units, Appl. Catal. B Environ. 96 (2010)
476–485, https://doi.org/10.1016/j.apcatb.2010.03.008.
[3] Z. Liu, L. Xu, L. Yu, S. Xie, W. Xin, S. Huang, S. Zhang, Transformation of isobutyl
alcohol to aromatics over zeolite-based catalysts, ACS Catal. 2 (2012) 1203–1210,
https://doi.org/10.1021/cs300048u.
[4] M.D. Boot, M. Tian, E.J.M. Hensen, S. Mani Sarathy, Impact of fuel molecular
structure on auto-ignition behavior – design rules for future high performance
gasolines, Prog. Energy Combust. Sci. 60 (2017) 1–25, https://doi.org/10.1016/j.
pecs.2016.12.001.
[5] A. Maneffa, P. Priecel, J.A. Lopez-Sanchez, Biomass-derived renewable aromatics:
selective routes and outlook for p-xylene commercialisation, ChemSusChem 9
(2016) 2736–2748, https://doi.org/10.1002/cssc.201600605.
[6] C.A. Mullen, A.A. Boateng, Production of aromatic hydrocarbons via catalytic
pyrolysis of biomass over Fe-modified HZSM-5 zeolites, ACS Sustain. Chem. Eng. 3
(2015) 1623–1631, https://doi.org/10.1021/acssuschemeng.5b00335.
[7] C.L. Williams, C. Chang, P. Do, N. Nikbin, S. Caratzoulas, D.G. Vlachos, R.F. Lobo,
W. Fan, P.J. Dauenhauer, Cycloaddition of biomass-derived furans for catalytic
20
Microporous and Mesoporous Materials 323 (2021) 111216
production of renewable p -xylene, ACS Catal. 2 (2012) 935–939, https://doi.org/
10.1021/cs300011a.
[8] S. Fegade, B. Tande, A. Kuba, W. Seames, E. Kozliak, Novel two-step process for the
production of renewable aromatic hydrocarbons from triacylglycerides, Ind. Eng.
Chem. Res. (2015), https://doi.org/10.1021/acs.iecr.5b01932.
[9] A. Bhan, W.N. Delgass, Propane aromatization over HZSM-5 and Ga/HZSM-5
catalysts, Catal. Rev. Sci. Eng. 50 (2008) 19–151, https://doi.org/10.1080/
01614940701804745.
[10] G. Caeiro, R.H. Carvalho, X. Wang, M.A.N.D.A. Lemos, F. Lemos, M. Guisnet,
F. Ramôa Ribeiro, Activation of C2–C4 alkanes over acid and bifunctional zeolite
catalysts, J. Mol. Catal. A Chem. 255 (2006) 131–158, https://doi.org/10.1016/j.
molcata.2006.03.068.
[11] H. Borwitzky, G. Schomburg, Separation and identification of polynuclear aromatic
compounds in coal tar by using glass capillary chromatography including
combined gas chromatography-mass spectrometry, J. Chromatogr. A 170 (1979)
99–124, https://doi.org/10.1016/S0021-9673(00)84242-9.
[12] J.H. Lunsford, Catalytic conversion of methane to more useful chemicals and fuels:
a challenge for the 21st century, Catal. Today 63 (2000) 165–174, https://doi.org/
10.1016/S0920-5861(00)00456-9.
[13] S.K. Maity, Opportunities, recent trends and challenges of integrated biorefinery:
Part I, Renew. Sustain. Energy Rev. 43 (2015) 1427–1445, https://doi.org/
10.1016/j.rser.2014.08.075.
[14] S.K. Maity, Opportunities, recent trends and challenges of integrated biorefinery:
Part II, Renew. Sustain. Energy Rev. 43 (2015) 1446–1466, https://doi.org/
10.1016/j.rser.2014.08.075.
[15] M. Inaba, K. Murata, M. Saito, I. Takahara, Ethanol conversion to aromatic
hydrocarbons over several zeolite catalysts, React. Kinet. Catal. Lett. 88 (2006)
135–142, https://doi.org/10.1556/RKCL.88.2006.1.18.
[16] K. Ji, J. Xun, P. Liu, Q. Song, J. Gao, K. Zhang, J. Li, The study of methanol
aromatization on transition metal modified ZSM-5 catalyst, Chin. J. Chem. Eng. 26
(2018) 1949–1953, https://doi.org/10.1016/j.cjche.2018.03.024.
[17] C.M. Lok, J. Van Doorn, G. Aranda Almansa, Promoted ZSM-5 catalysts for the
production of bio-aromatics, a review, Renew. Sustain. Energy Rev. 113 (2019)
109248, https://doi.org/10.1016/j.rser.2019.109248.
[18] K.K. Ramasamy, Y. Wang, Catalyst activity comparison of alcohols over zeolites,
J. Energy Chem. 22 (2013) 65–71, https://doi.org/10.1016/S2095-4956(13)
60008-X.
[19] W.R. da S. Trindade, R.G. dos Santos, Review on the characteristics of butanol, its
production and use as fuel in internal combustion engines, Renew. Sustain. Energy
Rev. 69 (2017) 642–651, https://doi.org/10.1016/j.rser.2016.11.213.
[20] M. Mascal, Chemicals from biobutanol: technologies and markets, Biofuels
Bioprod. Biorefin. 6 (2012) 483–493, https://doi.org/10.1002/bbb.1328.
[21] J. Mora Vargas, L.H. Tofaneli Morelato, J. Orduna Ortega, M. Boscolo, G. Metzker,
Upgrading 1-butanol to unsaturated, carbonyl and aromatic compounds: a new
synthesis approach to produce important organic building blocks, Green Chem. 22
(2020) 2365–2369, https://doi.org/10.1039/d0gc00254b.
[22] V.C.S. Palla, D. Shee, S.K. Maity, Conversion of n-butanol to gasoline range
hydrocarbons, butylenes and aromatics, Appl. Catal. A Gen. 526 (2016) 28–36,
https://doi.org/10.1016/j.apcata.2016.07.026.
[23] M. John, K. Alexopoulos, M.F. Reyniers, G.B. Marin, Mechanistic insights into the
formation of butene isomers from 1-butanol in H-ZSM-5: DFT based microkinetic
modelling, Catal. Sci. Technol. 7 (2017) 1055–1072, https://doi.org/10.1039/
c6cy02474b.
[24] M. John, K. Alexopoulos, M.F. Reyniers, G.B. Marin, First-principles kinetic study
on the effect of the zeolite framework on 1-butanol dehydration, ACS Catal. 6
(2016) 4081–4094, https://doi.org/10.1021/acscatal.6b00708.
[25] V.C.S. Palla, D. Shee, S.K. Maity, Production of aromatics from n-butanol over
HZSM-5, H-β, and γ-Al2O3 : role of silica/alumina mole ratio and effect of pressure,
ACS Sustain. Chem. Eng. 8 (2020) 15230–15242, https://doi.org/10.1021/
acssuschemeng.0c04888.
[26] Y. Jiang, J. Liu, W. Jiang, Y. Yang, S. Yang, Current status and prospects of
industrial bio-production of n-butanol in China, Biotechnol. Adv. 33 (2015)
1493–1501, https://doi.org/10.1016/j.biotechadv.2014.10.007.
[27] B. Ndaba, I. Chiyanzu, S. Marx, n-Butanol derived from biochemical and chemical
routes: a review, Biotechnol. Rep. 8 (2015) 1–9, https://doi.org/10.1016/j.
btre.2015.08.001.
[28] J. Sun, Y. Wang, Recent advances in catalytic conversion of ethanol to chemicals,
ACS Catal. 4 (2014) 1078–1090, https://doi.org/10.1021/cs4011343.
[29] P. Dejaifve, A. Auroux, P.C. Gravelle, J.C. Védrine, Z. Gabelica, E.G. Derouane,
Methanol conversion on acidic ZSM-5, offretite, and mordenite zeolites: a
comparative study of the formation and stability of coke deposits, J. Catal. 70
(1981) 123–136, https://doi.org/10.1016/0021-9517(81)90322-5.
[30] J.M. Fougerit, N.S. Gnep, M. Guisnet, Selective transformation of methanol into
light olefins over a mordenite catalyst: reaction scheme and mechanism,
Microporous Mesoporous Mater. 29 (1999) 79–89, https://doi.org/10.1016/
S1387-1811(98)00322-9.
[31] Y. Gao, B. Zheng, G. Wu, F. Ma, C. Liu, Effect of the Si/Al ratio on the performance
of hierarchical ZSM-5 zeolites for methanol aromatization, RSC Adv. 6 (2016)
83581–83588, https://doi.org/10.1039/c6ra17084f.
[32] M. Conte, J.A. Lopez-Sanchez, Q. He, D.J. Morgan, Y. Ryabenkova, J.K. Bartley, A.
F. Carley, S.H. Taylor, C.J. Kiely, K. Khalid, G.J. Hutchings, Modified zeolite ZSM-5
for the methanol to aromatics reaction, Catal. Sci. Technol. 2 (2012) 105–112,
https://doi.org/10.1039/c1cy00299f.
[33] T. Liang, H. Toghiani, Y. Xiang, Transient kinetic study of ethane and ethylene
aromatization over zinc-exchanged HZSM-5 catalyst, Ind. Eng. Chem. Res. 57
(2018) 15301–15309, https://doi.org/10.1021/acs.iecr.8b03735.
T. Kella and D. Shee
[34] A. Mehdad, R.F. Lobo, Ethane and ethylene aromatization on zinc-containing
zeolites, Catal. Sci. Technol. 7 (2017) 3562–3572, https://doi.org/10.1039/
c7cy00890b.
[35] Y. Ono, H. Kitagawa, Y. Sendoda, Transformation of but-1-ene into aromatic
hydrocarbons over ZSM-5 zeolites, J. Chem. Soc. Faraday Trans. 1 Phys. Chem.
Condens. Phases 83 (1987) 2913, https://doi.org/10.1039/f19878302913.
[36] T. Wang, X. Tang, X. Huang, W. Qian, Y. Cui, X. Hui, W. Yang, F. Wei, Conversion
of methanol to aromatics in fluidized bed reactor, Catal. Today 233 (2014) 8–13,
https://doi.org/10.1016/j.cattod.2014.02.007.
[37] L.M. Lubango, M.S. Scurrell, Light alkanes aromatization to BTX over Zn-ZSM-5
catalysts: enhancements in BTX selectivity by means of a second transition metal
ion, Appl. Catal. A Gen. 235 (2002) 265–272, https://doi.org/10.1016/S0926-
860X(02)00271-5.
[38] S. Tamiyakul, T. Sooknoi, L.L. Lobban, S. Jongpatiwut, Generation of reductive Zn
species over Zn/HZSM–5 catalysts for n–pentane aromatization, Appl. Catal. A
Gen. 525 (2016) 190–196, https://doi.org/10.1016/j.apcata.2016.07.020.
[39] J.A. Biscardi, G.D. Meitzner, E. Iglesia, Structure and density of active Zn species in
Zn/H-ZSM5 propane aromatization catalysts, J. Catal. 179 (1998) 192–202,
https://doi.org/10.1006/jcat.1998.2177.
[40] J. Liu, A.S.N. La Hong, N. He, G. Liu, C. Liang, X. Zhang, H. Guo, The crucial role of
reaction pressure in the reaction paths for i-butane conversion over Zn/HZSM-5,
Chem. Eng. J. 218 (2013) 1–8, https://doi.org/10.1016/j.cej.2012.12.037.
[41] N. Viswanadham, A.R. Pradhan, N. Ray, S.C. Vishnoi, U. Shanker, T.S.R. Prasada
Rao, Reaction pathways for the aromatization of paraffins in the presence of H-
ZSM-5 and Zn/H-ZSM-5, Appl. Catal. A Gen. 137 (1996) 225–233, https://doi.org/
10.1016/0926-860X(95)00287-1.
[42] B.S. Liu, Y. Zhang, J.F. Liu, M. Tian, F.M. Zhang, C.T. Au, A.S.-C. Cheung,
Characteristic and mechanism of methane dehydroaromatization over Zn-Based/
HZSM-5 catalysts under conditions of atmospheric pressure and supersonic jet
expansion, J. Phys. Chem. C 115 (2011) 16954–16962, https://doi.org/10.1021/
jp2027065.
[43] P. He, J.S. Jarvis, S. Meng, Q. Li, G.M. Bernard, L. Liu, X. Mao, Z. Jiang, H. Zeng, V.
K. Michaelis, H. Song, Co-aromatization of methane with propane over Zn/HZSM-
5: the methane reaction pathway and the effect of Zn distribution, Appl. Catal. B
Environ. 250 (2019) 99–111, https://doi.org/10.1016/j.apcatb.2019.03.011.
[44] M. Xin, E. Xing, Y. Ouyang, X. Gao, G. Xu, Y. Luo, X. Shu, Insight into interactions
among P, Zn and ZSM-5 during bi-component modification on ZSM-5, New J.
Chem. 44 (2020) 20785–20796, https://doi.org/10.1039/D0NJ04136J.
[45] J. Liu, N. He, W. Zhou, L. Lin, G. Liu, C. Liu, J. Wang, Q. Xin, G. Xiong, H. Guo,
Isobutane aromatization over a complete Lewis acid Zn/HZSM-5 zeolite catalyst:
performance and mechanism, Catal. Sci. Technol. 8 (2018) 4018–4029, https://
doi.org/10.1039/c8cy00917a.
[46] Q.T. Cheng, B.X. Shen, H. Sun, J.G. Zhao, J.C. Liu, Methanol promoted naphtha
catalytic pyrolysis to light olefins on Zn-modified high-silicon HZSM-5 zeolite
catalysts, RSC Adv. 9 (2019), https://doi.org/10.1039/c9ra02793a, 20818–20828.
[47] F.L. Bleken, S. Chavan, U. Olsbye, M. Boltz, F. Ocampo, B. Louis, Conversion of
methanol into light olefins over ZSM-5 zeolite: strategy to enhance propene
selectivity, Appl. Catal. A Gen. (2012) 447–448, https://doi.org/10.1016/j.
apcata.2012.09.025, 178–185.
[48] Y. Kolyagin, V. Ordomsky, Y. Khimyak, A. Rebrov, F. Fajula, I. Ivanova, Initial
stages of propane activation over Zn/MFI catalyst studied by in situ NMR and IR
spectroscopic techniques, J. Catal. 238 (2006) 122–133, https://doi.org/10.1016/
j.jcat.2005.11.037.
[49] M. Akçay, The surface acidity and characterization of Fe-montmorillonite probed
by in situ FT-IR spectroscopy of adsorbed pyridine, Appl. Catal. A Gen. 294 (2005)
156–160, https://doi.org/10.1016/j.apcata.2005.07.019.
21
Microporous and Mesoporous Materials 323 (2021) 111216
[50] E.-M. El-Malki, R.A. van Santen, W.M.H. Sachtler, Introduction of Zn, Ga, and Fe
into HZSM-5 cavities by sublimation: identification of acid sites, J. Phys. Chem. B
103 (1999) 4611–4622, https://doi.org/10.1021/jp990116l.
[51] H. Coqueblin, A. Richard, D. Uzio, L. Pinard, Y. Pouilloux, F. Epron, Effect of the
metal promoter on the performances of H-ZSM5 in ethylene aromatization, Catal.
Today 289 (2017) 62–69, https://doi.org/10.1016/j.cattod.2016.08.006.
[52] K. Wang, M. Dong, X. Niu, J. Li, Z. Qin, W. Fan, J. Wang, Highly active and stable
Zn/ZSM-5 zeolite catalyst for the conversion of methanol to aromatics: effect of
support morphology, Catal. Sci. Technol. 8 (2018) 5646–5656, https://doi.org/
10.1039/c8cy01734d.
[53] A.A. Gabrienko, S.S. Arzumanov, A.V. Toktarev, I.G. Danilova, I.P. Prosvirin, V.
V. Kriventsov, V.I. Zaikovskii, D. Freude, A.G. Stepanov, Different efficiency of Zn2
+
and ZnO species for methane activation on Zn-modified zeolite, ACS Catal. 7
(2017) 1818–1830, https://doi.org/10.1021/acscatal.6b03036.
[54] N. Wang, Y. Hou, W. Sun, D. Cai, Z. Chen, L. Liu, B. Ge, L. Hu, W. Qian, F. Wei,
Modulation of b-axis thickness within MFI zeolite: correlation with variation of
product diffusion and coke distribution in the methanol-to-hydrocarbons
conversion, Appl. Catal. B Environ. 243 (2019) 721–733, https://doi.org/10.1016/
j.apcatb.2018.11.023.
[55] P. He, J. Jarvis, S. Meng, A. Wang, S. Kou, R. Gatip, M. Yung, L. Liu, H. Song, Co-
aromatization of methane with olefins: the role of inner pore and external surface
catalytic sites, Appl. Catal. B Environ. 234 (2018) 234–246, https://doi.org/
10.1016/j.apcatb.2018.04.034.
[56] N.R. Meshram, Selective toluene disproportionation over ZSM-5 zeolites, J. Chem.
Technol. Biotechnol. 37 (1987) 111–122, https://doi.org/10.1002/
jctb.280370206.
[57] N.R. Meshram, S.B. Kulkarni, P. Ratnasamy, Transalkylation of toluene with C9
aromatic hydrocarbons over ZSM-5 zeolites, J. Chem. Technol. Biotechnol. Chem.
Technol. 34 (1984) 119–126, https://doi.org/10.1002/jctb.5040340307. A.
[58] T.-C. Tsai, W.-H. Chen, S.-B. Liu, C.-H. Tsai, I. Wang, Metal zeolites for
transalkylation of toluene and heavy aromatics, Catal. Today 73 (2002) 39–47,
https://doi.org/10.1016/S0920-5861(01)00516-8.
[59] T. Tsai, Disproportionation and transalkylation of alkylbenzenes over zeolite
catalysts, Appl. Catal. A Gen. 181 (1999) 355–398, https://doi.org/10.1016/
S0926-860X(98)00396-2.
[60] H. Zhang, S. Shao, R. Xiao, D. Shen, J. Zeng, Characterization of coke deposition in
the catalytic fast pyrolysis of biomass derivates, Energy Fuels 28 (2014) 52–57,
https://doi.org/10.1021/ef401458y.
[61] C. Yang, M. Qiu, S. Hu, X. Chen, G. Zeng, Z. Liu, Y. Sun, Stable and efficient
aromatic yield from methanol over alkali treated hierarchical Zn-containing HZSM-
5 zeolites, Microporous Mesoporous Mater. 231 (2016) 110–116, https://doi.org/
10.1016/j.micromeso.2016.05.021.
[62] M. Guisnet, P. Magnoux, Organic chemistry of coke formation, Appl. Catal. A Gen.
212 (2001) 83–96, https://doi.org/10.1016/S0926-860X(00)00845-0.
[63] D. Bibby, Coke formation in zeolite ZSM-5, J. Catal. 97 (1986) 493–502, https://
doi.org/10.1016/0021-9517(86)90020-5.
[64] P. Castaño, G. Elordi, M. Olazar, A.T. Aguayo, B. Pawelec, J. Bilbao, Insights into
the coke deposited on HZSM-5, Hβ and HY zeolites during the cracking of
polyethylene, Appl. Catal. B Environ. 104 (2011) 91–100, https://doi.org/
10.1016/j.apcatb.2011.02.024.
[65] L. Palumbo, F. Bonino, P. Beato, M. Bjørgen, A. Zecchina, S. Bordiga, Conversion of
methanol to hydrocarbons: spectroscopic characterization of carbonaceous species
formed over H-ZSM-5, J. Phys. Chem. C 112 (2008) 9710–9716, https://doi.org/
10.1021/jp800762v.
[66] H.G. Karge, W. Nießen, H. Bludau, In-situ FTIR measurements of diffusion in
coking zeolite catalysts, Appl. Catal. A Gen. 146 (1996) 339–349, https://doi.org/
10.1016/S0926-860X(96)00175-5.