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Investigation of effective parameters on SAPO-34 nanocatalyst in the

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 Rev Inorg Chem 2020; aop

Zhidong Yang, Liehui Zhang, Yuhui Zhou*, Hui Wang, Lichen Wen and Ehsan Kianfar*

Investigation of effective parameters on SAPO-34

nanocatalyst in the methanol-to-olefin conversion
process: a review
https://doi.org/10.1515/revic-2020-0003 to optimize the catalyst performance by modifying the
Received February 11, 2020; accepted May 25, 2020 synthesis conditions. In this article, we will introduce
the MTO process and the factors affecting the production
Abstract: Light olefins such as ethylene, propylene and
of light olefins.
butylene are mainly used in the petrochemical industry.
Due to the growing need for light olefins in the industry Keywords: crystallinity; light olefins; MTO process;
and the future shortage of petroleum resources, the pro- SAPO-34; selectivity.
cess of converting methanol to olefins (MTO) using non-
oil sources has been considered as an alternative. Coal
and natural gas are abundant in nature and the methods
of converting them to methanol are well known today.
Introduction
Coal gasification or steam reforming of natural gas to
One of the new methods of producing light olefins that
produce synthetic gas (CO and hydrogen gas) can lead to
have recently made significant progress is the metha-
methanol production. Methanol can also be catalytically
nol-to-olefin (MTO) and methanol-to-propylene (MTP)
converted to gasoline or olefins depending on the effec-
process. The importance of MTO and MTP processes for
tive process and catalyst factors used. Due to the use of
the conversion of MTO and propylene have been dem-
crude methanol in the MTO unit and because the feed
onstrated commercially in recent years. The gas is syn-
does not require primary distillation, if the MTO unit is
thesized after being converted to methanol using the
installed alongside the methanol unit, its capital costs
Fischer-Tropsch reaction and acid catalysts are converted
will be reduced. The use of methanol can have advan-
to olefins, isoparaffins, gasoline products and aromatics
tages such as easier and less expensive transportation
(Dubois et al. 2003, Park et al. 2009, Fatourehchi et al.
than ethane. Among the available catalysts, SAPO-34 is
2011). This process has advantages over thermal cata-
the most suitable catalyst for this process due to its small
lytic cracking with steam, naphtha and light petroleum
cavities and medium acidity. One of the problems of MTO
cuttings because it provides a wider and more flexible
units is the rapid deactivation of SAPO-34, which can
range for the ethylene to propylene ratio (Alwahabi 2003,
also be affected by the synthesis factors, so it is possible
http://www.uop.com/mto-process-flow-scheme). Figure 1
shows an overview of the conversion of methanol to light
olefins.
*Corresponding authors: Yuhui Zhou, Yangtze University, Wuhan,
Hubei, China, e-mail: yuhuijiy@163.com; and Ehsan Kianfar, Other advantages include‫ ‏‬the production of limited
Department of Chemical Engineering, Arak Branch, Islamic Azad byproducts compared to other fracturing methods
University, Arak, Iran; and Young Researchers and Elite Club, resulting in simpler recycling and purification systems,
Gachsaran Branch, Islamic Azad University, Gachsaran, Iran, simpler unit use than conventional units due to low par-
e-mail: e-kianfar94@iau-arak.ac.ir, Ehsan_kianfar2010@yahoo.com.
affin content do and no need for propane/propylene and
https://orcid.org/0000-0002-7213-3772
Zhidong Yang: State Key Laboratory of Oil and Gas Reservoir ethane separator systems. Ethylene is another character-
Geology and Exploitation, Southwest Petroleum University, istic of the process due to the production of propylene
Chengdu, China; and The No. 1 Oil Production Plant, Petro China and ethylene with a purity of more than 98%. Of course,
Xinjiang Oilfield Company, Karamay, China there are other methods such as oxidative methane
Liehui Zhang: State Key Laboratory of Oil and Gas Reservoir Geology
coupling (OCM), oxidative dehydrogenation of kinds of
and Exploitation, Southwest Petroleum University, Chengdu, China
paraffin and internal conversion of olefins that are not
Hui Wang: The No. 2 Oil Production Plant, Petro China Xinjiang
Oilfield Company, Karamay, China currently commercially used (Dahl and Kolboe 1993,
Lichen Wen: Yangtze University, Wuhan, Hubei, China Jean 2005).
2 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst

Ethylene –– Parallel type mechanism

Higher olefins 2CH3OH → C2H4 + 2H2O
Methanol Dimethylether (minute amounts)
3CH3OH → C 3H6 + 3H2O 
Paraffin Propylene
4CH3OH → C4H8 + 4H2O (3)

Figure 1: Conversion of methanol to olefins (Fatourehchi et al. 2011).

In 1993, Dahl (1993) showed that sequential reactions

Mechanism and description of are not suitable for the MTO process, so they proposed a
mechanism called the common carbon mechanism, which
methanol-to-olefin (MTO) conversion is a branch of parallel reactions (Figure 2). In this model,

process in a dynamic state, carbon spaces are formed within the

shelves in the structure. These carbon compounds regu-
larly increase reactants and product production. Figure 3
Methanol is one of the main chemicals in the production
shows a simple outline of the MTO process for the UOP/
of a wide range of chemicals. The production of olefins
Hydro semi-industrial unit. Other companies, such as
from methanol was first carried out in 1977 by the mobile
ExxonMobil and Lurgi, employ other types of catalytic
company to develop the methanol-to-gasoline (MTG) con-
and process systems. As the figure shows, fresh methanol
version process. This process provides an indirect method
feed is combined with reclaimed water and fed to a flu-
of converting fossil resources into valuable industrial
idized bed catalyst reactor. The system is equipped with
olefins and other valuable products (Alwahabi 2003),
a catalyst regenerator and a return reactor. The reactor
whereby light olefins can be obtained significantly by
generally operates at 350°C and 30 PSIG pressure. With
taking water from methanol. This process is performed
the proprietary UOP/Hydro catalytic system, methanol
in the presence of zeolites as catalysts (Jean 2005). The
conversion is high and selectivity is about 80% for ethyl-
general outline of this process is as follows:
ene and propylene. The ratio of ethylene to propylene pro-
−H 2 O
→ −H 2 O duced can be changed from 1.5 to 0.6. The reactor outlet
2CH3OH ← CH3OCH3 →
+H2O for cooling water is cooled and the unreacted methanol
iso − paraffins returns with the return current. Reactor outlet catalysts
 
C2 − C 5 →  aromatics  (1)
− −
are driven to the regenerator where the coke burns with
 C + Olefins  the air. The restored catalysts are returned to the reactor
 6 
for reuse. The cooled outlet comes out of the condensed
reactor, carbon dioxide and water. Following compression
The main steps of the methanol conversion reaction to
operations, we have higher pressures, which lead to the
hydrocarbons can be summarized as follows:
liquidation of hydrocarbon compounds for distillation.
1. Dehydration of methanol and its conversion to dime-
Methanol is a major chemical building block used to man-
thyl ether (DME).
ufacture formaldehyde, methyl tert-butyl ether (MTBE),
2. Formation of equilibrium mixtures consisting of
acetic acid and a wide range of other chemical products.
methanol, DME and water.
The slowdown in MTBE demand, mainly due to the deci-
3. Convert balance equilibrium to light olefins.
sion taken by California and later by other states in the
4. The conversion of light olefins into paraffin, aromatics,
US to eliminate its use in the gasoline, is causing some of
naphtha and heavy olefins by reactions such as hydro-
the producers in the world to explore alternate utilization
gen exchange, alkylation and successive cooling.

In this process, we see the formation of C-C bonds. The

reactions through which these bonds are formed are C2H4

divided into two general categories of parallel and sequen-

tial reactions (Dahl and Kolboe 1993): CH3OH (CH2)n C3H6
–– Sequential type mechanism
Saturated hydrocarbons
2C1 → C2H4
C4H8 Coke
C 2 H 4 + C 1 → C 3H 6
C 3H6 + C 1 → C 4 H8 (2) Figure 2: Carbon pool mechanism (Dahl 1993).

 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst
Phase CO2 Removal
Separator Compressor
(STG 1–3)
Water
Flue
gas
Dryer
Reactor
Regenerator
Depropanizer
Crude (Recycle)
MeOH Air
Figure 3: A view of the UOP/Hydro MTO unit (http://www.netl.doe.gov/technologies/coalpower/gasification/gasifipedia/6-apps/6-5-2_
coal-to-derivative.html).
of their existing methanol plants. One such utilization
is the conversion of MTO. The production of light olefins
from methanol was first realized around 1977, during the
development of Mobil’s MTG process. In the MTG process,
where Zeolite Socony Mobil-5 (ZSM-5) is used as a cata-
lyst, methanol is first dehydrated to DME. The equilibrium
mixture of methanol, DME and water is then converted
to light olefins. A final reaction step leads to a mixture of
higher olefins, n/iso-paraffins, aromatics and naphthenic.
In this study, the authors tried to address some
researchers who worked on the investigation of effective
parameters on SAPO-34 nanocatalyst performance of light
olefin production through methanol. After that, the authors
compare them, as described in the following sections.
Factors influencing the MTO process
Influence of temperature on MTO reaction
In the process of MTO conversion, if ethylene is the major
production material, the heat of reaction required is less
than when propylene is considered to be a major com-
ponent of the product. In this process, to produce more
propylene than ethylene, measures such as feed contact
time with the catalyst, higher reaction temperature and
greater methanol partial pressure in contact with the cata-
lyst should be considered to obtain propylene as the main
product. Simple operational changes can be customized to
product ratio. Because the process of converting methanol
3
Compressor
(STG 4–5)
Demethanizer
Flue
gas Ethylene
Acetylene C2 Splitter
Converter
Deethanizer
Ethane
Propylene
Oxygen
Removal unit
C3 Splitter
Propane
C4′S
C5–
Debutanizer
to hydrocarbons is exothermic, there are different temper-
ature patterns in the catalytic substrate. In the meantime,
the rate of inactivation of the catalyst particles depends
on the maximum process temperature, which increases
linearly with the increase of this maximum temperature
(Echevskii et al. 1988). When using the SAPO-34 catalyst,
the catalyst deactivation rate increases with increasing
temperature and the selectivity of light olefins is reduced.
The effect of pressure on the rate of
methanol conversion to olefins
Choosing the best pressure is an important factor in
achieving the highest catalyst stability and selectivity
required in the MTO process. The lower the pressure,
the higher the number of gaseous hydrocarbons, while
the higher the pressure, the higher the production of
hydrocarbons with five carbon atoms and more. Based
on research in the fixed bed reactor, the process of con-
verting MTO at high pressures produces more aromatic
products. This is due to the increased selectivity of aro-
matics in the breakdown of C5+ hydrocarbons for high
pressures (Chang et al. 1979). Meanwhile, the amount of
coke formed on the catalyst also increases with increas-
ing pressure (Lok et al. 1984, Cornell 1990, Comelli et al.
1991, Demuth et al. 1995, Girnus et al. 1995, Casady and
Johnson 1996, Coluccia et al. 1999, Wei et al. 2007, Wilson
2009, Utchariyajit and Wongkasemjit 2010, Hang et al.
2011, Topuz et al. 2013, Wang et al. 2013, Hajfarajollah
et al. 2014).
4 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst

Effect of feed input composition on the reactor
Studies show that when the diluents in the feed stream
decrease with partial methanol inlet feed, the selectivity
of olefins increases (Liu et al. 1984, Marchi and Froment
1991), with studies conducted in a tube reactor showing
that the presence of ethylene in the feed reduces the selec-
tivity of ethylene and increases the selectivity of propylene
and butylene, and the presence of propylene with metha-
nol in the feed intake significantly reduces the selectivity
of propylene and increases the amount of butylene (Wu
and Anthony 2001). Other diluents can be nitrogenated.
Wu and Anthony (2001) noted that it has little effect on
thermodynamics, but causes separation problems. Of
all the diluents available, water is the best option as it is
readily available and its vapor has a high thermal capac-
ity and can remove a large amount of reaction heat (Park
and Froment 2001). Adding water to the inlet feed reduces
coke production and increases catalyst activity. In 1992,
Froment et al. (1992), by examining the MTO reaction on
a fixed bed, found that the presence of water in the inlet
feed could increase the production of olefins and reduce
Figure 4: Comparison of hydrocarbons produced by SAPO-34 and
ZSM-5 catalysts (Chen et al. 2005).
the selectivity to aromatics and paraffin. They attributed
this to the competition for water with olefins in adsorption
on strong acidic sites. In this case, some of the acid-active
sites on the catalyst surface are occupied by polar water
molecules, thereby preventing coke production on the
active sites. Therefore, more olefins are produced in the
reactor and the coke formation on the catalyst is reduced.
The catalyst in the MTO process
Methanol conversion reactions to hydrocarbons were
first performed in the early 1970s using ZSM-5 (MFI)
catalysts. In the 1980s, scientists at Union Carbide dis-
covered the SAPO-34 catalyst, a molecular sieve based
on silicoaluminophosphate. Research has shown that
this molecular sieve is a good catalyst for the conversion
of methanol to ethylene and propylene. The structure of
SAPO-34 with small cavity size (about 4 Å) and specific
shape provides favorable conditions for methanol con-
version. The small size of the catalyst holes limits the
penetration of heavy or chain hydrocarbons and results
in increased selectivity of light olefins. The use of the
ZSM-5 molecular sieve in other processes because of its
larger cavities (about 5.5 Å) shows lower yields for light
olefins. Figure 4 shows the difference in the number of
hydrocarbons produced by the SAPO-34 and ZSM-5 cata-
lysts. Another key feature of SAPO-34 is its good acidity
compared to zeolite aluminosilicates. Optimal acidity
in SAPO-34 reduces the production of paraffinic by-
products by preventing hydride transfer reactions (Chen
et al. 2005). The comparison of our catalytic behavior
in the MTO reaction with those catalytic performance
results of SAPO-34, ZSM-5 and several catalysts by other
researchers is reported in Table 1.

Table 1: Catalytic performance results of SAPO-34, ZSM-5 and several catalysts.

Catalyst structure Temperature (°C) WHSV (h − 1) Conversion (%) C2H4 (%) C3H6 (%) C4H8 (%) Reference

HZSM-5 399.85 – 38 1.35 3.47 1.89 (Zaidi and Pant 2005)

HZSM-5 370 8 88 16.5 32 15 (Bjørgen et al. 2008)
SAPO-34 450 1 99.8 48.7 37.1 8.6 (Li et al. 2015)
ZSM-5 450 1 99 2.7 43.7 23.3 (Li et al. 2015)
ZSM-5R 350 1.8 99 15 27 14 (Bleken et al. 2012)
ZSM-5N 350 1.8 100 14 23 11 (Bleken et al. 2012)
ZSM-5MS 350 1.8 99 12 30 18 (Bleken et al. 2012)
ZSM-5F 350 1.8 98 7 36 23 (Bleken et al. 2012)
SSZ-39-1 350 0.8 99.8 – – – (Martín et al. 2016)
SSZ-39-1 350 0.8 99.8 – – – (Martín et al. 2016)
SSZ-13 350 0.8 99.8 – – – (Martín et al. 2016)
ZSM-22 449.85 0.5 99 1 3.47 15 (Dyballa et al. 2016)
 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst
Factors affecting the performance
of SAPO-34 catalyst
Template materials
Template materials can play a structural, charge-compen-
sating and filling role in the synthesis of molecular sieve
(Pastore et al. 2005). Therefore, template materials have an
important role in the structure and properties of the mole-
cular sieve. Much research has been done to understand
the reasons for how these materials affect the acidity of
SAPO-34 [i.e. the influence of template materials on silicon
(Si) binding and distribution]. The positive charge created
by the template materials determines the amount of nega-
tive charge on the grid. This effect also results in differ-
ent Si substitutions in the structure [substituting Si with
phosphorous (P) or 2Si instead of P and Al]. Therefore, the
number of moles of template materials will to a certain
extent affect the amount of product Si (Guangyu et al.
2012) and the amount of product Si will largely determine
the properties and performance of the catalyst process.
Al and Si precursors
Various Si precursors in the synthesis of SAPO-34 can be
tetraethyl orthosilicate (TEOS), silicic acid, SiO2 powder,
silica fume, silica colloid, silica gel, etc. Aluminum (Al)
can also be used for precursors such as aluminum isopro-
poxide, pseudoboehmite, metallic Al, sodium aluminate
and so on. The use of different Si and Al precursors can
have a significant impact on the Si content of the finished
products. To explain this, for example, using aluminum
isopropoxide produces the lowest amount of Si in the final
product, whereas when using pseudoboehmite as the Al
precursor, the highest Si content will be observed in the
final product. This may be due to the higher reactivity of
the monomeric Al precursor (aluminum isopropoxide)
with H3PO4 than the polymeric precursor Al (pseudoboe-
hmite). Therefore, the precursor used can be effective in
mixing materials. However, for example, silica sol, as
a low-rate polymeric precursor, produces less active Si
species in the composition (Guangyu et al. 2012, Rostami-
zadeh et al. 2018, Sun et al. 2018).
The role of water in gel synthesis
Water plays a solvent role in hydrothermal synthesis
(HTS). For different zeolites in the initial gel, water varies
5
over a certain period. The concentration of the reactants
also varies with the amount of water, so the crystallin-
ity of the zeolite particles is also affected. Generally, by
diluting the synthesis of the synthesis gel, supersatura-
tion is reduced and the crystals grow against nucleation
and larger crystals will be created. The change in water
content can also result in the crystallinity of the zeolite
phases (Xu et al. 2006, Sun et al. 2014, Wang et al. 2015,
2018, Epelde et al. 2017, Kianfar 2018, 2019a–d, Kianfar
et al. 2018a,b, 2019, Li et al. 2018).
Modification of catalyst with metals
One of the ways to improve the performance of the cata-
lyst is to modify it using metals. The metal incorpora-
tion into the zeolite structure results in a decrease in
the acidity of the compound, which results in increased
ethylene selectivity, reduced coke formation and thus
increased catalyst life (Inui and Kang 1997, Djieugoue
et al. 1999, Salmasi et al. 2011). Much research has been
done to extend the catalyst life and increase the selectiv-
ity of light olefins by modification of SAPO-34 catalysts
with different cations but different synthesis condi-
tions such as modification methods (interpolation, ion
exchange and saturation), raw material sources and
time and the reaction temperature can produce different
results (Cola et al. 2006). The addition of metal cations to
the SAPO-34 structure also modifies the acidic properties
and catalyst performance (Hochtl et al. 2001, Rostamiza-
deh et al. 2018). Scientists attribute this particular selec-
tivity after catalyst modification to the strength of acidic
sites that are much weaker than unmodified SAPO-34.
These sites are weaker than they can be to generate aro-
matics (Wilson and Barger 1999, Chaida-Chenni et al.
2018, Rami et al. 2019).
The effect of SiO2/Al2O3 ratio on SAPO-34
catalyst
The structure of the aluminophosphate molecular sieve
(AlPO4) is electrically neutral and cannot exchange ion.
As Si atoms enter the compound and replace them with
P atoms, the charge of the network becomes negative.
In the process of calcination of catalysts by decompos-
ing organic template materials and releasing the proton,
hydroxyl groups are formed as Bronsted acid sites and the
charge of negative centers is neutralized. In the case of
SAPO-34, at least two types of hydroxyl groups with differ-
ent infrared (IR) absorption bonds (3625 and 3600 cm−1)
6 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst
have been observed (Zubkov et al. 1991, Zibrowius et al.
1992). The amount of Si/Al in the synthesis gel can affect
the size of the crystals, the degree of crystallinity and the
purity of the resulting compound. In their study, Liu et al.
(2008) observed that when Si is not incorporated into
the structure, the only materials created are amorphous
compounds. When the initial gel is 0 < SiO2/Al2O3 < 0.1,
SAPO-34 appears with impurities in the product, and pure
SAPO-34 occurs only when SiO2/Al2O3 > 0.1. The acidity of
the SAPO molecular sieve can be changed by controlling
their Si content. However, there is no direct relationship
between the number of acidic sites and the amount of Si
compound (Dahl et al. 1999), but for low amounts of Si
in SAPO, usually the Si substitution is isolated and there
will be one acidic site per Si. Si atoms are expected to
enter the SAPO-34 structure by three mechanisms. The
first mechanism occurs with the placement of the a-Si
atom instead of an Al atom (SM1), although no empiri-
cal evidence has been reported for this mechanism. In
the second mechanism, Si and H are replaced by P atoms
(SM2) and the released proton binds to O in the Si-O-Al
bond and forms a Bronsted acid site. The third mecha-
nism occurs with the replacement of two Si atoms instead
of the P and Al atoms (SM3). The type of mechanisms in
the composition can alter the number and strength of
acidic sites, thus optimizing the synthesis conditions to
determine the catalytic acidity to produce the desired
products (Sastre et al. 1997).
Crystallization temperature and time
The amount of time the gel is given for the crystallization
process affects the crystallinity of the finished product.
Hajiashrafi and Kharat (2013) showed that with
increasing crystallinity time from 24 to 72 h, SAPO-34 crys-
tallinity increased. As the process lengthens further, the
crystallinity of SAPO-34 and the byproducts will decrease.
The short duration and high temperatures in the crys-
tallization process slow down the growth of the nuclei,
producing small size crystals. Low temperatures require
longer crystals to compensate for the low reaction speed
(Emrani et al. 2011). Generally, at lower temperatures, the
tendency of the gel to nucleate is lower due to the high
activation energy required for the growth of the crystals
(Tan et al. 2002) and the short duration of the hydrother-
mal process at low temperatures results in incomplete
crystals resulting in reduced crystallinity (Emrani et al.
2011). Therefore, to have products with the right charac-
teristics, right time and temperature are needed for the
crystallization process.
Gel time
The gel synthesis time is the length of time the synthesis
gel usually remains at ambient temperature and stirring
before entering the crystallization process. Research in
this area demonstrates the importance of this factor in the
synthesis and function of the catalyst reactor (Hajiashrafi
and Kharat 2013).
A review of past research
In this study, we briefly review the research on the produc-
tion of SAPO-34 catalysts and the MTO process.
In recent years, with the rise in crude oil prices and the
growing demand for light olefins, the use of new methods
of producing light olefins has attracted much attention.
Converting methanol to light olefins (MTO) using metha-
nol from natural gas and coal is among the successful pro-
cesses in the production of light olefins. In recent decades,
catalyst engineering, reactor and catalytic reaction in the
MTO process have been seriously investigated. The distri-
bution of products in the MTO process can be controlled
by adjusting the reaction variables. Although significant
advances have been made in this area, SAPO-34 is rapidly
deactivated due to the acidic sites being covered and coke
closures. The catalytic performance of SAPO-34 is directly
affected by the morphology, crystal size, acid strength
and some other structural properties, and these proper-
ties can be altered during the synthesis process depending
on the type of material used and the operating condi-
tions of the synthesis. By adjusting the acidity, the cata-
lyst deactivation is reduced or delayed. The acidity of the
SAPO molecular sieve can be altered by isomorphic cation
substitution, cation exchange and Si/Al ratio adjustment.
Adjusting the acidity by changing the Si/Al ratio in the
SAPO compound is easier and cheaper and requires no
additional material. Also, the amount of water in the gel
as a solvent can change the morphology and structure of
the catalyst. The crystallinity rate and the pure phase per-
centage of SAPO-34 can be adjusted by the temperature
and time of crystallization, or the degree of crystallinity
of the initial gel and the amount of Si gel. Typically, the
higher the crystallinity percentage and the pure phase
of SAPO-34 and the less flawed structures, the higher the
methanol conversion rate and selectivity of the desired
components. The size of the crystals is a parameter affect-
ing the stability and conversion rate of methanol. Because
for the very small size of the crystals, the pore size is also
very small and there will be resistance to penetration for
 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst
methanol, on the other hand for the larger crystals, the
penetration path is long and the possibility of secondary
reactions for desirable products along the exit pathway
(and the production of larger molecules and cavity block-
ing) so crystals must have an optimal size. Based on these
investigations of effective parameters, the main results are
summarized below:
1. SAPO-34 is directly affected by the morphology, crys-
tal size, acid strength and some other structural prop-
erties, and these properties can be altered during the
synthesis process depending on the type of material
used and the operating conditions of the synthesis.
2. By adjusting the acidity, the catalyst deactivation is
reduced or delayed. The acidity of the SAPO molecu-
lar sieve can be altered by isomorphic cation substitu-
tion, cation exchange and Si/Al ratio adjustment.
3. Water in the gel as a solvent can change the morphol-
ogy and structure of the catalyst.
4. The crystallinity rate and the pure phase percentage
of SAPO-34 can be adjusted by the temperature and
time of crystallization, or the degree of crystallinity of
the initial gel and the amount of Si gel.
5. Typically, the higher the crystallinity percentage and
the pure phase of SAPO-34 and the less flawed struc-
tures, the higher the methanol conversion rate and
selectivity of the desired components.
6. The size of the crystals is a parameter affecting the
stability and conversion rate of methanol. Because
of the very small size of the crystals, the pore size is
also very small and there will be resistance to penetra-
tion for methanol; on the other hand, for the larger
crystals, the penetration path is long and there is pos-
sibility of secondary reactions for desirable products
along the exit pathway (and the production of larger
molecules and cavity blocking) so crystals must have
an optimal size.
7. Increasing the temperature and crystallization time
generally increases the particle size of the Sapo-34
catalyst.
The effect of Si/Al ratio
Izadbakhsh et al. (2009a) prepared SAPO-34 catalyst
with different Si/Al ratios (0.5–0.5) at a crystallization
temperature of 215–190°C by hydrothermal method and
obtained samples by various X-ray diffraction (XRD),
scanning electron microscopy (SEM)/energy-dispersive
X-ray spectroscopy (EDX) experiments. NH3-tempera-
ture-programmed desorption (TPD), Fourier-transform
infrared spectroscopy (FTIR) and nitrogen uptake were
7
investigated. EDX data showed that increasing the Si/Al
ratio in the initial gel blend increased the Si content in the
product. According to XRD and SEM results, the crystal-
linity of the samples increased with increasing Si/Al ratio.
Of course, the relative increase in the ratio of Si to Al did
not only increase the crystallinity but also decreased it.
The results obtained in the study of the catalyst perfor-
mance in the reactor with a reaction temperature of 400°C
and methanol discharge WHSV = 1 h−1 showed that the
SAPO-34 crystallinity affected by the change of Si/Al ratio
is an important factor in the coke production of methanol
to coke process. It is olefins. High crystallinity samples
(Si/Al = 0.13–0.22) lead to longer catalyst life in the reactor
of 3 h, which is longer than the life of the less crystalline
samples (1 h).
Shen et al. (2012) investigated the effect of Si on the
acidic properties of SAPO-34 using solid-state nuclear
magnetic resonance (NMR) analysis. The results
showed that there are two types of Bronsted acidic sites
in SAPO-34, one of which is stronger than the acidic site
in ZSM-5. Si species and their distribution in the compo-
sition structure depend on the Si content. Si islands are
mostly formed when the Si content is high, while the
low Si content only generates four Si (OAL) species. Si
has little effect on the strength of the SAPO-34 Bronsted
acids but can alter the catalyst acidity.
Wilson and Barger (1999) investigated the effec-
tive properties of SAPO catalysts on reactor performance
such as shape selectivity, acidic site strength, acidic site
content, crystal size and Si content in the catalyst. Evalua-
tion of small completely molecular sieve in the methanol-
to-olefin conversion process shows that SAPO-34 due to its
high selectivity to C2–C3 olefins, low production of paraf-
fin and aromatic byproducts and favorable conditions for
catalyst recovery compared to other catalyst species per-
forms best. Decreasing the amount of Si results in reduced
olefin production and increased the catalyst life. There is
also no direct relationship between the amount of Si in the
composition and the number of acidic sites, although in
low Si there is usually an acidic site per Si in the structure.
Wang et al. (2012a) investigated the effect of Si on the
Cu/SAPO-34 and HSAPO-34 catalyst properties. In the three
ratios tested for Si/Al in the experiments, it was found that
the sample had the smallest crystal size with a Si/Al ratio
of 0.3. The TPD experiment showed that the sample had
the highest amount of Si at the Si/Al = 0.85 ratios. As for
the Cu/SAPO-34 catalyst, studies showed that the number
of acidic sites increased with increasing Si content in the
samples. The EPR and H2-TPR results showed that the Si
and Al values affect the number of individual Cu2+ ions in
the catalyst.
8 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst
Izadbakhsh et al. (2009b) produced a low-Si SAPO-34
catalyst by hydrothermal method. The examination of
the samples showed that the total acidity in the samples
with low Si was much lower than the samples with higher
Si. Bronsted acid sites remained almost constant after a
threshold value for Si, with changes below these thresh-
old values reported.
Xu et al. (2008) synthesized SAPO-34 molecular
sieves with different forms of Si by changing the SiO2/
Al2O3 molar ratio in the initial gel. The crystal structure,
initial composition and different forms of Si deposition in
the synthesized samples were investigated by XRD, SEM,
XRF and NMR analysis. The SAPO-34 molecular sieve was
formed when the SiO2/Al2O3 ratio in the gel was higher
than 0.075. By varying the SiO2/Al2O3 ratio, the Si forma-
tion in the catalyst network was different, and when the
SiO2/Al2O3 molar ratio in the initial gel was in the range
of 0.15–0.075, SAPO-34 was formed with only Si (4Al)
structure.
Effect of water on the catalyst composition
Heyden et al. (2008) prepared nano-scale SAPO-34 cata-
lysts from colloidal solutions under different hydrother-
mal conditions in conventional and microwave ovens.
The smallest catalyst size was obtained by microwave
in a solution with the highest concentration of material
and the lowest amount of water (1 Al2O3:2 P2O5:0.6 SiO2:2
TEA2O:75 H2O). The effect of particle size on the adsorption
properties of SAPO-34 crystals by physical adsorption of
argon at 87°C showed that the volume of excess adsorbed
argon depends on the degree of particle porosity.
Hirota et al. (2010) prepared and compared SAPO-34
nanocatalysts in two HTS and dry gel conversion (DGC)
methods. The results showed that for the DGC sample,
cubic crystals were formed without any amorphous com-
position, so the crystallinity was high in this sample.
Due to the low growth rate of the crystals after nuclea-
tion in the DGC method, the average crystallite size of
the final DGC samples was about 75 nm, which was sig-
nificantly lower than that of the hydrothermal method
(8000 nm).
Lin et al. (2010) investigated the effect of the H2O/
Al2O3 ratio on the SAPO-34 catalyst initial gel by micro-
wave production method. They showed that water as a
solvent in the catalyst gel can affect the morphology and
particle size. Experiments showed that when TEOS was
used as the silica source, the morphology of the SAPO-34
crystals shifted to microspheres as the H2O/Al2O3 ratio
increased.
The effect of Si and Al precursors
Popova et al. (1998) investigated the acidic and catalytic
properties of SAPO-34s prepared with various organic
and inorganic precursors of Al and Si in the MTO process.
The results showed that the catalysts prepared with
organic precursors deactivated more rapidly and pro-
duced more methane, while the catalysts with high crys-
tallinity mineral content were more stable and had more
acidic sites. Therefore, they work better in producing light
olefins.
Hajiashrafi and Kharat (2013) investigated the effect
of Al and Si precursors. The results showed that the use
of silica fume resulted in higher production of SAPO-18,
whereas TEOS due to its high solubility in the gel could
be a good option for the formation of SAPO-34. Among
the Al precursors (aluminum isopropoxide and aluminum
hydroxide), aluminum isopropoxide also results in higher
purity products and higher surface area.
Effect of precursor template materials
Salmasi et al. (2011) prepared the SAPO-34 hydrothermal
catalyst using two template materials tetraethylammo-
nium hydroxide (TEAOH) and morpholine. The results
showed that the combination of TEAOH and morpholine
in comparison to template materials resulted in higher
crystallinity and smaller particle size in the final product.
Lee et al. (2007) investigated the effect of template
materials on the catalytic performance of SAPO-34 in
the conversion of MTO. SAPO-34 catalysts with 1 Al2O3:1
P2O5:0.6 SiO2:x morpholine:(2-x) molar ratio of TEAOH:52
H2O were prepared. Compared to template materials l, the
use of template materials combines to reduce particle size
and geometric deformation and to transform them into
spherical particles. The reactor performance and catalyst
synthesized by mixing 75% and 25% tetraethylammonium
morpholine hydroxide had the greatest lifetime.
Shirazi et al. (2011) investigated the effect of template
materials type on the catalytic performance of SAPO-34
in the process of methanol conversion to light olefins at
different temperatures. The catalysts were prepared by
hydrothermal method using morpholine, TEAOH and
dipropyl amine template materials with molar gel 1 Al2O3:1
P2O5:0.6 SiO2:2 template:50 H2O. Their characteristics were
evaluated by XRD, SEM, NH3-TPD and thermogravimet-
ric analysis-differential thermal analysis (TGA-DTA). The
results showed that the type of template materials influ-
enced the final catalyst characteristics such as crystal
size, morphology, crystallinity and purity of the product,
 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst
and the use of morpholine as template materials produced
larger crystals than other template materials. The reaction
of methanol to light olefins was carried out in the vicinity
of the HSAPO-34 catalyst with various template materi-
als at temperatures of 250–250°C, atmospheric pressure
and WHSV = 1 h−1. The results of the reactor experiments
showed that all the catalysts had relatively similar activity
and product distribution. The lowest catalyst lifetime was
also reported for the sample synthesized with morpholine
template materials.
Nishiyama et al. (2009) investigated the effect of size
control of SAPO-34 crystals on the catalyst lifetime during
methanol reaction to olefins. Experiments have shown
that by preparing hydrothermal mixtures of TEAOH and
morpholine the size of SAPO-34 crystals can be controlled
from 1.5 to 7 μm. Small crystals of SAPO-34 (800 nm in
size) are formed when tetraethyl ammonium hydroxide
is used. The smaller SAPO-34 crystals show a longer life-
time in the MTO process. The amount of coke reported on
the SAPO-34 catalyst increases with a further decrease in
crystal size, so the catalyst yield can be optimally reduced
by decreasing the SAPO-34 crystal size.
Wang et al. (2012b) used a combination of two tem-
plate materials of triethylamine (TEA) and TEAOH to
improve the performance of the SAPO-34 catalyst. To
investigate the catalyst process performance, a fixed
bed reactor at 450°C was used. The results showed that
the catalyst shape, crystal size and Si incorporated in
the structure could be changed by the TEAOH/TEA ratio.
The catalyst prepared with TEAOH/TEA = 0.1 ratios had
more selectivity to light olefins in addition to having a
larger surface area, medium acidity and smaller crystal
size and longer shelf life and lower coke production
rates.
Zibrowius et al. (1992) prepared the SAPO-34 mole-
cular sieve using diethylamine (DEA) and in their study
investigated the effect of different template material ratios
and Si values. Purified SAPO-34 was obtained only when
n (DEA)/n (Al2O3) was 51.5 and n (SiO2)/n (Al2O3) was
>0.1. The addition of more DEA to the initial gel [when n
(SiO2)/n (Al2O3) >3) had a negative effect on the crystallin-
ity and yield of the crystals. The results showed that the
synthesis of SAPO-34 with DEA resulted in more Si incor-
poration into the structure and enhanced the hydrother-
mal and thermal stability of the catalyst.
Zubkov et al. (1991) investigated SAPO-34 and SAPO-5
catalysts with different crystal sizes under HTS condi-
tions and the influence of crystal size on the catalyst
performance, especially on the conversion rate, lifetime
and selectivity of MTO conversion reaction According to
their results, SAPO-5 had less acidic sites available and
9
less activity than SAPO-34. Larger-sized catalysts have a
shorter lifespan and less selectivity than light olefins.
Liu et al. (2008) investigated the effect of template
materials on the chemical-physical properties, crystal
size parameters of hydrothermal catalyst crystals synthe-
sized from TEA and TEAOH. TEAOH, methyl amyl (MA),
diisopropylamine (DPR) and DEA were used as template
materials and evaluated the performance of catalysts syn-
thesized in the MTO process. Results from XRD, FTIR and
TPD, Si NMR, TGA and MTO process showed that all the
catalysts had high activity and selectivity toward light
olefins and all of them did not have a long lifetime. Yet
can be said that the outer surface, crystal size and acidity
have a great influence on the activity, selectivity and life-
time of the samples and on the other hand, the sample
synthesized with template materials (TEAOH) has the best
catalytic performance due to the higher outer surface size.
It has smaller crystals and higher acidity.
Modification of SAPO-34 catalysts with
metals
Salmasi et al. (2011) modified the SAPO-34 catalyst with
Ni and Mg metals and introduced it into the MTO process.
The results showed that the metal-modified catalysts had
higher selectivity of light olefins than the unmodified cat-
alysts and had longer process life. Between the two modi-
fied catalysts, NiSAPO-34 had the best performance and
94% by weight of 100% methanol conversion, ethylene
and propylene production efficiency was reported for this
catalyst.
In his thesis, Jean (2005) investigated the modifica-
tion effect of SAPO-34, SAPO-44, SAPO-47 and SAPO-56
catalysts with Ru-catalysed oxidative cyclisation, palla-
dium (Pd) and platinum (Pt) catalysts. Reactions with the
catalyst modified by Ru-mediated metal did not improve
much compared to the unmodified catalyst. While the
catalysts modified with Pd and Pt metals performed better
in the process.
Effect of operating conditions on
SAPO-34 synthesis and MTO process
Marchi and Froment (1991) investigated the effect of the
porous structure, temperature, ratio of Si to Al and amount
of feed water on methanol-to-hydrocarbon conversion on
SAPO-34 and SAPO-11 catalysts. In the case of SAPO-34,
water appears to compete with olefins for stronger acidic
sites, thereby preventing them from reacting again and
10 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst
producing coke. In this way, increasing the feed water
content will increase the yield of alkenes. The same result
was obtained by increasing the reactor temperature and
reducing the ratio of Si to Al.
Jean (2005) in his thesis examined the effect of process
variables on the reaction of methanol to light olefins with
SAPO catalysts. All experiments were performed at atmos-
pheric pressure with a catalyst bed temperature of 400°C
in a fixed bed reactor using a variety of SAPO catalysts
namely SAPO-34, SAPO-44, SAPO-47 and SAPO-56 (SiO2/
Al2O3 = 0.3–0.9) was performed. One of the factors inves-
tigated was the effect of particle size on the reaction.
Except for SAPO-56, all SAPOs tested showed an increase
in the lifetime and catalyst activity with decreasing crystal
size. This effect also resulted in increased selectivity of
light olefins and improved methanol conversion at a tem-
perature range of 300–500°C. The effect of Si content on
SAPO-56 was tested with three ratios of 0.3, 0.6 and 0.9,
and the best selectivity of olefins was obtained in Si 0.6.
Also, the performance of a consumed catalyst was inves-
tigated and it was shown that by using it in the output
product, there would be DME and methanol resulting in
the filling of many catalyst active sites with coke.
ZSM-5 are microporous crystalline aluminosilicates
with pore sizes ranging from 3 to 7 Å. About 176 frame-
work structures have been listed in the most recent Atlas of
Zeolite Framework Types. The most important characteris-
tic properties of these solid materials are the well-defined
structure, high surface area, selective sorption of small
molecules (molecular sieves) and ion exchange. Zeolite
is composed of TO4 tetrahedra (T=Si, Al) which are inter-
linked through oxygen atoms to have a three-dimensional
(3D) network. SAPO-34 zeolite is a molecular sieve com-
posed of elements of Si, Al and P and has a natural zeolite
structure. This structure has small cavities and chambers
and is highly selective compared to light olefins. This small
structure of the cavity limits the transfer of larger molecules
from the entrance of the cavities, while the medium struc-
tures of the cavity show no resistance to the penetration
of larger molecules. This zeolite molecular sieve has a 3D
structure with oval-shaped chambers (10 Å × 10 Å) which
are connected by eight-member rings (with eight oxygen)
at the entrance of 3.8 Å × 3.8 Å holes. Each compartment is
connected to six adjacent empty spaces.
Hajiashrafi and Kharat (2013) various variables such
as the effect of molding materials and their use with dif-
ferent ratios, different silica and alumina precursors,
the effect of gel time before entering the crystallization
process, and the hydrothermal reaction under conditions.
Static or stirring studies as well as the role of crystal growth
inhibitors on the morphology and size SAPO-34 crystals
were investigated. They then introduced the catalysts into
the MTO process and compared their performance with
the ZSM-5 catalyst. The results showed that SAPO-34 had
better selectivity than propylene and had fewer paraffin
products and higher percentages of olefins.
Alvaro-Munoz et al. (2014) investigated the effect of
crystal size on the catalytic performance of SAPO-34, and
in particular on the time of catalyst induction and deac-
tivation. For this purpose, three catalysts with the same
acidity and size of different crystals were prepared. The
large crystals (7 μm) activated and rapidly deactivated
after a given induction period, whereas the small crystals
(4 μm) had complete conversion without significant induc-
tion time and remained active for a longer time. They main-
tained that this was due to the size of the outer surface and
more surface cavities in this sample.
Dargahia et al. (2011) prepared the SAPO-34 catalyst
using DEA and investigated the effect of variables such
as the amount of H3PO4, water, Al precursors and Si. The
results showed that pure SAPO-34 could be formed under
the conditions of 0.7 ≤ n (P2O5)/n (Al2O3) ≤ 1.2 and 25%
n (H2O)/(Al2O3) ≤ 100. The Al precursor is effective in deter-
mining the final compound. The specificity of the catalyst
prepared with DEA was compared with other molding
materials. The results showed that the increase in Si
placement in the structure was SAPO-34 (DEA) > SAPO-
34 (MOR) > SAPO-34 (TEA), respectively. The amount
of Si (4Al) species in the product composition was also
reported as SAPO-34 (DEA), SAPO-34 (MOR) > SAPO-34
(TEA), respectively.
Wu and Anthony (2001) investigated the effect of
adding ethylene, propylene and water to methanol in
the MTO process with the SAPO-34 catalyst. The results
showed that the addition of ethylene to the feed of meth-
anol and water reduced the selectivity of ethylene and
produced more propylene and butylene. As propylene
is added to the feed, selectivity to propylene decreases
and ethylene and butylene increase. The reason for this
increase is the reaction of ethylene and propylene with
methanol in the SAPO-34 catalyst. These reactions require
stronger acidic sites than methanol conversion to olefins.
The presence of propylene in the feed prevents the reac-
tion of ethylene with methanol due to competition on the
more acidic sites. Adding water to the feed reduces the rate
of coke production and increases selectivity to olefins. The
optimal molar percentage of water in the feed was esti-
mated to be 73–80. In this ratio, the amount of methanol
that can be converted per catalyst mass unit is eight times
that of pure methanol.
Lee et al. (2009) prepared SAPO-34 by microwave
and hydrothermal methods. The sample prepared by
 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst
microwave method had crystals of 130 nm size and surface
area of 593 m2/h while the hydrothermal method of cubes
with a size of 1.5–2.5 m and surface area of 708 m2/g was
obtained. Both samples had similar levels of acidic active
sites but the amount of weak acidic sites was lower in the
hydrothermal sample. MTO reaction was carried out on
two samples at 450°C and 1 h−1. The results showed that
the selectivity of olefins and the catalyst lifetime were
highest for the sample prepared under microwave condi-
tions, due to the shortening of the penetration path in this
catalyst, which resulted in reduced olefin conversion and
coke production.
Guangyu et al. (2012) investigated the influence of
synthesis parameters, including temperature and time of
crystallization and molding concentration, on the selec-
tivity of SAPO-34 and SAPO-5 in HTS. The results showed
that with increasing temperature, SAPO-5 crystals became
crystals due to their smaller size and more thermody-
namic stability than SAPO-34 structure. Also given the
initial mole ratios, 1 Al2O3:1 P2O5:0.6 SiO2: XTEA: 70 H2O, by
increasing the TEA molar ratio from 2 to 6, the unfavorable
phase rate decreased, increasing crystallization and des-
orption, resulting in a decrease in the crystallite size. This
is so that the crystals grow as time goes by because they
have enough time to grow.
Lei et al. (2013) used the hydrothermal dilution of
the synthesis solution to reduce the size of the SAPO-34
catalyst crystals, thereby extending the catalyst lifes-
pan and improving the catalyst performance. Ludox and
TEOS as well as different amounts of TEAOH molar ratio
were used as template material agents. According to
the study on catalysts synthesized with low amounts of
TEAOH and with AlCl3 source, due to the high acidity of
the synthesized gel and the reduction of SAPO-34 crystal-
lization and condensation phase formation, subsequent
synthesis of high amounts of TEAOH was carried out to
adjust the gel acidity. The synthesis was also used. Also,
by examining the silica sources, the TEOS source was
selected as the optimal source due to the production of
smaller crystals and the AlCl3 source as the AL source,
due to the greater stability of the catalysts synthesized
by this source.
Valizadeh et al. (2014) synthesized SAPO-34 catalysts
in four different crystal sizes from 20 nm to 8 μm using
1 Al2O3:2 P2O5:4 TEAOH:0.6 SiO2:140 H2O initial gel. Radia-
tion and colloidal silica and TEOS were used as silica
sources and for the synthesis of medium-sized catalysts
Na2SiO3 was used as silica source under hydrothermal or
assisted-microwave conditions. According to the results,
the SAPO-34 nanocatalysts last a lifetime. It had more
than average-sized catalysts and nano-plate catalysts with
11
a thickness of 20 nm significantly increased the lifetime.
And the methanol usage displayed on the formation of
coke on the catalyst nanoparticles is very low during the
process that has been the further conversion of methanol.
Also in the nanostructured catalysts, the catalyst surface
is more exposed to the reactant and this results in the pro-
duction of the products as well as the methanol conver-
sion rate.
Alvaro-Munoz et al. (2012) synthesized the SAPO-34
catalyst in both autoclaved and mobile autoclave at low
temperature with a molar ratio of 1 Al2O3:1 P2O5:0.4 SiO2:2
TEAOH:71.5 H2O using the hydrothermal method. The
influence of the temperature change and the synthe-
sis system on the purity, particle size and surface area
of the crystals are investigated. The results showed that
the highest crystallinity was at 200°C and decreased
with increasing synthesis temperature but under these
conditions, they synthesized from mobile autoclave but
at a lower temperature (equivalent to 130°C). The results
showed that although this temperature is much lower
than the solution temperature for SAPO-34 synthesis, the
surface area obtained by this method was very high and
this result could be due to homogeneous environment
during synthesis because the homogeneity of the environ-
ment has had a great impact on de-nucleation and growth
process.
Yang et al. (2013) used a two-step hydrothermal
method for the synthesis of SAPO-34 nanocatalysts at
160–160 nm scale. They first performed two basic syn-
theses with the initial Al2O3:0.6 SiO2:P2O5:0.5 TEAOH:65
H2O gels in two steps, one step, and two step. It was
smaller, had a larger surface area and more acidic sites
than the previous sample. After this study, they used
centrifugation and dilution with distilled water between
the two steps of synthesis, and then crystallized the gel
into the second step. The difference between the third
and fourth samples was higher than the synthesis tem-
perature of the first stage of the fourth sample. Exami-
nation of the synthesized samples indicated that the
use of two-stage crystallization method had an effect
on the chemical composition of the samples and with
the rate of gel dilution, the rate of growth kinetics of the
crystals decreased, resulting in smaller crystal size and,
by increasing the temperature of the first step for the
fourth sample, the SAPO-34 production efficiency for
low temperature was increased due to the lower crystal-
lization process kinetics at low temperature and at the
same time. The c­ omparison of our catalytic behavior in
the MTO reaction with those SAPO-34 samples prepared
with different soft templates by other researchers is
reported in Table 2.
12 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst

Table 2: Catalytic performance results of SAPO-34 samples modified with different soft templates.

Reference Additive Lifetime (min) Olefin selectivity Operating conditions Lifetime definition

(Chen et al. 2019) TPAOC 300 81.93% (C2–C3) T = 450°C Conv > 99%
WHSV = 3 h−1
(Yu et al. 2019) CO2-based polyurea 320 85% (C2–C3) T = 420°C Conv = 100
WHSV = 1.5 h−1
(Rami et al. 2019) Triton X-100 290 83.22% (C2–C3) T = 450°C Conv > 95%
WHSV = 4 h−1
MeOH:H2O = 50 wt%
(Wang et al. 2018) CTAB 225–350 85.9% (C2–C3) T = 400°C Conv > 50%
WHSV = 2 h−1 Conv = 100
(Guo et al. 2018) PDADMAX 426 82.5% (C2–C3) T = 400°C Conv = 100
WHSV = 2 h−1
(Wu et al. 2017) PZPMS 376 83.65% (C2–C3) T = 450°C Conv > 99%
WHSV = 2 h−1
(Wang et al. 2016) DPHAB 292 80% (C2–C3) T = 450°C Conv > 99%
WHSV = 3 h−1
(Mousavi et al. 2018) PEG4000 320 90% (C2–C4) T = 400°C Conv = 100
WHSV = 3 h−1

Conclusion Typically, the higher the crystallinity percentage and the

In recent years, with the rise in crude oil prices and the
growing demand for light olefins, the use of new methods
of producing light olefins has attracted much attention.
Converting methanol to light olefins (MTO) using metha-
nol from natural gas and coal are among the successful
processes in the production of light olefins. In recent
decades, catalyst engineering, reactor and catalytic reac-
tion in the MTO process have been seriously investigated.
The distribution of products in the MTO process can be
controlled by adjusting the reaction variables. Although
significant advances have been made in this area, SAPO-34
is rapidly deactivated due to the acidic sites being covered
and coke closures. The catalytic performance of SAPO-34
is directly affected by the morphology, crystal size, acid
strength and some other structural properties, and these
properties can be altered during the synthesis process
depending on the type of material used and the operat-
ing conditions of the synthesis. By adjusting the acidity,
the catalyst deactivation is reduced or delayed. The
acidity of the SAPO molecular sieve can be altered by iso-
morphic cation substitution, cation exchange and Si/Al
ratio adjustment. Adjusting the acidity by changing the
Si/Al ratio in the SAPO compound is easier and cheaper
and requires no additional material. Also, the amount of
water in the gel as a solvent can change the morphology
and structure of the catalyst. The crystallinity rate and
the pure phase percentage of SAPO-34 can be adjusted by
the temperature and time of crystallization, or the degree
of crystallinity of the initial gel and the amount of Si gel.
pure phase of SAPO-34 and the less flawed structures,
the higher the methanol conversion rate and selectivity of
the desired components. The size of the crystals is a para-
meter affecting the stability and conversion rate of metha-
nol. Because of the very small size of the crystals, the pore
size is also very small and there will be resistance to pen-
etration for methanol; on the other hand, for the larger
crystals, the penetration path is long and there is possi-
bility of secondary reactions for desirable products along
the exit pathway (and the production of larger molecules
and cavity blocking) so crystals must have an optimal size.
Based on these investigations of effective parameters, the
main results are summarized below:
8. SAPO-34 is directly affected by the morphology, crys-
tal size, acid strength and some other structural prop-
erties, and these properties can be altered during the
synthesis process depending on the type of material
used and the operating conditions of the synthesis.
9. By adjusting the acidity, the catalyst deactivation is
reduced or delayed. The acidity of the SAPO molecu-
lar sieve can be altered by isomorphic cation substitu-
tion, cation exchange and Si/Al ratio adjustment.
10. Water in the gel as a solvent can change the morphol-
ogy and structure of the catalyst.
11. The crystallinity rate and the pure phase percentage
of SAPO-34 can be adjusted by the temperature and
time of crystallization, or the degree of crystallinity of
the initial gel and the amount of Si gel.
12. Typically, the higher the crystallinity percentage
and the pure phase of SAPO-34 and the less flawed
 Z. Yang et al.: Investigation of effective parameters on SAPO-34 nanocatalyst
structures, the higher the methanol conversion rate
and selectivity of the desired components.
13. The size of the crystals is a parameter affecting the
stability and conversion rate of methanol. Because
of the very small size of the crystals, the pore size is
also very small and there will be resistance to penetra-
tion for methanol; on the other hand, for the larger
crystals, the penetration path is long and there is pos-
sibility of secondary reactions for desirable products
along the exit pathway (and the production of larger
molecules and cavity blocking) so crystals must have
an optimal size.
14. Increasing the temperature and crystallization time
generally increases the particle size of the SAPO-34
catalyst.
Acknowledgments: The authors gratefully acknowledge
the Department of Chemical Engineering, Arak Branch,
Islamic Azad University, Arak, Iran and Young Research-
ers and Elite Club, Gachsaran Branch, Islamic Azad Uni-
versity, Gachsaran.
Funding: There is no funding to report for this submission.
Conflict of interest: The authors declare that they have no
conflict of interest.
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