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Chemical Engineering Science 172 (2017) 385394

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Chemical Engineering Science


journal homepage: www.elsevier.com/locate/ces

Influence of recycle streams of C5/C6 and C4 hydrocarbon cuts on the


performance of methanol to propylene (PVM) reactors
Abolghasem Kazemi a,, Masoud Beheshti a,b,, Reza Khalili c
a
Department of Chemical Engineering, University of Isfahan, Isfahan, Iran
b
Process Engineering Institute, University of Isfahan, Isfahan, Iran
c
Petrochemical Research and Technology Company, Mahshahr, Iran

h i g h l i g h t s

 Effects of operating parameters are investigated on methanol to propylene reaction.


 C5/C6 and C4 hydrocarbon cuts are co fed to the reactors.
 Effects of co feeding hydrocarbon cuts on product distribution are investigated.
 Conditions of steady state recycle streams of hydrocarbon cuts are determined.

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

Article history: Conversion of methanol to propylene combined with cracking of C5/C6 and C4 hydrocarbon cuts was stud-
Received 23 February 2017 ied on a commercial Sd-Chemie Germany ZSM-5 catalyst. The C5/C6 hydrocarbon cut consisted of hydro-
Received in revised form 17 June 2017 carbons with 5 and 6 carbons in their structure (27.74% i-pentene, 43.14% i-hexene, 3.70% i-pentane and
Accepted 30 June 2017
7.37% i-hexane). The C4 hydrocarbon cut consisted of both olefinic and paraffinic molecules. A fraction of
Available online 1 July 2017
the feed hydrocarbon mixture was converted to other hydrocarbons while the conversion of methanol
was remained close to 100%. It was observed that co feeding of the hydrocarbons mixture with methanol
Keywords:
considerably increase propylene selectivity. Propylene selectivity up to 61% was gained in the propylene
Propylene
Methanol
via methanol (PVM) process by co feeding of C5/C6 hydrocarbon cuts. For the C4 hydrocarbon cut, propy-
PVM lene selectivity up to 65% was obtained. However, these values do not represent the actual selectivity at
C5/C6 hydrocarbons actual flow rates of recycle streams. Based on third order polynomials, effects of steady state recycle
Feed effects streams of these cuts are also predicted in this paper. At the best conditions of a steady state recycle
Selectivity stream, 47.7% selectivity was obtained for propylene in the PVM reactors.
2017 Elsevier Ltd. All rights reserved.

1. Introduction for production of propylene has increased in recent years (Wu


et al., 2013). Processes such as dehydrogenation of propane,
Propylene is one of the basic materials in petrochemical indus- methanol to olefins and propylene via methanol (PVM) are being
try. Because of great demands of propylene derivatives such as developed (Buyevskaya et al., 2000; Chang, 1984; Chen et al.,
acrylonitrile, propylene oxide and polypropylene, the demand for 2005; Corma et al., 2005; Wu et al., 2004). Methanol can be pro-
this material has increased in recent years (Mei et al., 2008; duced from the natural gas in very large scale plants (mega metha-
Plotkin, 2005). The main processes for production of propylene nol plants). Processes of production of propylene with methanol
are steam cracking of naphta and FCC process (in these processes feed have attracted much attention because of availability of
propylene is a byproduct) (Komatsu et al., 2001; Ren et al., methanol (Li et al., 2008; Hadi et al., 2012).
2006). Because of increasing oil prices and increasing market Many studies have been dedicated to examining different types
demand for propylene, the need for development of new processes of zeolite catalyst for transformation of methanol to light olefins.
Based on the results of these studies; ZSM-5 zeolite does have a
great performance in transforming methanol to olefins (Bleken
Corresponding authors at: Department of Chemical Engineering, University of et al., 2012; Jiao et al., 2012; Kaarsholm et al., 2007; Lee et al.,
Isfahan, Isfahan, Iran (M. Beheshti).
2013; Papari et al., 2011; Wei et al., 2011).
E-mail addresses: abolghasemkazemi@gmail.com (A. Kazemi), masbeh@yahoo.
com, m.behshti@eng.ui.ac.ir (M. Beheshti).

http://dx.doi.org/10.1016/j.ces.2017.06.051
0009-2509/ 2017 Elsevier Ltd. All rights reserved.
386 A. Kazemi et al. / Chemical Engineering Science 172 (2017) 385394

Combined reactions of various hydrocarbons (i-butane, n- purified in a batch distillation column, separate from the other
butane, ethylene and a mixture of n-butane and n-butene) along equipment. The feed to this distillation column was provided by
with methanol, have been the topic of recent studies (Gong et al., accumulation of the organic phase at the outlet of the PVM reac-
2012; Li et al., 2008; Mier et al., 2010; Roohollahi et al., 2013; tors. The C5/C6 hydrocarbon cut consisted of hydrocarbons with 5
Wu and Anthony, 2001). Synergies in exothermic production of and 6 carbons in their structure (27.74% i-pentene, 43.14% i-
propylene from methanol combined with endothermic reactions hexene, 3.70% i-pentane and 7.37% i-hexane). Composition of pro-
of cracking of other hydrocarbons such as i-pentene and i-hexene duced mixture is shown in Tables 1 and 2.
is an interesting route to propylene production. Since hydrocar- Also, the C4 hydrocarbon cut was purchased from Amirkabir
bons with 4, 5 and 6 carbons in their structure have a significant Petrochemical Company (APC). The C4 hydrocarbon cut consisted
selectivity in methanol to propylene (MTP) process, addition of of both olefinic and paraffinic molecules. Composition of this
these materials to feed is expected to suppress production of these hydrocarbon cut is shown in Table 3.
unwanted products in PVM process. Also, these materials could be
cracked into lighter hydrocarbons (Konno et al., 2012; Lee et al., 2.2. Methanol conversion setup
2013). Another advantage of this change in the feed of this reactor
is the possibility of finding a new way to utilize these The experiments were carried out in 12 adiabatic, fixed bed
hydrocarbons. reactors (6 parallel dimethyl ether (DME) reactors and 6 PVM reac-
Roohollahi et al. (2013) investigated effects of addition of i- tors). The reactors were cylindrical, with reactor and shell diame-
butene to the feed of methanol to propylene reactors. They ters of 42.4 and 133 mm, respectively. Across each reactor, 4
observed that by addition of i-butene to the feed, selectivity of temperature indicators (TI) were placed for proper monitoring of
propylene in the process is enhanced. In a similar study, Mier the reactions conditions. Also, at the bottom and top of the catalyst
et al. (2010) utilized n-butane and co fed this component with beds, some ceramic pellets were placed for having uniform flow in
methanol. In another research, Gong et al. (2012) studied effects the reactors. The methanol feed flow rate (in gaseous state) was
of co feeding of a mixture of n-butanes and n-butylenes. A number controlled with mass flow controllers at maximum of 1.35 kg/h
of similar studies can be found in the literature (Li et al., 2008; Wu while reduced to 0.9 kg/h for some of the experiments. The outlet
and Anthony, 2001). However, the results of these studies do not of the DME reactors entered the six PVM reactors; Water is also
represent behavior of actual recycle streams. Not only composition introduced to the first PVM reactor with a constant flow rate, con-
of co fed material in none of these studies was similar to actual trolled by mass flow controllers at 0.738 kg/h. The flow sheet of
recycle streams, but also co feeding of a material can lead to impos- experimental set up is shown in Fig. 1.
sible steady state operation of recycle streams. In this research, In the first set of reactors, methanol was dehydrated to produce
these issues are considered in order to make the results of the the intermediate product dimethyl ether (DME) over c-alumina
research suitable for practical applications of recycle streams. catalyst. The inlet and outlet temperatures of these reactors were
One of the aims of this research was to improve propylene 285 and 298300 C, respectively. Also, the reactors pressure were
selectivity in the PVM process with addition of a mixture of C5/C6 adjusted at 1.3 bar. The DME production reaction from methanol is
hydrocarbon cuts. This mixture was produced from purification in accordance to Eq. (1) (Pontzen et al., 2011).
of the organic phase at the outlet of the 3 phase separator in the
PVM process. Determination of the effects of recycle stream (rather 2MeOH $ DME water 1
than material co-feed) of unwanted C5 and C6 products on the per- DME produced in DME reactors entered PVM reactors as feed. In
formance of the PVM reactor is also one of the main aims of this PVM reactors, it was converted to propylene along with a wide
study. Although co feeding of different materials along with range of other hydrocarbons at temperature range of 400490 C
methanol has been studied by other researchers, evaluation of and pressure of 1.3 bar. The temperature of the feed streams of
effects of recycle streams has not been carried out in previously the reactors were monitored and controlled by TICs, however the
published studies. The co-fed C5/C6 mixture in this study was the inlet temperature set points were adjusted in such a way to yield
top product of a distillation column in which the feed was the desired outlet temperatures. Six fixed beds of commercial HZSM-
organic phase product of the 3 phase separator in the PVM process. 5 zeolites (prepared by Sd-Chemie Germany) were used as the
Thus, this mixture has a composition close to actual recycle stream catalyst. Previous studies show that the following reactions along
of this process. The same procedure was carried out for evaluation with a series of other reactions occur in the process of production
of effects of C4 recycle stream. In this study, instead of simply co of propylene from dimethyl ether(Chang, 1980; Mihail et al., 1983;
feeding of hydrocarbons with methanol, influence of steady state Schoenfelder et al., 1994).
recycle streams of C5/C6 and C4 hydrocarbon cuts have been inves-
tigated. This issue makes the results of this study suitable to be uti- 3CH3 AOACH3 ! 2CH3 ACH@CH2 3H2 O 2
lized in actual methanol to propylene plants.
nCH3 AOACH3 ! 2Cn H2n nH2 On 2 . . . 8 3
2. Materials and methods
CH2 CH3 OH ! C2 H4 H2 O 4
Conversion of methanol to propylene combined with cracking
of C5/C6 and C4 hydrocarbon cuts was studied on a commercial
3C2 H4 ! 2C3 H6 5
Sd-Chemie Germany ZSM-5 catalyst.
3C4 H8 ! 4C3 H6 6

2.1. Materials 3C5 H10 ! 5C3 H6 7

H-ZSM5 catalyst (Sd-Chemie) was used in this study. The


3C6 H12 ! 6C3 H6 8
results of NH3-TPD test showed 0.524 mmoles/g absorption of
NH3. Further analysis showed that 0.271 mmoles/g were absorbed The PVM reactors product stream which was in gaseous state
on weak/medium acidic sites and 0.253 mmoles/g were absorbed was then cooled to a temperature of about 35 C, resulting in
on strong acidic sites of the catalyst. C5/C6 hydrocarbon cuts were appearance of three phase of products (aqueous, organic and gas-
A. Kazemi et al. / Chemical Engineering Science 172 (2017) 385394 387

Table 1
Composition of C5/C6 mixture at the outlet of PVM reactors.

Aromatics Isoparafins Naphtenes Olefins Oxygenates Paraffins Unknowns


Mol% 0.477 10.886 12.692 71.516 2.622 0.699 1.109

Table 2
Composition of the C5/C6 mixture based on different hydrocarbon cuts in outlet of PVM reactors.

Number of carbon atoms in the structure of molecules 4 5 6 7 8 9


Mol% 0.948 39.766 55.562 1.026 0.059 0.018

Table 3 eous phases), which are separated by a three phase separator. The
Composition of C4 hydrocarbon cut. three phases separated at the three phase separator, were analyzed
Component MW Molar percentage by VARIAN 3800 gas chromatographs.
i-butane 58.1 11.82
n-butane 58.1 18.29
t-2-butene 56.1 5.13 3. Results and discussion
1-butene 56.1 17.57
Isobutene 56.1 43.55 3.1. Calculations
Cis-2-butene 56.1 3.3
1,3 butadiene 54.1 0.16
C6+ 100.2 0.18
Water is one of the main products of PVM process (Pontzen
et al., 2011), however the products selectivity were calculated
Average Total
56.78 100
based on Eq. (9) and based on this formula, selectivity of water is
not taken into account since no carbon atom is present in waters

Fig. 1. Experimental setup of methanol to propylene reactors in PVM process.


388 A. Kazemi et al. / Chemical Engineering Science 172 (2017) 385394

molecular structure. The main idea for using this formula is to Table 5
determine the carbon efficiency of the process which means that, A sample of carbon balance results based on 12 h of steady state operation
(N = Avogadros number).
the fraction of feed methanol which is converted to water or other
materials without carbon atoms in their structure is not taken into Number of carbon atoms Number of carbon atoms output
account. input
Parameter Value Parameter Calculated
N/h
ni  Foi
selectiv ityi 9 Carbon atoms input 28.09 Carbon atoms output in gas 22.02
Fi methanol  Fo methanol 2Fo DME from methanol phase
Carbon atoms input 0 Carbon atoms output in organic 5.35
In which, ni is the number of carbon atoms present in the from water phase
molecular structure of component i, and Fi and Fo indicate the Carbon atoms in aqueous phase 0.04
number of moles of the component i entering or going out of the (unreacted methanol)
Total 28.09 Total 27.04
reactor, respectively.
The weight hourly spaced velocity (WHSV) was calculated
based on the feed methanol flow rate and the weight of catalyst
loaded in the reactors. In this study the methanols WHSV varied 3.3. Parameters under investigation
between the values of 0.60.9 h1. WHSV was calculated based
on Eq. (10). Effects of temperature and WHSV on the selectivity of methanol
to propylene conversion was investigated by previous studies
(Gong et al., 2012; Mier et al., 2010; Roohollahi et al., 2013;
Mass flow rate of methanol Sardesai and Lee, 2005; Wu et al., 2004). These studies suggest that
WHSV 10 temperature and WHSV do have significant effects on the product
Net weight of the six catalyst beds
selectivity of the process of production of light olefins from metha-
nol. Thus, the effect of temperature and WHSV were investigated.
Along with these two parameters, it was necessary to investigate
the effects of the flow rate of the co fed mixture (molar ratio of
3.2. A sample mass and carbon balance results methanol to the mixture).

The system was operated continuously. Therefore, it was


required to check the validity of the calculations prior to have 3.4. Effect of temperature
any discussions on the obtained results. In this section, a mass bal-
ance is presented based on the results of a sample experiment. The As suggested by (Wu et al., 2013), when reaction temperature
desired operating conditions were applied on the system. It took decreases from 460 C to 380 C, the space time should be doubled
several hours to reach steady state conditions (based on the new to keep the methanol conversion at the same level. Thus, because
operating conditions). After reaching steady state conditions, the of the limitations due to performance of the catalyst and the extent
system was operated for 12 h. The outlet of the reactors was cooled of conversion in this reaction, in this study, the reactors outlet tem-
down to about 35 C, leading to appearance of three phases: gas- perature varied between the values of 470 C and 490 C. Prior to
eous, aqueous and organic. These phases were separated using a addition of C5 and C6 hydrocarbon cuts, the effect of temperature
three phase separator. Aqueous and organic phases were accumu- was investigated. Influence of temperature on products selectivity
lated in two separate tanks. Also, total volume of gaseous phase is shown in Fig. 2. As shown in Fig. 2, as the temperature was
was measured using a gas flow meter. Based on the analysis of increased between 470 C and 480 C, no considerable change in
the gaseous phase, average molecular weight of the gas phase propylene selectivity occurred. However when the temperature
was calculated, 42.75. In this experiment, the system had two feed was increased further to 490 C, propylene selectivity was
streams, water vapor and methanol with 738 and 900 g/h, respec- increased. This observation is consistent with the results of previ-
tively. A detailed mass and carbon balance is carried out to see the ous studies (Roohollahi et al., 2013; Wu et al., 2013) and could be
accuracy of the measurements and calculations (Tables 4 and 5). attributed to higher rates of heavy hydrocarbon cracking reactions.
Average molecular weight of the organic phase was calculated, In Fig. 2, it is also clear that the higher temperature suppresses pro-
85.61 based on the results of analysis. Also, average carbon number duction of heavier hydrocarbons such as C5, C6 and aromatics and
of the molecules in gas and organic phase were calculated to be at this temperature, the rate of heavy hydrocarbons cracking to
3.21 and 6.79, respectively. Based on the results presented in produce light hydrocarbons such as light olefins is higher. Based
Table 4, the mass balance across the system is properly established on the results shown in Fig. 2, increasing temperature between
based on the measurements and calculations. The little error in the two temperature boundaries results in lower wastes of feed
mass balance is attributed to accuracy of timings (it took about and higher rates of production of the desired product (propylene)
two minutes to discharge the tanks) and also accuracy of gas vol- and thus the temperature of 490 C is selected for the next exper-
ume measurement device. Also, Tables 4 and 5 show that the iments. However, influence of this change on catalyst deactivation
results show less than 4% of error. rate should be evaluated.

Table 4
A sample of mass balance results based on 12 h of steady state operation.

Inlet flow rates Outlet volume of gaseous phase and mass of accumulated organic and aqueous phases
Stream Mass flow rate (g/h) Parameter Measured value (12 h) Calculated g/h
Methanol 900.0 Gas phase flow rate 645,052 liters 293.3
Water vapor 738.0 Organic phase 811 g 67.5
Aqueous phase 15590 g 1299.1
Total 1638.0 Total 1659.9
A. Kazemi et al. / Chemical Engineering Science 172 (2017) 385394 389

Fig. 2. Influence of temperature on the product selectivity (without co feeding hydrocarbon cuts).

3.5. Effect of co feeding C5 and C6 hydrocarbon cuts trend. As shown in Fig. 4, as the molar ratio of the co feed mixture
to methanol feed increased from 0 to 0.2421, the propylene selec-
After investigating effects of temperature, a mixture of hydro- tivity increased from 36.0% to 60.7%. High selectivity of products
carbons having 5 and 6 carbon atoms in their structure and with was attributed to partial conversion of co fed mixture.
average molecular weight of 77.126 was fed to the reactor along
with methanol. The outlet temperature of the reactors was con- 3.6. Effect of WHSV
trolled at the 490 C.
The main idea for the introduction of a mixture with the intro- It was suggested by (Gong et al., 2012; Mier et al., 2010;
duced composition to the reactor, was to suppress production of Roohollahi et al., 2013) that WHSV plays a significant role in the
hydrocarbons with 5 and 6 carbons in their structure and conver- product selectivity of the process of production of light olefins
sion of these cuts to other hydrocarbons such as light olefins. It is from methanol. Thus, influence of WHSV on product selectivity
expected that when a material present at one side of an equilib- was also investigated. It is shown in Fig. 5 that as the methanol
rium is introduced to the equilibrium, the equilibrium moves WHSV in this process was increased from 0.6 to 0.75 h1, the
toward neutralizing the effects of this change and moves toward propylene selectivity decreased considerably. Increasing WHSV of
the other side (Chatelier, 1884). Thus, when C5 and C6 hydrocarbon methanol further did not have a tangible effect on the selectivity
cuts were introduced to the reactor, it was expected to have lower of the desired product. This observation could be due to the fact
produced C5/C6 hydrocarbon cuts. Another reason for this change that light olefins are the primary products of the methanol conver-
in the reactors feed was to exploit the possible conversion of these sion reactions and other products are produced based on light ole-
materials to light olefins along with methanol. Based on the previ- fins. Thus, it can be expected that when methanol concentration in
ous studies, C5 and C6 hydrocarbons can be cracked to other hydro- the reactors is increased, the selectivity of the light olefins reach a
carbons over ZSM-5 catalyst (Konno et al., 2012; Lee et al., 2013). maximum at a certain concentration of methanol. When the
The molar ratio of the mixture to feed methanol varied between methanol concentration increases further, due to increasing the
0 and 0.2421. As shown in Fig. 3, when the mixture was fed to the concentration of light olefins (because of the increase in their
reactor along with methanol, a fraction of the mixture was con- selectivity), the rate of the other reactions consuming light olefins
verted to other hydrocarbons. It is also clear from Fig. 3 conversion to produce heavier hydrocarbons increases which means lower
of these hydrocarbon cuts increased upon increasing ratio of the overall light olefin selectivity. Also it is clear that maximum selec-
mixture to feed methanol. It was expected that addition of small tivity of C4 hydrocarbons and minimum selectivity of ethylene
amounts of the mixture suppress production of C5 and C6 hydro- occur at methanol WHSV = 0.75 h1. At methanols WHSV equal
carbons. However it was expected that addition of large amounts to 0.6 h1, a propylene selectivity of 58.1% was obtained.
of these cuts, result in conversion of a large fraction of the mixture.
The observed behavior of the system is consistent with the
3.7. Finding the real recycle stream conditions
expected behavior of the reactions.
As shown in Fig. 3, the introduced hydrocarbon mixture was
As observed in Section 3.5, when the co-feed mixture was intro-
mainly converted to other hydrocarbons such as light olefins. Thus,
duced to the PVM reactor, a significant conversion of these materi-
recycling these materials to the PVM reactors with ratio of mixture
als was observed. However the aim of this study was to investigate
to methanol between 0.07 and 0.24 is not possible. The steady state
the effects of recycle stream of unwanted products on the perfor-
recycle to methanol molar ratio is determined in the next sections.
mance of the reactor. A flow rate equal to the feed flow rate of
Influence of co feeding the mixture on product selectivity is
the mixture of C5 and C6 hydrocarbon cuts at the outlet of the reac-
shown in Fig. 4. As shown, selectivity to propylene was increased
tor should be available for applying a steady state recycle stream of
upon increasing ratio of the introduced mixture to feed methanol.
these cuts. Thus, the fact that the mixture was converted in the
Also selectivity of ethylene and hydrocarbons with 4 carbon atoms
reactor is not consistent with the assumption that the mixture
in their structure, produced in this process follow an increasing
was a recycle stream. The next step in this study was to determine
390 A. Kazemi et al. / Chemical Engineering Science 172 (2017) 385394

Fig. 3. Conversion of C5/C6 hydrocarbons cuts in the reactor.

Fig. 4. Influence of molar ratio of C5/C6 to methanol feed on the products selectivity.

Fig. 5. Influence of WHSV of methanol on the products selectivity.


A. Kazemi et al. / Chemical Engineering Science 172 (2017) 385394 391

Fig. 6. Ratio of C5/C6 to methanol feed at the outlet of the reactor versus ratio of C5/C6 to methanol feed at the inlet of the reactor.

Fig. 7. Influence of molar ratio of recycled C4 to methanol on conversion of C4 cut.

the steady state recycle stream flow rate at which the equal flow 3.8. Effect of co feeding C4 hydrocarbon cut
rate of the C5 and C6 hydrocarbon cuts was available for applicabil-
ity of steady state recycle stream. The results of the experiments In this section, influence of co feeding a C4 hydrocarbon cut to
(ratio of C5 and C6 hydrocarbon cuts at the outlet and inlet of the the reactors is investigated. As shown in Table 3, the utilized C4 cut
reactor to feed methanol flow rate) were fitted with a 3rd order mainly consisted of alkenes which are more reactive than alkanes.
polynomial. The polynomial is show in Fig. 6. This issue can lead to consumption of some of the co fed materials.
The equation of the polynomial, shown in Fig. 6 was derived This issue must be taken into account in case of considering steady
(Eq. (11)). state recycle streams. Conversion of olefinic and paraffinic parts of
the utilized C4 cut was calculated in each experiment (Fig. 7). As
shown, the paraffinic part of this cut is not consumed in the reac-
tor. However, the olefinic part is consumed to a great extent
Ro=M 0:4019R3i=M 0:5964R2i=M 0:1841Ri=M 0:0490 11
depending on the ratio of C4 to methanol. As shown in Fig. 7, con-
In which Ro/M is the ratio of mass flow rate of the C5/C6 hydro- version of the olefinic part of the cut is increased from 0% to more
carbon cuts at the outlet of the reactor to the feed methanol and Ri/ than 70% by increasing the molar ratio of C4 to methanol from 0.03
M is the ratio of mass flow rate of the C5/C6 hydrocarbon cuts at the
to 0.3.
inlet of the reactor to the feed methanol. Using Eq. (11), the steady Co feeding of this cut influences the products selectivity in the
state recycle stream to methanol mass flow rate ratio is calculated reactors. Influence of co feeding of different ratios of this cut on
to be equal to 0.063. An experiment has been carried out at this product selectivity is shown in Fig. 8. As shown, selectivity of
ratio of the mixture to methanol at temperature of 490 C and propylene is enhanced to 65% at the best conditions. Selectivity
WHSV = 0.9 h1, and at this conditions, the propylene selectivity of ethylene follows the same trend. However, selectivity of C5/C6
is calculated to be 37.7%. cuts exhibits a minimum at ratio of 0.03.
392 A. Kazemi et al. / Chemical Engineering Science 172 (2017) 385394

Fig. 8. Influence of molar ratio of C4 to methanol on products selectivity.

Fig. 9. Influence of WHSV of methanol on products selectivity.

Fig. 10. Ratio of C4 to methanol feed at the outlet of the reactor versus ratio of C4 to methanol feed at the inlet of the reactor.
A. Kazemi et al. / Chemical Engineering Science 172 (2017) 385394 393

Fig. 11. Conversion of methanol and DME vs time for (a) no recycle streams, (b) C5/C6 recycle streams and (c) C4 recycle stream.

Effects of WHSV of methanol on product selectivity are shown of the recycle streams on catalyst deactivation rate. Conversions
in Fig. 9. As shown in this figure, products selectivity is affected of methanol and DME vs time are reported in Fig. 11. Based on
by WHSV of methanol. Selectivity of propylene and C5/C6 cuts exhi- the presented results, it took 15.5 days, to have a methanol conver-
bit a maximum while selectivity of ethylene follows a decreasing sion lower than 94%. Also, when recycle streams of C5/C6 and C4
trend. This observation is attributed to conversion of produced were applied, this time interval was 11.5 and 12 days, respectively.
ethylene in side reactions of reacting pool. These results show that application of the both recycle streams
Based on the obtained data from the performed experiments, result in increased catalyst deactivation rates. However, influence
feasible flow rate of the recycle stream at steady state is calculated. of C5/C6 cuts on the catalyst deactivation rate was higher, com-
The results are shown in Fig. 10. A polynomial of 3rd order is used pared to C4 cut.
for regression of the data. Based on these results, by applying
steady state recycle stream of C4 hydrocarbon cut, maximum selec- 4. Conclusions
tivity of 47.7% for propylene can be obtained.
The presented results showed that application of recycle This study was carried out with the primary aim of minimizing
streams of C4 and C5/C6 can lead to enhanced selectivity of propy- the wasted methanol in the process of conversion to olefins by
lene in the process. However, there is another parameter, affecting introducing mixtures of unwanted products of the process as recy-
economics of the process. It was required to investigate influence cle streams. It was revealed that at the maximum applicable tem-
394 A. Kazemi et al. / Chemical Engineering Science 172 (2017) 385394

perature (490 C), propylene selectivity would be maximum. Also Jiao, Y., Jiang, C., Yang, Z., Zhang, J., 2012. Controllable synthesis of ZSM-5 coatings
on SiC foam support for MTP application. Microporous Mesoporous Mater. 162,
the highest propylene selectivity was obtained at WHSV = 0.6 h1
152158.
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However, the changes in temperature, methanols WHSV and the Phosphorous modified ZSM-5: deactivation and product distribution for MTO.
ratio of the mixture to the feed methanol resulted in reduction of Chem. Eng. Sci. 62 (18), 55275532.
Komatsu, T., Ishihara, H., Fukui, Y., Yashima, T., 2001. Selective formation of alkenes
the length of catalyst cycle. through the cracking of n-heptane on Ca2+-exchanged ferrierite. Appl. Catal. A
The steady state ratio of the recycle stream of C5/C6 hydrocar- 214 (1), 103109.
bon cuts to the methanol feed flow rate was calculated to be Konno, H., Okamura, T., Kawahara, T., Nakasaka, Y., Tago, T., Masuda, T., 2012.
Kinetics of n-hexane cracking over ZSM-5 zeolites effect of crystal size on
0.063. At this ratio of the mixture to methanol, selectivity of propy- effectiveness factor and catalyst lifetime. Chem. Eng. J. 207, 490496.
lene was 37.7%. This value, in case of recycle stream of C4 hydrocar- Lee, J., Hong, U.G., Hwang, S., Youn, M.H., Song, I.K., 2013. Catalytic cracking of C5
bon cut was also calculated to be 47.7%. However, with co feeding raffinate to light olefins over lanthanum-containing phosphorous-modified
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(not steady state recycle) of these cuts, propylene selectivity up to 195.
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This study was supported by Iranian Petrochemical Research Mier, D., Aguayo, A.T., Gayubo, A.G., Olazar, M., Bilbao, J., 2010. Synergies in the
production of olefins by combined cracking of n-butane and methanol on a
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Comparison of two methods of iridium impregnation into HZSM-5 in the
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(MTP) Process: Proceedings of the 4th International Conference on
Nanostructures (ICNS4), 1214 March, 2012, Kish Island, I.R. Iran.