A new process for enhancing conversion of methyl vinyl ether to propylene yields with Al2O3 hollow spheres

Article abstract of DOI:10.1039/c5ra25100a

Al₂O₃ hollow spheres were successfully synthesized via a simple template method and used to catalyze a new process from methyl vinyl ether to propylene. In this study, it not only indicated that a two-step integration process from acetylene and methanol to propylene is feasible but the prepared catalyst could also adjust the distribution of the products. First, colloidal carbon spheres were formed by the hydrothermal synthesis method, and then the template was used to prepare hollow spheres of Al₂O₃. EDS, XRD, SEM, and TEM all showed that the catalyst was composed of only O and Al and the structures were hollow spheres. In the new process tests, the low carbon olefins are detected as the main products, alkanes are nearly not observed. The participation of Al₂O₃ hollow spheres could significantly enhance the selectivity of olefins especially for propylene compared to the results without catalysts. Furthermore, the effects of temperature on the products were also investigated, and a possible radical-involved reaction mechanism is discussed in detail at the end.

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A New Process of Methyl Vinyl Ether - to - Propylene with
Enhancing Propylene Yield by Hollow Spheres Al2O3
Yang Wang a, Wenyu Zhang a, Daoan Zha b, Jiaji Hu a, Wei Li c, Wubiao Duan a, Bo Liu a,*
Received 00th January 20xx,
Accepted 00th January 20xx
Hollow spheres Al2O3 was successfully synthesized via a simple template method and used to catalyze a new process from
methyl vinyl ether to propylene. In this study, it not only indicated that a two-step integration process from acetylene and
methanol to propylene is feasible but also could adjust the distribution of the products by the prepared catalyst. Firstly,
the colloidal carbon spheres were formed by hydrothermal synthesis method, and then the template was used to prepare
hollow spheres Al2O3, EDS, XRD and SEM, TEM which showed the component of the catalyst were only O and Al and the
structure was hollow spheres, respectively. In the new process tests, the low carbon olefins are detected as the main
products, alkanes are nearly not observed. The participation of hollow spheres Al2O3 could significantly enhance the
selectivity of olefins especially for propylene compared to the results without catalysts. Furthermore, the effects of
temperature on the products were also investigated, and a possible radical-involved reaction mechanism is discussed in
DOI: 10.1039/x0xx00000x
www.rsc.org/
detail
at
the
end.
researchers have been trying to integrate acetylene and other
small molecular compounds to produce propylene. In early
years, Belavin et al investigated the feasibility of the reaction
of acetylene and methane to form propylene in one step,
however, they failed to realize the assumption when using Fe,
Co, Ni and Cr2O3 as the catalyst and conclude that the one step
reaction is infeasible.14 Afterwards, Yang et al disclosed an
approach to produce propylene using acetylene and carbon
dioxide as materials, the remodeled nitrogenase was used to
catalyze the reaction. Findings suggest that when CO2 was
used as substrate, propylene was detected as the major
product after adding appropriate amount of acetylene.15 Also,
the integration of acetylene and carbon monoxide was
studied, Zhang et al used Fischer–Tropsch Synthesis, they
illustrated that with the participation of carbon monoxide,
acetylene can form ethylene, propylene and butylene.16 In our
study, the new integrate reaction of acetylene and methanol
to form propylene was proposed.
As reported,17-19 acetylene reacts with methanol under alkaline
conditions at below 300 ºC could produce MVE (methyl vinyl
ether) which is a kind of widely used material for industry. The
researchers firstly found that MVE monomer is easy to
polymerize at low temperatures and the polymers have good
physicochemical properties which could apply in adhesive,20, 21
plasticizer,22 pesticides,23 biomedical,24 dielectric material25
and UV curing fields.26 Due to the characteristic of easily
polymerization in low temperature, the subjects almost focus
on MVE as precursor prepared for polymers. However, the
catalytic properties of MVE at high temperature were greatly
ignored. As we know, there is no research group have reported
Introduction
Light olefins such as ethylene, propylene and butylene are
valuable feedstock for the petrochemical industry,1, 2 especially
for propylene, which can be used in the manufacture of
polypropylene, acrylonitrile, propylene oxide, cumene and
acrylic acid, etc. The growth rate of propylene demand is
estimated at 4-5% per year.3, Currently, about 70% of
4
propylene worldwide production comes from steam crackers,
28% from refinery fluid catalytic cracking (FCC) units.5
However, the petroleum route is unable to meet the
increasing demand of propylene, therefore, various types of
new processes for preparing propylene from cost-effective
resources have been developed as alternatives to the
traditional petroleum decomposition. Producing propylene
through simple raw materials has gradually become a hot
topic, for example, the conversion of methanol to propylene,6,
7 and dehydrogenation of propane.8-11 Especially, Taoufik et al.
reported a new and efficient catalytic reaction which can
directly develop ethylene into propylene with selectivity higher
than 95%.12 He et al. used CH4 as the material, disclosed a two-
step reaction route that catalyzed by modified CeO2
nanocrystals, and achieved the conversion from CH4 to
propylene via monohalogenomethane.13
Acetylene, as one of the most common chemical raw
materials, receives continuous attention as well. Many
the products of MVE via
a catalytic process in high
temperatures. As an intermediate from acetylene and
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Pyrolysis experiments
Methyl vinyl ether is employed as the only starting material.
methanol, it is reasonable to think it is feasible to generate
propylene by MVE. In our previous study, the joint reaction of
methanol and MVE on Ba/ZSM-5 has already been investigated Experiments were performed in clean and dry quartz tube furnace,
and we have found the potential of MVE on production of
olefins.27
the volume of the tube is 1 L. Before the experiments, the reactor
was purged with nitrogen to exhaust air for 30min, then the furnace
temperature was pre-set at certain values (200°C, 300°C, 350°C,
400°C, 500°C, 600°C and 700°C). WHSV (weight hourly space
velocity) was controlled at 1.2L/h, under atmospheric pressure,
added the gaseous reactant methyl vinyl ether to the reactor when
the temperature is stable. When the reaction was stable, the
gaseous product was collected with the gas collection pocket of
aluminum foil. After sealing, the samples were examined by GC -
MS detection. See Fig. 1.
In this paper, we propose a feasible process with acetylene
and methanol as the starting materials to produce propylene
in two steps. An intermediate, methyl vinyl ether (MVE), is
generated in the first step, and then MVE is further converted
to propylene. Herein, the second-step conversion from MVE to
propylene is our major concern. At first, we show that
propylene can be produced by thermal cracking MVE directly
without using any catalysts. This process is greatly simplified,
the products in the pyrolysis reaction are alkenes and
aldehydes which are easy to be separated compared to the
MTP method. Moreover, hollow spheres Al2O3 was used in
order to enhance the selectivity of propylene. The results
showed that the yield of propylene could increase nearly three
times, the mechanism is also proposed to explain the data we
got in the end.
Catalytic experiments
The prepared hollow spheres Al2O3 mixed with an appropriate
amount of quartz sand fill in the middle of the reactor, other
operate conditions are same to the pyrolysis experiments. The
temperature were set at 250°C, 350°C, 400°C, 500°C, 600°C and
700°C, respectively.
7)
6)
Experimental
Preparation of colloidal carbon spheres
3)
2)
1)
In the synthesis of colloidal carbon spheres,28 60g glucose
(C6H12O6•H2O) was dissolved in 300 mL of deionized water. The
resultant solution was transferred to a 500 mL of Teflon-sealed
autoclave and maintained at 180°C for 12 h. Subsequently, the dark
brown liquid products were wahsed with ethanol and deionized
water for several times using centrifugal treatment, until the filtrate
become colorless. Finally the solid products were dried at 80°C for
12 h and grounded to powder for use.
5)
4)
Fig.1 Apparatus for catalytic reactions. (1) High-purity nitrogen (2) Methyl vinyl
ether (3) Tubular furnace (4) Fixed bed reactor (5) Gas-liquid separator (6) GC-MS
(7) shut-off valve
Preparation of hollow spheres Al2O3
Results and Discussion
45g Al(NO3)3•9H2O dissolved in 300 mL of anhydrous ethanol, then
the 1g of prepared carbon spheres were added into the solution
followed by ultrasonic dispersion for 2h to become a brown mixture
solution. Then the mixture was placed at room temperature for 24h.
The obtained product was washed with deionized water repeatedly
and dried at 80°C for 6 h. And the final dried powder product was
calcined at a ramp heating rate of 3 °C /min in static air from room
temperature to 500°C and maintained at 500°C for 4 h.
Catalyst characterization
Characteristics of catalysts
EDS analysis (Fig .2 (a)) showed that the prepared sample have two
peaks which represent O and Al, respectively. C element was not
detected which means the template was removed completely after
calcination. As shown in Fig .2 (b), no strong diffraction peaks
appear, indicating that the catalysts are in a form of agraphitic Al2O3.
Powder X-ray diffraction (Rigaku Ultima IV) was used to characterize
the crystallinity and chemical composition of the
materials studied. The intensity data were collected over a 2θ range
of 20-80°, The step size was 0.025° with a time duration per step of
0.8 s. The surface structure of the Ca-based materials was
characterized using SEM (HITACHI SU8010). The samples were
placed on a double-sided carbon tape mounted on a sample holder,
subsequently coated for 30s using a gold semi-high resolution
coater. Transmission electron microscopy (TEM) was employed to
gain insigh ts into the detailed structure of the sorbent powders.
The BET analysis of the sample was using Micromeritics Instrument
Corporation Tristar II 3020 at 77K, the pore diameters were
determined by means of BJH method.
Fig.2 Structure features of alumina hollow spheres (a) EDS spectrum of alumina
hollow spheres (b) XRD pattern of alumina hollow spheres.
The morphology of colloidal carbon spheres and hollow spheres
Al2O3 were shown as Fig. 3 and Fig. 4. Due to the abundant -OH and
C=O on the colloidal carbon spheres external surface, Al3+ would be
easy to adsorb on the surface of the template untill the thickness of
2 | J. Name., 2012, 00, 1-3
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250
200
150
100
50
the adsorbed layer reaches a certain value and the balance was
done. When come to the template removal process, carbon will
transform to CO2 in the air atmosphere leaving the hollow structure.
Obviously, most hollow spheres Al2O3 keep tact shape, the hollow
structure could be seen from the TEM and the ruptured hollow
spheres. Due to the process of removing the template, the volum of
the spheres shrinked with the release of CO2 compared to colloidal
carbon, the surface of the catalysts was not smooth also, all of them
kept folded surface. The BET surface area and pore size distribution
of the two samples were present in Fig.5 (a)-(d). The BET surface
areas of the hollow spheres Al2O3 was up to 194m2/g which was
larger than the commercial γ-Al2O3(about 120 m2/g). Moreover PSD
analysis (pore size distribution) indicates that these spheres have
average pore diameter of 12.3 nm that was conducive to abosorb
the reactant in the hollow structure compare to 6.1 nm for γ-Al2O3.
0.4
0.3
0.2
0.1
0.0
(d)
(c)
0
20 40 60 80 100 120 140 160 180 200
PoreDiameter(nm)
γ
-Al2O3
0.0
0.2
0.4
0.6
0.8
1.0
P/P
0
Fig.5 (a) Nitrogen adsorption/desorption isotherms and (b) The pore size
distribution of hollow spheres Al2O3。(c) Nitrogen adsorption/desorption
isotherms and (d) The pore size distribution of γ- Al2O3
。
The effects of temperature in pyrolysis experiments
Firstly, the decomposition and the selectivity rate of propylene by
thermal cracking MVE were studied in different temperatures. The
pyrolysis products include ethylene, propylene, isobutylene,
acetaldehyde, and propanal. Table 1 shows the content of each
component in the mixture. It can be found that the selectivity of
propylene and the conversion rate of MVE were low but still show a
very gradual increment as temperature rose until 400°C. When the
temperature stays higher than 400°C, both the selectivity and the
conversion rate are improved dramatically. The maximum
selectivity of propylene is around 13.8% at 600°C (see Fig. 6).
20
Selectivity of propylene(%)
Conversion rate of MVE (%)
100
80
60
40
20
Fig.3 SEM images of the prepared catalysts (a) (b) Colloidal carbon spheres (c) (d)
(e) hollow spheres Al2O3.
15
10
5
0
-5
-10
200
400
500
700
300Tempreture C 600
(° )
Fig.6 The dependence of selectivity of propylene and conversion rate of MVE on
the temperature. The experiments were conducted at atmospheric pressure and
the weight hourly space velocity is 1.2L/h without catalyst. The temperatures are
200°C, 300°C, 350°C, 400°C, 500°C, 600°C and 700°C, respectively. ■
selectivity of propylene. △ conversion rate of methyl vinyl ether.
Fig.4 TEM images of the hollow spheres Al2O3
400
0.4
0.3
0.2
0.1
(b)
(a)
350
300
250
200
150
100
50
Table 1. The yield distribution of main products in different temperatures with no
catalysts
= a
= b
= c
CO
[%]
C2
C3
C4
CH3CH
O [%]
CH3CH
2CHO
[%]
MVE
d
0
20 40 60 80 100 120 140 160 180 200
[%]
[%]
[%]
Pore Diameter (nm)
[%]
68.5
64.7
61.3
200°C
300°C
350°C
1.7
2.3
8.2
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Hollow sphere Al2O3
0
0.0
0.2
0.4
0.6
0.8
1.0
0.06
0.01
0.08
0.01
P/P
0
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50
400°C
10.8
17.0
39.7
43.1
ꢀ
0.4
0.03
3.5
0.14
2.8
1.5
0.3
0.02
1.4
0.3
ꢀ
58.5
40%
40
30
20
10
0
500°C
600°C
700°C
13.0
14.4
27.3
13.0
13.8
12.0
46.1
31.5%
2.7
ꢀ
ꢀ
0.2
a C2= represents ethylene. b C3= represents propylene. c C4= represents isobutene. d
MVE represents methyl vinyl ether.
The effects of hollow spheres Al2O3
Hollow Sphere Al O
2 3
γ
-Al O
2 3
Hollow spheres Al2O3 which not only has high specific surface area
but could keep stable at higher temperatures was regarded as good
catalyst according to the proposed mechanism below. We found
the catalyst’s participation can significantly adjust the distribution
of the products. Based on hollow spheres Al2O3, the pyrolysis at
different temperatures (250°C, 350°C, 400°C, 500°C, 600°C and
700°C) was conducted. As a contrast, commercial Al2O3 with lower
BET surface (120m2/g) was also tested which was presented in Fig.8.
Table 2 showed the operating conditions and the main products.
The comparison on the selectivity of ethylene and propylene for
two tests is shown as Fig. 7 (a), the catalyst obviously enhanced the
olefin yield even at lower temperatures. However, the conversion
of MVE is the same up to 99% in higher temperatures that are
shown in Fig. 7 (b).
Fig.8 The comparison of the commercial γ-Al2O3 and hollow sphere Al2O3
Table 2. The selectivity of propylene and conversion of MVE in catalytic
experiments catalyzed by hollow spheres Al2O3.
Tempera
ture
Pressure
(MPa)
WHSV e
(L/h)
Selectivity
of
Selectivity
of
Convers
ion of
MVE
ethylene
propylene
(°C )
[%]
[%]
[%]
250°C
350°C
400°C
500°C
600°C
700°C
0.3
0.3
0.3
0.3
0.3
0.3
1.2
1.2
1.2
1.2
1.2
1.2
ꢀ
0.4
17.2
26.5
29.8
40.0
2.0
41.0
98.8
15.4
15.2
13.1
23.5
17.8
>99.0
>99.9
>99.9
>99.9
Fig. 7 (c) and (d) illustrated the differences of C3=/C2= and C3= yield
between catalytic and pyrolysis test. It is found that in the pyrolysis
experiments, the highest yield of propylene is 13.8% at 600°C and
31.5% with the catalysed with commercial Al2O3 (Fig. 8).However, it
could reach 40% at 600°C with hollow spheres Al2O3, which triple
the yield in addition to the enhanced selectivity of ethylene.
e weight hourly space velocity
=
Moreover, C3 /C2= in catalytic test is higher than pyrolysis test
The proposed mechanism
indicating the selectivity of propylene increased.
Blades et al. had investigated the thermal decomposition of vinyl
ethyl ether into ethylene and acetaldehyde，however, they failed
to establish a mechanism for the reaction.29 Lauer et al. found the
thermal decomposition of phenyl vinyl ether at 260-300ºC produces
phenol, acetaldehyde diphenylacetal and an unknown substance of
high molecular weight. 30 Murad reported the photolysis of ethyl
vinyl ether and suggested that some radical combination reactions
are responsible for the formation of the products. 31 Herein, the
mechanism of MVE catalyzed by hollow spheres Al2O3 was
proposed as Fig. 9.
Fig.7 The production distribution of the process catalysed by hollow spheres
Al2O3 (a) The comparison of the selectivity of ethylene and propylene (b) The
comparison of the conversion of MVE (c) The comparison of propylene/ethylene,
"*" represents there is no ethylene or data (d) The comparison of the selectivity
of propylene
Fig.9 Proposed mechanism for the methyl vinyl ether to propylene process.
Actually, the catalysis process is regarded accomplished by two
steps. In the first step, it is believed the pyrolysis on Al2O3 is the
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[%]
0.1
0.1
0.5
0.3
0.2
ꢀ
[%]
[%]
0.1
0.04
0.04
0.1
ꢀ
[%]
0.1
0.1
0.1
0.1
ꢀ
[%]
[%]
26.3
28.3
30.7
27.4
ꢀ
mainly process and the active intermediate is playing a vital role in
the propylene and other by-products’ forming process. By analyzing
the product components in different temperatures, the formation
of the active intermediates is proposed, then the thermal cracking
mechanism of MVE is suggested as below in Equations (1).
200°C
300°C
350°C
400°C
500°C
600°C
700°C
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
(b)
(c)
.
+
2H
.
2C
CH2
CH
CH
CH
)
a
(
C
°
0
.
0
ꢀ
4
OCH3
<
(1)
>400°C
(d)
C
CH2
CH2
CH2 CH OCH3
ꢀ
ꢀ
.
CH
O
CH2
)
g
(
.
>
CH3
4
0
0
°
C
(h)
.
O
8.3
11.8
ꢀ
ꢀ
ꢀ
ꢀ
CH
CH2
CH2
+
CO
C
O
CH2
(f)
ꢀ
ꢀ
ꢀ
3.0
ꢀ
In this step, there is a competition between propylene formation
and ethylene formation. Propylene only comes from the
intermediate CH2=CH upon combined with CH3 free radicals.
Generally, there are three ways of generating ethylene. The first
When the temperature below 400°C, the predict products of
dimethyl ether and acetylene did exist especially the amount of
acetylene was very large which highly in accordance with the theory.
Due to the active intermediates generated in the pyrolysis of MVE
change with the temperatures, the MVE decomposition rate is low
as the temperature didn’t come to the pyrolysis point, at this
condition, process (a) dominates, small amount of CH3 radicals are
generated. The main product in this process is OCH3. Therefore it is
very difficult to form propylene that below 1% shown in Table1.
Another important evidence was the significant reduction of
acetylene when the temperature is above 400°C which could be
exactly predicted by process (c). The generated hydrogen took part
in the formation of olefins that lead to the dramatic increased olefin
yields shown in Table 1. In this condition, process (d) and (e) occur
dominantly while process (b) is greatly suppressed, which results in
the significant reduction of acetylene.
results from the reaction between CH2=CH and H. The second is the
dehydration of dimethyl ether and the last is the cracking of
butylenes. See Equations (2).
（
i）
.
.
CH2
CH2
CH2
CH2 CH2
CH + H
（
j
）
.
.
CH3OCH3
CH3
+
OCH3
(2)
（
k）
.
CH3
CH2 CH
CH2
CH3
+
CH
（
p）
CH2
CH2
C
CH2 CH CH3
The competition also exists between the formation reactions of
acetaldehyde and propanal. Actually, the formation of acetaldehyde
and propanal is due to the reactions of CH2-CH=O with H and CH3
respectively. The reaction mechanisms are shown in Equations (3).
.
H
.
CH3CHO
CH2 CH
O
（ l）
(3)
.
CH3
.
CH2
O
CH
CHO
CH3CH2
（
m）
However, the routes to generate propylene were limited as
described in Equations (2). Considering the competition between
ethylene and propylene, as a consequence, the key to enhance the
selectivity was to make process (d) domains. In other words, make
MVE one-step dehydrates seems imperative. Therefore, hollow
spheres Al2O3 with large BET surface was chosen. During the
reaction, MVE molecular will absorb on Al2O3. Due to the reaction
between solid and liquid, the contact between the reactants was
very imperative. The hollow structure with pores formed by the
release of CO2 (Fig. 3d and Fig. 4) more likely to capture the
reactant molecular and causes the time of the reactants on the
catalyst is longer compared to irregular morphology like commercial
Al2O3. Therefore, the reaction would be more sufficient. Moreover,
Al2O3 combined with H2O was considered as exothermic reaction
which made the reaction tend to be stronger. As predicted, the
yield of propylene increased significantly (Table 2). It is because
hollow spheres Al2O3 made the dehydration of MVE to form
CH2=CH=CH2 become more obviously. Simultaneously, the sharp
drop of acetylene can lead to an increase of H, which is great for
producing propylene.
The formations of two kinds of butylene are more complicated and
very different from the above. We suggest that the participation of
CH2=C=CH2 plays an important role. CH2=C=CH2 undergoes the
cycloaddition with methylene carbene at first. Then, the product
will continue to react and generate two kinds of butene via a ring-
opening addition reaction due to the massive H in the mixture
Equations (4).
CH2
CH2 CH CH2CH3
.
CH
:
H
2
OR
C
C
CH2
CH2
CH2
CH2
C
(4)
（
o）
（
n）
CH3
CH2
CH3
In order to confirm the mechanism, a series of experiments were
done. According to the mechanism, temperature was a key factor
which could significantly affect the distribution of the products. For
example, when the temperature was low, there must be some
intimidates that couldn’t observed in higher temperatures due to
their instability. Therefore, the mechanism could be confirmed by
correctly predicting the products under various temperatures.
Therefore, the trace products were exhaustive investigated from
200°C to 700°C. As expected, the products did include acetylene,
dimethyl ether, methanol and water etc. that were shown in Table
3. The reasons were detailed discussed as below.
Conclusions
Table 3. The observed trace products at some temperatures without catalyst
We have shown that a catalyst-free approach to produce
propylene from MVE is achievable. The two-step process, from
Entry
CH3OCH3
CꢀC
H2O
CH3OH
C
≡CꢀC
C≡C
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26 G.K. Noren, ACS Symposium Series, 1997, 673, 121-132.
27 Y. Wang, G.X. Jian, Z.H. Peng, J.J. Hu, X. Wang, W.B. Duan, B.
Liu, Catal.Commun., 2015, 66, 34–37.
28 M.B. Zheng, J.M. Cao, X.Chang, J. Wang, J.S. Liu, X.J. Ma,
Mater. Lett., 2006, 60, 2991-2993.
acetylene and methanol to MVE and then to propylene, is
feasible. It was found that the products of the pyrolysis
process are closely connected with temperatures, the
selectivity of propylene is up to 13.8% when the temperature
reaches 600°C, the pyrolysis mechanism is also proposed
which is involved in radical reaction. Furthermore, we have
found that the distribution of the products can be significantly
altered by using some dehydrating agent, especially for
enhancing the yield of propylene. Using hollow spheres Al2O3
as the dehydrating agent, the selectivity of propylene is
enhanced by 40%. Compared to the traditional way to produce
propylene, the products in our process are much easier to
separate and purify which will significantly reduce the costs.
The exact mechanism of the catalytic reactions and the effect
of other catalysts are now still under investigation in our lab.
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DOI: 10.1039/C5RA25100A
The proposed mechanism for a new process of methyl vinyl ether to
propylene.