Chemical Engineering Journal 278 (2015) 217223

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Chemical Engineering Journal

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

Butadiene production from bioethanol and acetaldehyde over tantalum

oxide-supported spherical silica catalysts for circulating uidized bed
Tae-Wan Kim , Joo-Wan Kim, Sang-Yun Kim, Ho-Jeong Chae, Jeong-Rang Kim, Soon-Yong Jeong,
Chul-Ung Kim
Research Center for Green Catalysis, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Yuseong-gu, Daejeon 305-600, Republic of Korea

h i g h l i g h t s
 The effect of size and structural properties of Ta2O5/silica sphere was studied.
 The various ETB reaction conditions for Ta2O5/silica sphere were studied.
 Ta2O5/Q-6 catalyst showed good mechanical strength and catalytic performance.
 Ta2O5/Q-6 catalyst tested for hydrodynamic properties in the cold-bed CFB.

a r t i c l e

i n f o

Article history:
Available online 16 October 2014
Keywords:
Ethanol to butadiene
Spherical silica
Tantalum oxide
Circulating uidized bed

a b s t r a c t
The chemical 1,3-butadiene (BD) is usually produced from ethanol and acetaldehyde (ethanol to BD, ETB)
over Ta2O5/SiO2 catalyst in xed-bed system. However, the ETB process has a short catalyst-regeneration
cycle due to rapid deactivation of the catalyst by coke. To overcome this problem, a circulating uidizedbed (CFB) reactor could be used in the ETB reaction for continuous regeneration of deactivated catalyst.
The catalyst supplied to a CFB reactor must be spherical, show good catalytic performance, and be
mechanically strong. In this study, a series of samples of Ta2O5 catalyst on silica spheres with different
pore and particle sizes, were prepared. The catalysts were examined for mechanical strength by an
attrition test and in ETB reaction in the xed-bed reactor. The Ta2O5/Q-6 catalyst, with particles size of
75150 lm, showed good mechanical strength and the best catalytic performance. This optimum spherical catalyst was tested to examine its hydrodynamic properties in a cold-bed CFB reactor.
2014 Elsevier B.V. All rights reserved.

1. Introduction
The chemical 1,3-butadiene (BD) is an important chemical
intermediate in the petroleum industry because BD is a base material used for producing commercially important synthetic rubbers
and polymers [1]. The main application of BD is in the production
of acrylonitrile butadiene styrene and styrene butadiene rubber,
which is used for manufacturing automotive tires. Due to the continuous growth of the global economy, especially in China and
India, the global automotive tire market is also expected to glow
consistently and to reach about USD 180 billion by 2017. This
potential attracts many investors and researchers to the production of BD [2]. At present, the increasing rate of demand for BD
has created a serious decit in BD production by steam cracking
Corresponding authors. Tel.: +82 42 860 7257; fax: +82 42 860 7508
(T.-W. Kim). Tel.: +82 42 860 7504; fax: +82 42 860 7508 (C.-U. Kim).
E-mail addresses: twkim@krict.re.kr (T.-W. Kim), cukim@krict.re.kr (C.-U. Kim).
http://dx.doi.org/10.1016/j.cej.2014.09.110
1385-8947/ 2014 Elsevier B.V. All rights reserved.

of naphtha due to the depletion of petroleum, high price of oil,

and environmental issues. These conditions have motivated a push
to develop alternative technologies for BD production from renewable, and non-petroleum resources [1]. In addition, long-term
shortages of C4 chemicals are expected to be the outcome of the
availability of huge quantities of natural gas caused by recent
American shale-gas revolution. This has driven a shift to lighter,
gas-based feed-stocks; away from heavier, oil-based feed-stocks,
in the petrochemical industry [3]. This shift to lighter feed-stocks
has resulted in a signicant reduction of BD production because
BD is now primarily produced as a byproduct of ethylene cracking
of the oil-based feed-stocks [4]. Ethanol is the most abundant biobased, sustainable resource because industrial ethanol is mainly
produced via fermentation of biological-feed-stocks such as sugar
and corn [1,5]. The production of ethanol as a biofuel was greater
than 100 billion liters in 2011 and expected to increase 37%
annually in the years from 2012 to 2015 [6]. As the bioethanol
market grows rapidly, the manufacture of bio-ethanol-based

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T.-W. Kim et al. / Chemical Engineering Journal 278 (2015) 217223

building blocks for the chemical industry has attracted a lot of

attention. Therefore, if technological advances can be achieved in
the near future, BD production using bioethanol would be the most
promising, sustainable and renewable technology among various
on-purpose BD-production technologies [7].
The catalytic conversion of ethanol into BD (ETB) is a wellknown industrial process. The ETB process has been used from
the 1920s, but was scrapped due to lower oil prices enabled by
increasing oil production in early 1960s [1,5,814]. However, the
ETB process is now again becoming attractive as a potential alternative due to high oil prices and the generous supply of bioethanol
[1,5,7,15,16]. ETB processes are mainly divided into two kinds.
Lebedevs process has only one step, and Ostromyslenskys process
has two [1,5,815]. The latter was commercialized by the Carbide
and Carbon Chemicals Corporation in the United States [1722],
and involves two series of reactions (ethanol (EtOH) dehydrogenation to acetaldehyde (AA), and then EtOH-AA condensation
to BD) in a xed-bed system. Silica supported tantalum oxide
(Ta2O5/SiO2) is the best-known catalyst for the second step of the
ETB process [1722].
However, both ETB processes have short catalyst-regeneration
cycles (12 h for the one-step process, and 120 h for the two-step
process) because of the rapid deactivation of the catalyst by coke
formation [1722]. In order to continuously remove the coke from
the catalyst, a circulating uidized bed (CFB) reactor could be
applied to the ETB reaction. The CFB catalytic reactors were rst
tried to develop uid-catalytic-cracking (FCC) technology for the
production of gasoline from the oil to replace old bubbling-bed
reactors [23]. Since the 1960s, CFB reactors have been applied to
various chemical processes such as gasication and combustion
of methane, biomass and coal [24,25], FCC, FischerTropsch synthesis, and methanol-to-olen (MTO). The CFB reactor may easily
control the heat generated by exothermic reactions, enhance mass
transfer in a gassolid reaction system, and provide continuous
regeneration of the coke-choked catalyst [26]. However, the catalyst used in the CFB reactor need be resistant both to severe heat
and to mechanical stresses due to operating conditions that
include high temperature and high velocity ow. A catalyst with

Fig. 1. CFB reactor apparatus for 1,3-butadiene production from ethanol and
acetaldehyde (1: riser, 2: stripper, 3: regenerator, 4: stripper slide valve, 5:
regenerator slide valve, 6: stripper transfer line, 7: regenerator transfer line, 8: ue
gas control valve, 9: product gas control valve, 10: regenerator air inlet, 11: feed
inlet, 12: riser nitrogen inlet, 13: stripper nitrogen inlet, 14: ue gas outlet, 15:
product gas outlet).

low attrition resistance could cause many problems in the CFB system and could eventually shut down the overall process. Therefore,
it is essential that a spherical Ta2O5/SiO2 catalyst with both good
catalytic performance and signicant mechanical strength be provided as the ETB catalyst in CFB reactors.
In this study, we report for the rst time spherical-shaped tantalumsilica based catalysts in order to apply CFB reactor for the
continuous remove of coke in ETB reaction. The catalytic performance and mechanical strength of the Ta2O5/SiO2 spherical catalysts were examined using a xed-bed reactor and an attrition
test, respectively. After selection of the optimum spherical catalyst,
having both high catalytic activity and attrition resistance, we
evaluated the hydrodynamic properties of the optimum catalyst
using a cold-bed, circulating uidized bed reactor.
2. Materials and methods
2.1. Preparation of Ta2O5 supported spherical silica catalysts
Commercial silica spheres (CARiACT Q-n, where n stands for
the pore size of the silica) were obtained from Fuji Silysia. All

Fig. 2. Nitrogen sorption isotherms and pore size distributions of the catalysts.

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T.-W. Kim et al. / Chemical Engineering Journal 278 (2015) 217223

of the spherical silica-supported 2 wt% tantalum oxide (Ta2O5)

catalysts were prepared by an impregnation method using ethanol as a solvent. A measure (100 g) of spherical silica support
was added to 1000 ml of ethanol, which also contained 32 g of
tantalum pentachloride (TaCl5, Aldrich). After stirring for 2 h,
the ethanol was removed using a rotary evaporator and the samples were dried at 120 C for 10 h. The CARiACT Q-n-supported
Ta2O5 samples (Ta2O5/Q-n) were obtained by calcination at
500 C for 5 h.
2.2. Characterization
Nitrogen adsorption isotherms were measured at 196 C on a
Micromeritics Tristar 3000 volumetric adsorption analyzer. Before

Total conversion

BD selectivity

inch stainless steel (SUS) tube reactor [7]. The reaction temperature was controlled by a type-K thermocouple (Omega) and a PID
controller. A mixture of ethanol (99.9 wt%, Samchun) and acetaldehyde (85 wt%, Aldrich) with ethanol, to provide an acetaldehyde
molar ratio of 2.5 [17,21], was fed into the catalytic reactor at
0.66 ml/h by a high-performance liquid chromatography (HPLC)
pump. The catalyst (0.25 g) was loaded in the middle of the SUS
tube. Before the reaction, the catalyst was warmed up to the
reaction temperature (350 C, heating rate = 5.0 C/min) with a
5 ml/min ow of the carrier gas (N2). The reaction was then performed with a liquid hourly space velocity (LHSV) of 1.0 h1 at
350 C. The efuent gas products were measured using a gas chromatograph (6100GC, Young Lin Instrument Co.) equipped with a
ame ionization detector (FID). Products were detected by the

Total C moles  C moleunreacted EtOH C moleunreacted AA

 100
Total C moles

C moleBD in products
 100
Total C moles in products except for EtOH and AA

the adsorption measurements, all samples were outgassed at

300 C in a degassing station. The BrunauerEmmettTeller (BET)
equation was used to calculate the apparent surface area from
the adsorption data obtained at P/P0 between 0.05 and 0.2. The
total volume of micro- and mesopores was calculated from the
amount of nitrogen adsorbed at P/P0 = 0.95, assuming that adsorption on the external surface was negligible compared to adsorption
in the pores. The pore size distributions were calculated by analyzing the desorption branch of the N2 sorption isotherm using the
BarretJoynerHalenda (BJH) method. Scanning electron microscope (SEM) images were obtained with a Philips XL-30S eld
emission guns (FEG) SEM operated at 10 kV. The samples were
coated with gold before SEM measurement. The attrition test of
the spherical catalyst was determined using the ASTM D5757-95
method. After 50 g of the catalyst was uidized by air at 10 l/min
for 5 h, the amount of entrained catalyst collected in the thimble
lter was measured. The attrition rate is dened as the ratio of
the amount of entrained catalyst to the total amount of catalyst
(50 g) used [26]. The bulk density of the catalyst was determined
by measuring the mass and volume of a catalyst sample using a
balance and a graduated cylinder, respectively.
2.3. Catalytic test in a xed-bed reactor
The production of 1,3-butadiene (BD) from ethanol and acetaldehyde was performed in a xed bed reactor system with a 3/8

FID using a capillary HP Plot Q column (0.53 mm id  40 micron

thickness  30 m length). Total conversions and BD selectivities
were calculated using the following equations.
2.4. Catalyst circulation test in the CFB reactor
A schematic diagram of the pilot CFB plant (riser length: 4 m,
riser inner diameter: 14.6 mm) used in the experiments appears
in Fig. 1. Hydrodynamic properties such as the catalyst circulation
rate were examined by means of a cold-bed CFB test (without
heating). First, 2.6 kg of the optimum catalyst was prepared as in
Section 2.1 and loaded into the CFB reactor. The cold-bed test
was performed under 25 psig of N2 gas pressure in a CFB pilot plant
with a mechanical slide valve.
3. Results and discussion
3.1. Properties of the Ta2O5/Q-n catalysts
Fig. 2 shows the nitrogen physisorption isotherms and pore size
distributions for the three different Ta2O5/Q-n samples. The capillary condensation step increased and the amount of N2 adsorption
below P/P0 = 0.2 decreased with an increase in the pore diameter.
This indicates that the number of mesopores in the Ta2O5/Q-n sample increased, while the number of micropores decreased, with
increasing of pore size. The pore size distribution curves for the

Table 1
Physical properties of catalysts.

a
b
c
d
e
f

Samples

Ta (wt%)a

SBET (m2 g1)b

Vt (cm3 g1)c

wavg (nm)d

wBJH (nm)e

Dbulk (g/ml)f

Attrition test (%)

Ta2O5/Q-3
Ta2O5/Q-6
Ta2O5/Q-10

1.84
1.90
1.91

688
530
214

0.37
0.58
1.15

2.2
5.9
13.3

2.0
7.3
16.6

0.77
0.53
0.38

0.30
0.21
2.93

Ta, Ta loading measured by ICP-AES.

SBET, apparent BET specic surface area.
Vt, total pore volume.
wavg, the average pore size.
wBJH, the pore size calculated using the BJH method and deduced from the highest point of pore size distribution curve.
Dbulk, bulk density.

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T.-W. Kim et al. / Chemical Engineering Journal 278 (2015) 217223

Ta2O5/Q-n samples also show an increase in the mesopore volume

with increasing pore diameter. The detailed structural properties of
the Ta2O5/Q-n samples are summarized in Table 1. The average
pore sizes of the Ta2O5/Q-n catalysts are shown to range from 2.2
to 13.3 nm. The pore sizes of Ta2O5/Q-3 and Ta2O5/Q-6 calculated
by the desorption branch of the isotherm using the BJH method,
were larger than the average pore sizes due to overestimation by
the BJH method of the range of large mesopores [27]. The specic
surface area gradually decreased with an increase in pore diameter,

while the pore volumes signicantly increased from 0.37 to

1.15 cm3/g. This enlargement of pore volume was mostly caused
by the increase in the mesopore volume of the Ta2O5/Q-n catalysts.
The bulk density and mechanical strength of the Ta2O5/Q-n catalysts examined by attrition test are shown in Table 1. The Ta2O5/
Q-6 catalyst exhibited the highest attrition resistance (0.21%),
while Ta2O5/Q-10 showed the lowest attrition (2.93%). With an
increase of pore size, the surface area and bulk density decreased.
This indicates that larger pore size might lead to a mechanically

Fig. 3. SEM images of catalysts: (a) Ta2O5/Q-3, (b) Ta2O5/Q-5, and (c) Ta2O5/Q-10.

Fig. 4. EtOH/AA total conversion (open symbol) and BD selectivity (solid symbol) of Ta2O5/Q-n catalysts (circle: Ta2O5/Q-3, square: Ta2O5/Q-6, triangle: Ta2O5/Q-10).

Table 2
Catalytic performance of Ta2O5 supported Q-n catalysts in a xed bed reactor at 350 C, LHSV of 1 h1 at 30 h.
Sample

Ta2O5/Q-3
Ta2O5/Q-6
Ta2O5/Q-10
*

EtOH/AA conv. (%)

10.9
31.5
30.6

Carbon selectivity (C mol%)

Ethylene

Propylene

Butene isomers

1,3-BD

Ethoxy ethane

Ethyl acetate

Crotonaldehyde

Acetic acid

Others*

4.6
2.7
1.8

1.1
1.6
1.2

0.7
1.6
1.6

47.8
72.0
70.3

4.9
0.2
2.0

3.4
0.6
2.0

18.0
0.3
6.4

0.6
6.6
3.7

19.0
14.4
11.0

Unidentied compounds mainly consisting of heavier compounds than acetic acid in GC chromatography.

T.-W. Kim et al. / Chemical Engineering Journal 278 (2015) 217223

221

Fig. 5. SEM images of Ta2O5/Q-6 catalysts of different particle size: (a) 75150 lm, (b) 75200 lm, (c) 200300 lm, and (d) 300500 lm.

weak catalyst, resulting from a less dense silica framework given

similar-sized silica-support. Thus, the catalyst with the largest
pore size (Ta2O5/Q-10) showed the lowest attrition resistance.
SEM images of the tantalum-oxide-loaded spherical silica catalysts are displayed in Fig. 3. All SEM images of the Ta2O5/Q-n catalysts show a spherical morphology with a particle size around
200300 lm.

3.2. Catalytic test for ETB in the xed-bed reactor

To investigate the effects of the mesopore size, and to determine the optimum mesopore size, the catalytic activities of the catalysts (particle size 200300 lm) with different pore diameters
were examined for ETB reaction in the xed-bed reactor. Fig. 4
shows the total conversion of ethanol (EtOH) and acetaldehyde
(AA), and the 1,3-butadiene (BD) selectivity of three spherical silica-supported tantalum oxide catalysts with different pore diameters. The conversions for all samples gradually decreased with
time-on-stream due to the formation of coke in the catalysts, while
the selectivities of BD were almost constant over the entire reaction time. This clearly reveals that the CFB reactor needs to continuously regenerate catalyst deactivated by accumulation of coke.
Among the series of Ta2O5/Q-n catalysts, the total conversion and
the BD selectivity of the Ta2O5/Q-3 catalyst showed the lowest values among all catalysts due to its smaller pore size. The catalysts
with pore size above 6 nm showed good conversion and BD selectivity. The Ta2O5/Q-6 catalyst with the middle mesopore size (average pore size 5.9 nm) showed the highest catalytic performance
(total conversion = 31.5% and BD selectivity = 72.0%), which was
slightly higher than that of the Ta2O5/Q-10 catalyst (total conversion = 30.6% and BD selectivity = 70.3%). As shown in Table 1, the
mesopore size of the Ta2O5/Q-10 catalyst (13.3 nm) was over two
times larger than that of the Ta2O5/Q-6 catalyst (5.9 nm), whereas
the BET-specic surface area of the Ta2O5/Q-10 catalyst (214 m2/g)
was over two times less than that of the Ta2O5/Q-6 catalyst
(530 m2/g). From structural analyses of the catalysts and results
from the catalytic tests, the Ta2O5/Q-6 catalyst appears to be the
best candidate for ETB reaction because it has both a moderately
large mesopore size and a high surface area, which facilitate good
accessibility of the reactants and products, as well as good disper-

sion of tantalum oxide within the silica [7]. The detailed product
selectivities are shown in Table 2, including unidentied compounds. These were heavy compounds and would mainly cause
deactivation of the catalyst by creation of coke. The formation of
heavy compounds was gradually reduced with increasing mesopore size of the catalysts. This indicates that a catalyst with large
mesopores forms lesser amounts of heavy compounds compared
with catalysts with small mesopores, due to better accessibility
and diffusion of the reactants and the products [7].
The optimum spherical silica-supported tantalum oxide catalyst is Ta2O5/Q-6 because Ta2O5/Q-6 showed both good catalytic
performance and good mechanical strength, which are essential
for the catalyst in a CFB reactor. To investigate the effect of the particle size of the Ta2O5/Q-6 catalyst for the ETB reaction, we prepared four Ta2O5/Q-6 samples with different particle sizes
(Fig. 5): 75150, 75200, 200300, and 300500 lm. As shown
in Fig. 6 and Table 3, the conversions of particles less than
300 lm were 30.133.4% at a reaction time of 30 h, and the BD
selectivity increased with decreasing particle size of the catalyst.

Fig. 6. EtOH/AA total conversion (open symbol) and BD selectivity (solid symbol) of
Ta2O5/Q-6 catalysts of different particle size (circle: 75150 lm, square: 75
200 lm, triangle: 200300 lm, diamond: 300500 lm).

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T.-W. Kim et al. / Chemical Engineering Journal 278 (2015) 217223

Table 3
Catalytic performance of Ta2O5 supported Q-6 catalysts with different particle size in a xed bed reactor at 350 C, LHSV of 1 h1 at 30 h.
Particle size (lm)

75150
75200
200300
300500
*

EtOH/AA conv. (%)

33.4
30.1
31.5
24.6

Carbon selectivity (C mol%)

Ethylene

Propylene

Butene isomers

1,3BD

Ethoxy ethane

Ethyl acetate

Crotonaldehyde

Acetic acid

Others*

3.2
4.0
2.7
4.0

1.7
1.7
1.6
1.5

1.7
1.7
1.6
1.6

75.2
74.6
72.0
71.0

0.3
0.2
0.2
0.9

0.5
0.6
0.6
0.8

0.3
0.2
0.3
0.2

0.4
0.3
2.6
0.3

16.8
16.8
17.4
20.0

Unidentied compounds mainly consisting of heavier compounds than acetic acid in GC chromatography.

The smallest particle size, 75150 lm, for the Ta2O5/Q-6 catalyst,
shows the best catalytic performance, while the largest particle
size, 300500 lm, displayed the lowest catalytic activity. Small
particle sizes should facilitate the diffusion of reactants and products during the catalytic reaction, which is an effect similar to that
from large mesopores as discussed above [7]. In addition, the selectivity of heavy compounds (others in Table 3) in the particle size
range 300500 lm was 20.0%, which is the largest amount among
the catalysts due to relatively hard diffusion of reactants and products from the catalyst with large particle size, compared with that
of those with small particle size.

by the degree of opening of the slide valve in the bottom of the

regenerator (5) alone, which was determined from the measurement of differential pressure between the top and bottom of the
regenerator. A plot of the different pressure of regenerator versus
the catalyst weight loaded into the regenerator is shown in
Fig. 7. The differential pressures increase with the linear increase
in the catalyst weight (up to 1500 g) because the catalyst is lled
from the stand-pipe region of the regenerator, which has a constant pipe diameter. Above 1500 g of catalyst weight, the slope of
the different pressure per the catalyst weight decreased due to

3.3. Cold-bed CFB test

As discussed Sections 3.1 and 3.2, the optimum ETB catalyst for
a CFB reactor was Ta2O5/Q-6 with particle size 75150 lm. A 2.6 kg
portion of the optimum catalyst was prepared and loaded into the
circulating uidized bed (CFB) reactor, as shown in Fig. 1. First, to
evaluate catalyst circulation in the CFB reactor, we performed a
cold-bed test without heating the overall CFB reactor prior to
ETB reaction. The cold-bed test in the CFB reactor is important
because we can determine the rate of catalyst circulation from it,
which is connected with the ow rate of the riser gas and the
degrees of opening of the slide valve. The catalyst circulation rate
(CCR) is controlled by two mechanical slide valves located in the
regenerator bottom (5) and stripper bottom (4), as shown in
Fig. 1. When the degree of opening for the slide valve in the bottom
of the regenerator (5), and the gas velocity in the riser (1) were
xed, the CCR value could be kept constant by controlling the slide
valve in the bottom of the stripper (4) to keep a constant level of
catalyst in the stripper (2). Therefore, the CCR could be controlled

Fig. 7. Increase of differential pressure between top and bottom of the regenerator
with an increase in the amount of catalyst in the stand pipe region of the
regenerator.

Fig. 8. Decrease in the differential pressure of the regenerator with time for degree
of opening of the slide valve in the regenerator at 10 l/min of riser gas velocity.

Fig. 9. Effect of riser gas ow rate and degree of opening of the slide valve on the
catalyst circulation rate (CCR).

T.-W. Kim et al. / Chemical Engineering Journal 278 (2015) 217223

the increase of the pipe diameter in the regenerator. As the catalyst

in the regenerator is transferred to the stripper (2) by a certain gas
velocity of the riser through the slide valve in the bottom of the
regenerator (5) and the riser (1), the differential pressure of the
regenerator linearly decreases with time. Fig. 8 shows a
representative graph for this linear relationship between differential pressure and time at 10 l/min of riser gas velocity. Therefore,
the catalyst circulation rate could be determined from the following equation using these results [28].

Circulation rate kg=h

Weight of catalyst loaded into regenerator

Differential pressure of regenerator
Differential pressure of regenerator

Time

Fig. 9 displayed the effect of the riser gas-ow rate and degree
of opening of the slide valve on the CCR, calculated from above the
equation. The catalyst circulated well, when the riser gas velocity
was above 0.64 m/s, which is equal to a riser gas-ow rate of
6 l/min. The catalyst ow rates gradually increased with increasing
riser gas rate, up to 10 l/min. As the degree of opening of the slide
valve increased, the circulating rate of the catalyst also increased.
From the CCR results, the operating range of the CFB reactor using
Ta2O5/Q-6 catalyst can be controlled from 2.0 to 30 kg/h.
4. Conclusions
Spherical silica supported tantalum oxide samples with different pore and particle sizes were prepared and investigated as catalysts for a cold-bed test of a CFB reactor. The catalytic
performance of these catalysts was evaluated using a xed-bed
reactor to select an optimum catalyst for the CFB reactor. The catalyst having both moderately large mesopores and high surface
area showed good attrition resistance, as well as the highest catalytic activity due to the facile diffusion of reactants and products,
and the effective dispersion of the tantalum oxide. In addition,
the smallest particle size also exhibited the best catalytic performance for the ETB reaction because of an effect similar to that from
large pore size. The optimum catalyst was Ta2O5/Q-6 with
75150 lm particle size, and it was loaded into the CFB pilot plant
for the examination of its hydrodynamic properties before the ETB
hot-bed test. From the cold-bed CFB test, it was determined that
the Ta2O5/Q-6 catalyst could be circulated at rates from 2.0 to
30 kg/h in the CFB reactor. In the future, the additional studies
are needed to perform an ETB reaction in the hot-bed CFB reactor,
and to nd optimal process conditions for maximum production of
BD in the CFB reactor.
Acknowledgment
The authors would like to acknowledge funding from the project program of Korea Research Institute of Chemical Technology
(KRICT).
References

[3]

[4]

[5]

[6]

[7]

[8]

[9]
[10]
[11]

[12]
[13]

[14]

[15]

[16]

[17]
[18]

[19]
[20]
[21]
[22]
[23]
[24]

[25]

[26]

[27]
[28]

[1] E.V. Makshina, W. Janssens, B.F. Sels, P.A. Jacobs, Catalytic study of the
conversion of ethanol into 1,3-butadiene, Catal. Today 198 (2012) 338344.
[2] Transparency Market Research, Synthetic and Bio-Based Butadiene Market:
Industry Overview, Applications and Downstream Potential Opportunities,

223

20102018,
Transparency
Market
Research
website,
<http://
www.transparencymarketresearch.com/synthetic-and-bio-based-butadienemarket.html>.
P.C.A. Bruijnincx, B.M. Weckhuysen, Shale gas revolution: an opportunity for
the production of biobased chemicals?, Angew Chem. Int. Ed. 52 (2013)
1198011987.
J. Baker, Market Outlook: Bio-Based Routes to C4s Move Ahead, ICIS Website,
<http://www.icis.com/resources/news/2013/06/07/9676347/market-outlookbio-based-routes-to-c4s-move-ahead/>.
M.D. Jones, C.G. Keir, C.D. Iulio, R.A.M. Robertson, C.V. Williams, D.C. Apperley,
Investigations into the conversion of ethanol into 1,3-butadiene, Catal. Sci.
Technol. 1 (2011) 267272.
J.A. Posada, A.D. Patel, A. Roes, K. Blok, A.P.C. Faaij, M.K. Patel, Potential of
bioethanol as a chemical building block for bioreneries: preliminary
sustainability assessment of 12 bioethanol-based products, Bioresour.
Technol. 135 (2013) 490499.
H.-J. Chae, T.-W. Kim, Y.-K. Moon, H.-K. Kim, K.-E. Jeong, C.-U. Kim, S.-Y. Jeong,
Butadiene production from bioethanol and acetaldehyde over tantalum oxidesupported ordered mesoporous silica catalysts, Appl. Catal. B Environ. 150151
(2014) 596604.
S.K. Bhattacharyya, N.D. Ganguly, One-step catalytic conversion of ethanol to
butadiene in the xed bed. II BINARY- AND TERNARY-OXIDE CATALYSTS, J.
Appl. Chem. 12 (1962) 105110.
S.K. Bhattacharyya, B.N. Avasthi, One-step catalytic conversion of ethanol to
butadiene in a uidized bed, Ind. Eng. Chem. Process Des. Dev. 2 (1963) 4551.
S.K. Bhattacharyya, S.K. Sanyal, Kinetic study on the mechanism of the
catalytic conversion of ethanol to butadiene, J. Catal. 7 (1967) 152158.
B.B. Corson, H.E. Jones, C.E. Welling, J.A. Hinckley, E.E. Stahly, Butadiene from
ethyl alcohol. Catalysis in the one-and two-stop processes, Ind. Eng. Chem. 42
(1950) 359373.
H. Niiyama, S. Morii, E. Echigoya, Butadiene formation from ethanol over
silicamagnesia catalysts, Bull. Chem. Soc. Jpn. 45 (1972) 655659.
R. Ohnishi, T. Akimoto, K. Tanabe, Pronounced catalytic activity and selectivity
of MgOSiO2Na2O for synthesis of buta-1,3-diene from ethanol, J. Chem. Soc.
Chem. Commun. (1985) 16131614.
S. Kvisle, A. Aguero, R.P.A. Sneeden, Transformation of ethanol into 1,3butadiene over magnesium oxide/silica catalysts, Appl. Catal. 43 (1988) 117
131.
C. Angelici, B.M. Weckhuysen, P.C.A. Bruijnincx, Chemocatalytic conversion of
ethanol into butadiene and other bulk chemicals, ChemSusChem 6 (2013)
15951614.
G.O. Ezinkwo, V.F. Tretjakov, R.M. Talyshinky, A.M. Ilolov, T.A. Mutombo,
Creation of a continuous process for bio-ethanol to butadiene conversion via
the use of a process initiator, Catal. Commun. 43 (2014) 207212.
W.J. Toussaint, J.T. Dunn, D.R. Jachson, Production of butadiene from alcohol,
Ind. Eng. Chem. 39 (1947) 120125.
W.M. Quattlebaum, W.J. Toussaint, J.T. Dunn, Deoxygenation of certain
aldehydes and ketones: preparation of butadiene and styrene1, J. Am. Chem.
Soc. 69 (1947) 593599.
E.E. Stahly, H.E. Jones, B.B. Corson, Butadiene from ethanol, Ind. Eng. Chem. 40
(1948) 23012303.
H.E. Jones, E.E. Stahly, B.B. Corson, Butadiene from ethanol. Reaction
mechanism, J. Am. Chem. Soc. 71 (1949) 18221828.
B.B. Corson, E.E. Stahly, H.E. Jones, H.D. Bishop, Butadiene from ethyl alcohol,
Ind. Eng. Chem. 41 (1949) 10121017.
P.M. Kampmeyer, E.E. Stahly, Butadiene from ethyl alcohol: improved
production processes, Ind. Eng. Chem. 41 (1949) 550555.
D. Gidaspow, L. Huilin, Collisional viscosity of FCC particles in a CFB, AIChE J.
42 (1996) 25032510.
W. Zhou, C. Zhao, L. Duan, X. Chen, D. Liu, A simulation study of coal
combustion under O2/CO2 and O2/RFG atmospheres in circulating uidized
bed, Chem. Eng. J. 223 (2013) 816823.
B. Arstad, J. Prostak, R. Blom, Continuous hydrogen production by sorption
enhanced steam methane reforming (SE-SMR) in a circulating uidized bed
reactor: sorbent to catalyst ratio dependencies, Chem. Eng. J. 189190 (2012)
413421.
M. Kim, H.-J. Chae, T.-W. Kim, K.-E. Jeong, C.-U. Kim, S.-Y. Jeong, Attrition
resistance and catalytic performance of spray-dried SAPO-34 catalyst for MTO
process: effect of catalyst phase and acidic solution, J. Ind. Eng. Chem. 17
(2011) 621627.
L. Cao, M. Kruk, Short synthesis of ordered silicas with very large mesopores,
RSC Adv. 4 (2014) 331339.
J.J. Burkell, Solids Circulation Rate Measurement in a Circulating Fluidized Bed,
University of British Columbia, 1986.