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Article history:
Received 11 March 2013
Received in revised form 10 June 2013
Accepted 11 June 2013
Available online 2 July 2013
Keywords:
Catalytic conversion
Butene
Butane
Cracking
Propene
Aromatics
a b s t r a c t
The catalytic conversion of the C4 fraction from a uid catalytic cracking (FCC) unit over a commercial FCC equilibrium catalyst was investigated using a conned uidized bed reactor system. Butenes were easier to convert
than butanes, and 1-butene was the easiest to convert among the butene isomers. The ethene and propene yields
increased with increased reaction temperature and decreased with increased weight hourly space velocity
(WHSV). The formation of propene involved two successive steps: butene dimerization and large hydrocarbon
cracking. Aromatics were formed by the aromatization of the intermediate large olens. A mechanism parameter
RCA was proposed to describe the relative function of the cracking reaction to the aromatization reaction. RCA
increased with increased reaction temperature and decreased with increased WHSV. The cracking reaction
predominates on the aromatization reaction at high reaction temperatures.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Light olens (ethene and propene) and light aromatics (benzene,
toluene, and xylene) are basic materials in the petrochemical industry.
Light olens are traditionally produced by the steam cracking/pyrolysis
of ethane, propane, butane, naphtha, light diesel, or heavier hydrocarbons [1,2]. However, the steam pyrolysis process requires high reaction
temperatures and consumes large amounts of energy. Light aromatics
are traditionally produced by the catalytic reforming of naphtha. However, naphtha is in short supply in some regions, such as China, Korea,
and Japan.
Fluid catalytic cracking (FCC) is another important process for
propene production. The introduction of co-catalysts such as conventional ZSM-5, mesoporous ZSM-5, TNU-9, and SSZ-33 zeolite to a commercial equilibrium FCC catalyst can enhance the propene yield [3,4].
High yields of ethene and propene (>60 wt.%) have been achieved
when C4+ olens were cracked over hybrid catalysts at 610 C to
640 C [5].
The C4 fraction is an important fraction of FCC. C4 hydrocarbons
can potentially be used for producing light olens and light aromatics.
The catalytic conversion of C4 hydrocarbons offers an alternative to
steam cracking to produce light olens and aromatics.
The conversion of C4 hydrocarbons to light olens is attracting
considerable research interest. Butene is relatively easier to convert
Corresponding author at: State Key Laboratory of Heavy Oil Processing, China University
of Petroleum, Changping District, Beijing 102249, China. Tel.: +86 10 8973 1252 (ofce);
fax: +86 10 6972 4721.
E-mail address: lzch@cup.edu.cn (Z. Liu).
0378-3820/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2013.06.002
218
propene, and hydrogen are the primary products, and aromatics are
formed during a secondary process, namely, the oligomerization and
aromatization of butenes [17].
The C4 fractions are traditionally used as liqueed petroleum gas
(LPG). The market demand for LPG becomes weak as natural gas plays
more and more important role in the domestic fuel. Therefore, efciently
converting the C4 fraction has become an urgent problem. Lu et al.
proposed a method of converting n-butene into propene, i-butene,
i-butane, and gasoline on spent FCC catalyst in the stripper part. As
shown in simulation tests, high temperature and low WHSV favor the
formation of propene, i-butene, and i-butane, and the propene yield
reaches 10.22 wt.% at a reaction temperature of 500 C and a WHSV of
1.44 h1 [18]. Another possible method of efcient conversion of C4
fraction is to recirculate the C4 fraction to the FCC riser, where catalytic
conversion reactions occur. This process has the advantages of low
cost, easy operation, and high propene production.
This study investigated the catalytic conversion of the C4 fraction
from an FCC unit, as well as the inuence of reaction temperature
and WHSV on conversion and product yield. The main reactions and
reaction pathways of C4 fraction catalytic conversion were discussed
based on the above factors.
2. Experimental
2.1. Feedstock and catalyst
The C4 fraction collected from the FCC unit of a petrochemical company was used as the feed. The components of the C4 fraction are listed
in Table 1. The contents of butenes (1-butene, 2-butene, and i-butene)
and butanes (n-butane and i-butane) were 53.62 wt.% and 45.10 wt.%,
respectively. A commercial FCC equilibrium catalyst was used. The
physical properties and particle size distribution of the catalyst are
listed in Table 2.
2.2. Apparatus
The experiment was conducted in a uidized bed reactor with a lter on the bed top to prevent the catalyst from escaping. A diagram of
the apparatus is shown in Fig. 1. The apparatus consists of ve sections:
oil and steam input mechanisms, a reaction zone, a temperature control
system, and a product separation and collection system.
The experiments were conducted in batch mode. For each experiment, 60 g of catalyst was loaded into the reactor with an effective volume of approximately 580 mL. Distilled water was then pumped into
the steam furnace to form the steam used to uidize the catalyst in the
reactor. High-pressure nitrogen was injected into the C4 feed tank and
C4 buffer tank to keep the feedstock in a liquid state. A specic amount
of C4 feed was transferred from the C4 feed tank to the C4 buffer tank
by a pressure difference. An electronic balance under the C4 buffer tank
Table 2
Properties of the commercial FCC equilibrium catalyst.
Item
Value
Micro-activity index
Pore volume (cm3g1)
Surface area (m2g1)
Packing density (gcm3)
Coke content (wt.%)
Particle size distribution (wt.%)
020 m
2040 m
4080 m
80105 m
>105 m
60
0.22
88
0.91
0.04
0.8
16.2
54.6
15.8
12.6
was used to measure the mass of the C4 fraction fed into the reactor.
The C4 feed was then pumped and mixed with the steam. The mixture
was heated to approximately 350 C in a preheater and then fed into
the reactor. The reactions occurred as the feed made contact with the uidized catalyst. After reaction, the oil gas was cooled and separated into
gas and liquid samples. The spent catalyst was drawn out of the reactor
using a vacuum pump.
The experiments were conducted at various reaction temperatures between 400 and 700 C, various WHSVs from 1 h1 to 9 h1,
and a steam ow rate of about 10 wt.% of the C4 fraction.
10
N2
19
8
15
Table 1
Components in the C4 feed (wt.%).
Component
Content
Propane
Propene
i-Butane
n-Butane
2-Butene
1-Butene
i-Butene
C5+
Total
Butanes
Butenes
C4 hydrocarbons
0.35
0.39
35.84
9.26
22.28
12.86
18.48
0.54
100
45.10
53.62
98.72
11
12
2
1
16
13
14
17
18
Fig. 1. Experimental setup (1 water tank, 2 lter, 3 water pump, 4 steam furnace, 5
C4 feed tank, 6 electronic balance, 7 C4 buffer tank, 8 constant-pressure nitrogen, 9
C4 feed pump, 10 counterbalance valve, 11 preheater, 12 thermocouple, 13
reactor, 14 heater, 15 entrance and exit of catalyst, 16 condenser, 17 liquid
product sampler, 18 wet gas ow meter, and 19 gas sample bag).
25
i-butane
2-butene
i-butene
60
80
n-butane
1-butene
C4
40
20
-20
219
20
15
10
0
400
450
500
550
600
650
WHSV: 3 h-1
ethene
propene
aromatics
700
400
450
500
550
600
650
700
Table 3
Product yield as a function of reaction temperature at a WHSV of 3 h1 (wt.%).
Table 4
Product yield as a function of WHSV at a reaction temperature of 700 C (wt.%).
400
450
500
550
600
650
700
WHSV (h1)
Dry gas
C3
C4
Liquid
Coke
0.03
2.80
84.01
12.47
0.69
0.21
3.81
83.76
11.37
0.85
0.45
4.64
82.81
10.98
1.12
0.63
6.12
81.91
10.06
1.28
1.29
8.22
79.70
9.43
1.36
4.62
15.86
68.47
9.16
1.89
12.58
26.64
48.66
8.84
3.28
Dry gas
C3
C4
Liquid
Coke
14.05
28.39
45.10
8.85
3.61
12.58
26.64
48.66
8.84
3.28
11.62
26.07
50.16
9.06
3.09
11.34
25.38
51.24
9.24
2.80
10.97
24.84
52.06
9.45
2.68
220
0.5
25
20
700 oC
ethene
propene
aromatics
15
10
0.4
WHSV: 3 h-1
0.3
0.2
0.1
0.0
10
400
450
500
550
600
650
700
RCA
3
C4o
C8o
1
2
C4=
6
naphthenes
WHSV: 3 h-1
C12=
2
oligomers
700 oC
C8=
RCA
C2=, C3=
coke
aromatics
Fig. 5. Reaction network of C4 fraction catalytic conversion (1 hydrogen transfer reaction, 2 polymerization reaction, 3 cracking reaction, 4 aromatization reaction,
5 cyclization reaction, 6 condensation reaction).
400
450
500
550
600
650
700
5. Conclusions
Butenes were easier to convert than butanes on commercial FCC
equilibrium catalysts. High reaction temperature and low WHSV favored
the production of ethene, propene, and aromatics. Butenes initially
underwent dimerization into large olens, which then underwent cracking to produce propene and aromatization to produce aromatics. A yield
ratio of dry gas to C3 was proposed to describe the relative function of
thermal cracking to catalytic cracking. This ratio increased with increased reaction temperature, and the importance of thermal cracking
increased at high temperatures. A yield ratio of dry gas plus C3 to aromatics (RCA) was proposed to describe the relative function of cracking
reaction to aromatization reaction. RCA increased with increased reaction
temperature and decreased with increased WHSV. High reaction temperature and low WHSV favor cracking reaction.
Acknowledgment
Financial support was provided by the National Basic Research
Program of China (973 Program, No. 2012CB215001), the Program for
New Century Excellent Talents in University of China (NCET-12-0970),
and the Science Foundation of China University of Petroleum, Beijing
(Nos. KYJJ2012-03-23 and KYJJ2012-03-25).
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