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Ind. Eng. Chem. Res.

2009, 48, 1035910363 10359

Study on Several Mesoporous Materials Catalysts Applied to the Removal of


Trace Olefins from Aromatics and Commercial Sidestream Tests
Chang-wei Chen, Wen-juan Wu, Xian-song Zeng, Zhen-hong Jiang, and Li Shi*
The State Key Laboratory of Chemical Engineering, East China UniVersity of Science and Technology,
Shanghai 200237, Peoples Republic of China

Deep removal of trace olefins from aromatics using mesoporous materials and modified mesoporous materials
was studied with regard to the removal of trace olefins from aromatic hydrocarbons. The mesoporous materials
and the modified mesoporous molecular sieve materials were characterized by X-ray diffraction and Fourier
transform infrared (FT-IR) spectroscopy. Under the commercial sidestream test, the effects of four types of
mesoporous materials, with regard to the removal of olefins from the aromatics, were evaluated. The result
showed that the mesoporous materials that had surface areas larger than 300 m2/g and modified with AlCl3
were best, with regard to the effect on the removal of olefins from aromatics. The FT-IR results showed that
the modifier could increase the concentration of weak Lewis acid of mesoporous materials and obviously
enhance the effect of removing olefins and prolonging the reaction time.

1. Introduction Catalyst A had mesoporous material with surface areas of


>300 m2/g; catalyst C had mesoporous material with surface
In petroleum processing, aromatic streams are derived from areas of >200 m2/g; catalyst B was catalyst A that had been
processes such as naphtha reforming and thermal cracking. modified by AlCl3; and catalyst D was catalyst C that had been
These aromatic streams also contain undesirable olefin impurities modified by AlCl3.
that are very harmful to the followed technological processes 2.2. Catalysts Preparation. The mesoporous materials and
and applications of aromatics. Therefore, the impurities must different zeolites were mixed with adhesive -Al2O3, blended
be removed with suitable treatment technologies.1 Two pro- with the proper amount of a 10% HNO3 solution, which were
cesses have been discovered for the removal of trace olefins added to modify/alter the AlCl3 content, and the materials were
from aromatics (i.e., particulate clay treatment and catalytic squeezed into the form of strips to make a series of modified
hydrogenation treatment). However, these two processes have catalysts. These were calcined in a oven, in an air atmosphere
some drawbacks; for example, the clays have very limited at 723 K for 3 h, crushed, and screened to 20-40 mesh for
lifetimes. use.
A 450 000 t/a PX device (Sinopec Zhenhai Refining and 2.3. Catalytic Tests in Laboratory. The catalytic activity
Chemical Company) was employed, using the Eluxyl technology tests were performed in a fixed-bed tubular microreactor that
of the IFP Company, France. Simulated moving bed technology was equipped with flow controllers and a heating system. Two
was used to separate and produce PX with a highly selective milliliters of the synthesized catalyst was placed between two
patent adsorbent (SPX3000). The bromine index (BI) was quartz sands (40-60 mesh) and inserted into the reactor. The
600-1100. To protect the adsorbent, clay was used to remove reaction was carried out under the following conditions: reaction
trace olefins from the aromatic hydrocarbons before the aromatic temperature, 448 K; reaction pressure, 1 MPa; and weight hourly
hydrocarbons enter into the adsorption tower. However, the clay space velocity (WHSV), 30 h-1. Inlet and effluent liquids to
has a very limited lifetime. With increasing environmental and from the reactor were analyzed using a BI analyzer. In the
awareness and demands on the process of healthy economic commercial sidestream test, the reaction was heated by steam
development, some type of catalyst that protects the environment and the temperature was 433-441 K. The reaction pressure
and improves economic efficiency must be applied in this field.2 was 2.0-2.1 MPa, and the volume space velocity was 2 h-1.
Research at East China University of Science and Technology 2.4. Commercial Sidestream Tests: Process Flow and
has developed a series of mesoporous material catalysts, and Catalyst Loading. Figure 1 shows the flow scheme of the
we have conducted commercial sidestream tests beside the commercial sidestream test process. The commercial sidestream
industry clay tower of the Zhenhai Refining and Chemical tests were conducted beside the industrial clay tower. Aromatics
Company. The test provides a basis for future industrialization. enter into the reactor from the top, and flow out from the bottom
of the reactor after being treated in the reactor. The operating
2. Experimental Section temperature of the reactor was controlled by regulating the steam
2.1. Materials. The aromatic hydrocarbons were obtained Table 1. Aromatic Hydrocarbon Components
from the bottom of the naphtha reforming column at the Sinopec component content (wt %)
Zhenhai Refining and Chemical Company. The BI was 1400.
In the commercial sidestream tests, the aromatic hydrocarbons nonaromatics <1
were obtained from the bottom of the naphtha reforming column toluene <0.5
ethylbenzene 10
at the Shanghai Petrochemical Co., Ltd. (the BI is 700-1100, p-xylene 10
and the components are shown in Table 1). m-xylene 23
o-xylene 12
* To whom correspondence should be addressed. Tel.: 021- C9 aromatics 30
64252274. E-mail: yyshi@ecust.edu.cn. C9+ aromatics 14

10.1021/ie901062c CCC: $40.75 2009 American Chemical Society


Published on Web 09/28/2009
10360 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009

Figure 1. Flow scheme of the commercial sidestream test process.

Figure 2. Packing structure of different catalysts.


flow. The streams also enter into the reactor from the top of
reactor. The samples were collected from the bottom of the
Figure 3. Graph showing the conversion of different zeolites.
reactor after a heat exchange.
Figure 2 shows the packing structure of different catalysts. Table 2. Pore Diameter of Different Zeolites
The upper and lower parts of the fixed-bed reactor were filled
zeolite pore diameter (nm)
with ceramic balls of different sizes. Catalysts were loaded in
the center of the reactor. Different catalysts will be loaded each ZSM-5 0.5-0.6
time in the reactor. The internal reactor was purged by nitrogen 0.75
USY 0.9
before loading. MCM-22 1.5
2.5. Mesoporous Materials Activity Analysis: Bromine mesoporous materials 3-5
Index. The bromine index (BI) is an indicator of the olefin after desorption at 723 K, represents the strong acid sites (S).
content. The BI is determined according to ASTM Standard D The difference represents the weak acid sites (W).
2710-92 and is a measure of the milligrams of bromine
consumed by 100 g of sample, under the given conditions.
3. Results and Discussion
2.6. Acidity Characterization. The amount of acid, the acid
density, and the acid variety were measured via Fourier 3.1. Different Zeolites with Different Pore Size Catalytic
transform infrared (FT-IR) spectroscopy (Magna-IR550, Nicolet Activity. Figure 3 shows that mesoporous materials had the best
Company), using pyridine as the probe molecule. There are two effect on the removal of olefins in aromatics and ZSM-5 zeolite
varieties of acid: one is a Brnsted acid (denoted as B), whose was the worst. USY and zeolites have good initial activity
characteristic absorption peak is observed at 1540 cm-1, and but very limited reaction time. The MCM-22 zeolite and
the other is a Lewis acid (denoted as L), whose characteristic mesoporous materials have longer reaction times; this phenom-
absorption peaks are located at 1450 cm-1. The pyridine enon is because the zeolites have different pore diameters. (Table
adsorption, which is measured after desorption at 473 K, is the 2 gives the pore diameters of several zeolites and mesoporous
total acid sites (T). The pyridine adsorption, which is measured material.)
Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10361
aromatic molecules were refused access into the pore and cannot
participate in the alkylation reaction, so olefins cannot remove
from aromatics. As can be seen in Table 2, the pore diameter
of the mesoporous materials is 3-5 nm, which is much greater
than the size of the aromatic molecules, so the effect of removing
olefins is better for mesoporous materials than several other
zeolites.
3.2. Influence of Modifications with AlCl3 of Catalyst A
on Catalytic Activity. Catalyst A was mesoporous material that
had a surface area of >300 m2/g, and catalyst B was catalyst A
that had been modified with AlCl3. These samples were also
dried at 393 K for 6 h and finally calcined at 823 K for 3 h.
The results are shown in Figure 4.
Figure 4 shows that the olefin conversions of catalyst B are
higher than those of catalyst A. Furthermore, the activity
increases when catalyst A is modified by AlCl3. The catalytic
activities of the samples were almost the same initial olefin
conversions. However, after 4 h, the activity of catalyst A
Figure 4. Plot showing the influence of modification of catalyst A with decayed quickly. The conversions of olefins using sample A
AlCl3 on catalytic activity. were less than those observed using sample B. The olefin
conversions of catalyst B remained above 50% for 9 h, whereas
for catalyst A, after only 5.5 h, the activity increased by 60%.
These results demonstrated that the activity increases when
catalyst A was modified with AlCl3.
3.3. Influence of Modification with AlCl3 of Catalyst C
on Catalytic Activity. Catalyst C was mesoporous material that
had a surface area of >200 m2/g, and catalyst D was catalyst C
that had been modified with AlCl3. These samples were also
dried at 393 K for 6 h and finally calcined at 823 K for 3 h.
The results are shown in Figure 5.
Figure 5 shows the catalytic activities of two samples were
the same initial olefin conversions. However, after 2 h, the
activity of catalyst C decayed quickly. The olefin conversions
of sample C was less than that of sample D. As can be seen in
this figure, the catalytic activity of sample C has been improved
by modification with AlCl3.
3.4. XRD Analyses of Four Samples. Figure 6 shows XRD
patterns of four catalysts. The XRD analyses indicate that there
Figure 5. Plot showing the influence of modification of catalyst C with
AlCl3 on catalytic activity.
is no peak of impurities or other obvious changes for the catalyst
A samples, indicating that the framework structure of catalyst
The alkylation reaction occurs in the channel of zeolites, and A was barely damaged and well-maintained after AlCl3 modi-
its reaction performance is related to the pore diameter of the fication. There is no characteristic peak of AlCl3, because it is
catalyst. Aromatic molecules are 0.7 nm in diameter. Because present in a small quantity and highly dispersed.3 AlCl3 was
of the pore size limitations, when the diameter of the aromatic not detected in the XRD spectra of the catalyst D sample. The
molecules was greater than the pore size of the zeolite, the results also showed that the catalyst D sample presented peaks

Figure 6. XRD patterns of four catalysts (A, B, C, and D).


10362 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009

Figure 7. FT-IR spectra of four catalysts (A, B, C, and D) are compared at 473 and 723 K.

that were similar to those of the catalyst C sample, which


demonstrated that the crystal structure of catalyst D was same
as that of catalyst C. The mesoporous materials have large
surface areas and a very small amount of AlCl3, so that AlCl3
can be highly dispersed on the surface of catalyst C mesoporous
materials.
3.5. Pyridine FT-IR Spectra of Four Samples. To inves-
tigate the number of the surface acidic sites, FT-IR spectra
for the adsorption of pyridine at 473 and 723 K were obtained.
The spectrum displayed many bands in the wavenumbers
in the range of 1400-1600 cm-1, which attributed to the
interaction of pyridine with Lewis (L) and Brnsted (B) acid
sites on the sample surfaces. As shown in Figure 7, the spectra
present bands of adsorption at 1450 and 1490 cm-1, which is
typical of adsorbed pyridine.4 There is no band that is observed
at 1540 cm-1, as can be seen in Figure 7, so the amount of
total B acid could not be calculated. We mainly observe the
band at 1450 cm-1, which is due to the 19b (C-C) vibration
of pyridine adsorbed at Lewis acid sites.5 Figure 8. Plot showing the conversion of aromatics of four samples (and
It was shown that the amount of total L acid sites, strong L Lin-an clay) at a commercial sidestream test.
acid sites, and weak L acid sites all increased. However, catalyst, thus improving the capacity of removing trace olefins
compared to the strong L acid sites, the number of weak L acid from aromatics.
sites increases fast. As we can see from four samples, the 3.6. Commercial Sidestream Test Analyses. Figure 8 shows
changes in the total L acid sites were influenced mainly by the conversion of aromatics of four catalyst samples and Lin-an
weak L acid sites. Therefore, increasing the amount of the weak clay. The conversions of olefins with Lin-an clay remained
L acid sites contributed to the increase in the activity of the above 50% for four days. The reaction times of the four samples
Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10363
a
Table 3. Acidic Properties of Four Samples improved, compared to that of Lin-an clay. The result showed
Acidity (10-4mol/g) that catalyst B mesoporous material was the best, with regard
sample total L acid sites strong L acid sites weak L acid sites
to the effective removal of olefins in aromatics, and catalyst C
was the worst.
A 6.21 5.14 1.07 (4) The FT-IR analyses of the four catalyst samples showed
B 21.90 14.34 7.56 that the amount of total L acid sites, strong L acid sites, and
C 2.44 0.86 1.58
D 5.64 1.32 4.32 weak L acid sites all increased, especially that of weak L acid
a
sites. Thus, the activity of the catalysts and the capacity of
The term L acid denotes a Lewis acid.
removing trace olefins from aromatics have improved.
are all longer than that of Lin-an clay. The evaluation showed
that catalyst B has the best reaction time for 18 days and catalyst Literature Cited
C had the worst reaction time for 11 days. Compared to Lin-an
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Microporous Mesoporous Mater. 2006, 92, 117128.
(1) With regard to the physical and chemical properties of (5) Pranjal, K.; Narendra, M.; Gupta, R. K. Synergistic role of acid sites
zeolites, the pore size and surface acid strength are the most in the Ce-enhanced activity of meso-porous Ce-Al-MCM-41 catalysts in
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(2) Through modification, the activity and capacity of
removing trace olefins from the aromatics of mesoporous ReceiVed for reView July 6, 2009
materials have greatly improved. ReVised manuscript receiVed September 1, 2009
Accepted September 2, 2009
(3) The commercial sidestream test showed that the lifetime
of the four catalyst samples (A, B, C, and D) have greatly IE901062C