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 Uni
V
ersity of Science and Technology,Shanghai 200237, People’s Republic of China
Deep removal of trace olefins from aromatics using mesoporous materials and modified mesoporous materialswas studied with regard to the removal of trace olefins from aromatic hydrocarbons. The mesoporous materialsand the modified mesoporous molecular sieve materials were characterized by X-ray diffraction and Fouriertransform 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 resultshowed that the mesoporous materials that had surface areas larger than 300 m
2
/g and modified with AlCl
3
were best, with regard to the effect on the removal of olefins from aromatics. The FT-IR results showed thatthe modifier could increase the concentration of weak Lewis acid of mesoporous materials and obviouslyenhance the effect of removing olefins and prolonging the reaction time.
1. Introduction
In petroleum processing, aromatic streams are derived fromprocesses such as naphtha reforming and thermal cracking.These aromatic streams also contain undesirable olefin impuritiesthat are very harmful to the followed technological processesand applications of aromatics. Therefore, the impurities mustbe removed with suitable treatment technologies.
1
Two pro-cesses have been discovered for the removal of trace olefinsfrom aromatics (i.e., particulate clay treatment and catalytichydrogenation treatment). However, these two processes havesome drawbacks; for example, the clays have very limitedlifetimes.A 450 000 t/a PX device (Sinopec Zhenhai Refining andChemical Company) was employed, using the Eluxyl technologyof the IFP Company, France. Simulated moving bed technologywas used to separate and produce PX with a highly selectivepatent adsorbent (SPX3000). The bromine index (BI) was
∼
600
-
1100. To protect the adsorbent, clay was used to removetrace olefins from the aromatic hydrocarbons before the aromatichydrocarbons enter into the adsorption tower. However, the clayhas a very limited lifetime. With increasing environmentalawareness and demands on the process of healthy economicdevelopment, some type of catalyst that protects the environmentand improves economic efficiency must be applied in this field.
2
Research at East China University of Science and Technologyhas developed a series of mesoporous material catalysts, andwe have conducted commercial sidestream tests beside theindustry clay tower of the Zhenhai Refining and ChemicalCompany. The test provides a basis for future industrialization.
2. Experimental Section2.1. Materials.
The aromatic hydrocarbons were obtainedfrom the bottom of the naphtha reforming column at the SinopecZhenhai Refining and Chemical Company. The BI was
∼
1400.In the commercial sidestream tests, the aromatic hydrocarbonswere obtained from the bottom of the naphtha reforming columnat the Shanghai Petrochemical Co., Ltd. (the BI is
∼
700
-
1100,and the components are shown in Table 1).Catalyst A had mesoporous material with surface areas of
>
300 m
2
/g; catalyst C had mesoporous material with surfaceareas of
>
200 m
2
/g; catalyst B was catalyst A that had beenmodified by AlCl
3
; and catalyst D was catalyst C that had beenmodified by AlCl
3
.
2.2. Catalysts Preparation.
The mesoporous materials anddifferent zeolites were mixed with adhesive
γ
-Al
2
O
3
, blendedwith the proper amount of a 10% HNO
3
solution, which wereadded to modify/alter the AlCl
3
content, and the materials weresqueezed into the form of strips to make a series of modifiedcatalysts. These were calcined in a oven, in an air atmosphereat 723 K for 3 h, crushed, and screened to 20
-
40 mesh foruse.
2.3. Catalytic Tests in Laboratory.
The catalytic activitytests were performed in a fixed-bed tubular microreactor thatwas equipped with flow controllers and a heating system. Twomilliliters of the synthesized catalyst was placed between twoquartz sands (40
-
60 mesh) and inserted into the reactor. Thereaction was carried out under the following conditions: reactiontemperature, 448 K; reaction pressure, 1 MPa; and weight hourlyspace velocity (WHSV), 30 h
-
1
. Inlet and effluent liquids toand from the reactor were analyzed using a BI analyzer. In thecommercial sidestream test, the reaction was heated by steamand the temperature was
∼
433
-
441 K. The reaction pressurewas 2.0
-
2.1 MPa, and the volume space velocity was 2 h
-
1
.
2.4. Commercial Sidestream Tests: Process Flow andCatalyst Loading.
Figure 1 shows the flow scheme of thecommercial sidestream test process. The commercial sidestreamtests were conducted beside the industrial clay tower. Aromaticsenter into the reactor from the top, and flow out from the bottomof the reactor after being treated in the reactor. The operatingtemperature of the reactor was controlled by regulating the steam
* To whom correspondence should be addressed. Tel.: 021-64252274. E-mail: yyshi@ecust.edu.cn.
Table 1. Aromatic Hydrocarbon Components
component content (wt %)nonaromatics
<
1toluene
<
0.5ethylbenzene 10
p
-xylene 10
m
-xylene 23
o
-xylene 12C9 aromatics 30C9
+
aromatics 14
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2009,
48,
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10.1021/ie901062c CCC: $40.75
©
2009 American Chemical SocietyPublished on Web 09/28/2009
flow. The streams also enter into the reactor from the top of reactor. The samples were collected from the bottom of thereactor after a heat exchange.Figure 2 shows the packing structure of different catalysts.The upper and lower parts of the fixed-bed reactor were filledwith ceramic balls of different sizes. Catalysts were loaded inthe center of the reactor. Different catalysts will be loaded eachtime in the reactor. The internal reactor was purged by nitrogenbefore loading.
2.5. Mesoporous Materials Activity Analysis: BromineIndex.
The bromine index (BI) is an indicator of the olefincontent. The BI is determined according to ASTM Standard D2710-92 and is a measure of the milligrams of bromineconsumed by 100 g of sample, under the given conditions.
2.6. Acidity Characterization.
The amount of acid, the aciddensity, and the acid variety were measured via Fouriertransform infrared (FT-IR) spectroscopy (Magna-IR550, NicoletCompany), using pyridine as the probe molecule. There are twovarieties of acid: one is a Brønsted acid (denoted as B), whosecharacteristic absorption peak is observed at 1540 cm
-
1
, andthe other is a Lewis acid (denoted as L), whose characteristicabsorption peaks are located at 1450 cm
-
1
. The pyridineadsorption, which is measured after desorption at 473 K, is thetotal acid sites (T). The pyridine adsorption, which is measuredafter desorption at 723 K, represents the strong acid sites (S).The difference represents the weak acid sites (W).
3. Results and Discussion3.1. Different Zeolites with Different Pore Size CatalyticActivity.
Figure 3 shows that mesoporous materials had the besteffect on the removal of olefins in aromatics and ZSM-5 zeolitewas the worst. USY and
zeolites have good initial activitybut very limited reaction time. The MCM-22 zeolite andmesoporous materials have longer reaction times; this phenom-enon is because the zeolites have different pore diameters. (Table2 gives the pore diameters of several zeolites and mesoporousmaterial.)
Figure 1.
Flow scheme of the commercial sidestream test process.
Figure 2.
Packing structure of different catalysts.
Figure 3.
Graph showing the conversion of different zeolites.
Table 2. Pore Diameter of Different Zeolites
zeolite pore diameter (nm)ZSM-5 0.5
-
0.6
0.75USY 0.9MCM-22 1.5mesoporous materials 3
-
5
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The alkylation reaction occurs in the channel of zeolites, andits reaction performance is related to the pore diameter of thecatalyst. Aromatic molecules are
∼
0.7 nm in diameter. Becauseof the pore size limitations, when the diameter of the aromaticmolecules was greater than the pore size of the zeolite, thearomatic molecules were refused access into the pore and cannotparticipate in the alkylation reaction, so olefins cannot removefrom aromatics. As can be seen in Table 2, the pore diameterof the mesoporous materials is
∼
3
-
5 nm, which is much greaterthan the size of the aromatic molecules, so the effect of removingolefins is better for mesoporous materials than several otherzeolites.
3.2. Influence of Modifications with AlCl
3
of Catalyst Aon Catalytic Activity.
Catalyst A was mesoporous material thathad a surface area of
>
300 m
2
/g, and catalyst B was catalyst Athat had been modified with AlCl
3
. These samples were alsodried 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 arehigher than those of catalyst A. Furthermore, the activityincreases when catalyst A is modified by AlCl
3
. The catalyticactivities of the samples were almost the same initial olefinconversions. However, after 4 h, the activity of catalyst Adecayed quickly. The conversions of olefins using sample Awere less than those observed using sample B. The olefinconversions of catalyst B remained above 50% for 9 h, whereasfor catalyst A, after only 5.5 h, the activity increased by 60%.These results demonstrated that the activity increases whencatalyst A was modified with AlCl
3
.
3.3. Influence of Modification with AlCl
3
of Catalyst Con Catalytic Activity.
Catalyst C was mesoporous material thathad a surface area of
>
200 m
2
/g, and catalyst D was catalyst Cthat had been modified with AlCl
3
. These samples were alsodried 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 werethe same initial olefin conversions. However, after 2 h, theactivity of catalyst C decayed quickly. The olefin conversionsof sample C was less than that of sample D. As can be seen inthis figure, the catalytic activity of sample C has been improvedby modification with AlCl
3
.
3.4. XRD Analyses of Four Samples.
Figure 6 shows XRDpatterns of four catalysts. The XRD analyses indicate that thereis no peak of impurities or other obvious changes for the catalystA samples, indicating that the framework structure of catalystA was barely damaged and well-maintained after AlCl
3
modi-fication. There is no characteristic peak of AlCl
3
, because it ispresent in a small quantity and highly dispersed.
3
AlCl
3
wasnot detected in the XRD spectra of the catalyst D sample. Theresults also showed that the catalyst D sample presented peaks
Figure 4.
Plot showing the influence of modification of catalyst A withAlCl
3
on catalytic activity.
Figure 5.
Plot showing the influence of modification of catalyst C withAlCl
3
on catalytic activity.
Figure 6.
XRD patterns of four catalysts (A, B, C, and D).
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that were similar to those of the catalyst C sample, whichdemonstrated that the crystal structure of catalyst D was sameas that of catalyst C. The mesoporous materials have largesurface areas and a very small amount of AlCl
3
, so that AlCl
3
can be highly dispersed on the surface of catalyst C mesoporousmaterials.
3.5. Pyridine FT-IR Spectra of Four Samples.
To inves-tigate the number of the surface acidic sites, FT-IR spectrafor the adsorption of pyridine at 473 and 723 K were obtained.The spectrum displayed many bands in the wavenumbersin the range of 1400
-
1600 cm
-
1
, which attributed to theinteraction of pyridine with Lewis (L) and Brønsted (B) acidsites on the sample surfaces. As shown in Figure 7, the spectrapresent bands of adsorption at 1450 and 1490 cm
-
1
, which istypical of adsorbed pyridine.
4
There is no band that is observedat 1540 cm
-
1
, as can be seen in Figure 7, so the amount of total B acid could not be calculated. We mainly observe theband at
∼
1450 cm
-
1
, which is due to the 19b
ν
(C
-
C) vibrationof pyridine adsorbed at Lewis acid sites.
5
It was shown that the amount of total L acid sites, strong Lacid sites, and weak L acid sites all increased. However,compared to the strong L acid sites, the number of weak L acidsites increases fast. As we can see from four samples, thechanges in the total L acid sites were influenced mainly by theweak L acid sites. Therefore, increasing the amount of the weak L acid sites contributed to the increase in the activity of thecatalyst, thus improving the capacity of removing trace olefinsfrom aromatics.
3.6. Commercial Sidestream Test Analyses.
Figure 8 showsconversion of aromatics of four catalyst samples and Lin-anclay. The conversions of olefins with Lin-an clay remainedabove 50% for four days. The reaction times of the four samples
Figure 7.
FT-IR spectra of four catalysts (A, B, C, and D) are compared at 473 and 723 K.
Figure 8.
Plot showing the conversion of aromatics of four samples (andLin-an clay) at a commercial sidestream test.
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