Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Hejin Tangbo1 ,
Qiuying Wang2 ,
Shouhe Xiang1
1. Institute of New Catalytic Materials, Department of Material Chemistry, Nankai University, Tianjin, 300071, China
2. Catalytic Factory, Nankai University, Tianjin, 300071, China
[Manuscript received July 12, 2002; revised November 4, 2002]
Abstract: Physicochemical and catalytic properties of phosphorus and boron modified HZSM-5 zeolites
treated with 100% steam at 673 K were investigated. The acidity and distribution of acidic sites were studied by infrared spectroscopy using pyridine as probe molecule and temperature programmed desorption
(TPD) of ammonia. The structure of the samples was characterized by XRD, and the textural properties
of the catalysts were determined by nitrogen isothermal adsorption-desorption measurements and scanning
electron microscopy (SEM). The XRD results show that the modified samples have no novel crystalline
phase, indicating a high dispersion of phosphorus and boron species. After treatment, the microporous
volume and surface area of the samples markedly decrease, implying the blockage of the channel. The nitrogen adsorption-desorption measurements suggest that the isothermal type of all samples is a combination
of isothermal type I and IV, and all hysteresis loops resemble the H4-type in the IUPAC classification.
The total acidity of the modified samples, determined by pyridine adsorption IR and TPD of ammonia,
decreases in contrast to that of the parent HZSM-5. The conversion of n-heptane over P and B steammodified HZSM-5 is higher than that of P and B-modified HZSM-5 zeolites but lower than that of the
parent HZSM-5.
Key words: HZSM-5 zeolite, steam treatment, phosphorus, boron, secondary pore, texture, cracking
activity
1. Introduction
57
Micropore area
Mesopore area
Micropore volume
Mesopore volume
(m2 /g)
(m2 /g)
(m2 /g)
(cm3 /g)
(cm3 /g)
Parent 50
388.5
303.1
85.4
0.1209
0.0429
P501
318.9
231.2
87.7
0.0940
0.0532
P5014
324.1
226.6
97.5
0.0925
0.0740
Sample
B501
323.3
251.3
72.0
0.1016
0.0324
B5014
340.2
233.7
106.5
0.0958
0.0731
58
Renqing L
u et al./ Journal of Natural Gas Chemistry Vol. 12 No. 1 2003
Ratio
TPD (mmol/g)
Parent 50
1.643
0.79
P501
3.910
0.71
P5014
3.211
0.68
B501
1.321
0.60
B5014
1.144
0.54
59
60
Renqing L
u et al./ Journal of Natural Gas Chemistry Vol. 12 No. 1 2003
lite [27]. P501 has few cracks or faults, and this may
be because of the stronger acidity of H3 PO4 than that
of H3 BO3 . This clarified that the mesoporous volume
of P501 is higher than that of B501 and the heptane
cracking activity of P501 is higher than that of B501.
Figure 4. SEM pictures of all samples: (a) parent, (b) enlarged parent, (c) P501, (d) P5014, (e) B501, (f )
B5014
61
C1 -C2
C3
C=
3
C4
C=
4
C+
5
11.3
31.5
8.0
16.2
4.6
28.4
Conversion (%)
100
P501
10.9
30.5
5.7
17.3
4.9
30.7
93
P5014
12.5
36.5
6.1
17.9
4.2
22.9
94
B501
11.3
31.0
4.8
19.0
7.6
26.3
59.2
B5014
9.9
32.5
8.5
13.4
3.7
32.0
100
4. Conclusions
References
The BET surface area, microporous area and microprous volume of modified samples decreased pronouncedly in contrast to Parent50. Phosphorus and
boron species were highly dispersed over the HZSM5 (as suggested by XRD and SEM). The acidity of
treated samples (measured by FT-IR and TPD of ammonia) pronouncedly decreased. The isothermal type
of all samples is a complex of type I and IV, while
hysteresis loops belong to the H4 type. The heptane
cracking activity of a phosphorus or boron-modified
sample is lower than that of the parent zeolite. The
activity of steam-treated P5014 is higher than that
of only phosphorus-modified P501, while the activity
of steam-treated B5014 is remarkably enhanced compared to B501.
Acknowledgements
Financial support from Catalytic Key Laboratory
of China Petroleum and Natural Gas Group Corporation (University of Petroleum) was greatly appreciated. We thank the National Science Foundation
Committee for Grant NSFC 20233030.
62
Renqing L
u et al./ Journal of Natural Gas Chemistry Vol. 12 No. 1 2003