磷改性ZSM-5分子筛物化性质和裂解制乙烯性能的研究

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磷改性ZSM-5分子筛物化性质和裂解制乙烯性能的研究

柯明^a; 汪燮卿^b; 张凤美^b

^a State Key Laboratory of Heavy Oil Processing, University of Petroleum,
Beijing,102249,China
^b Research Institute of Petroleum Processing SINOPEC, Beijing,100083, China

收稿日期:1900-01-01 修回日期:1900-01-01 出版日期:2003-12-28 发布日期:2003-12-28
通讯作者: 柯明

Physicochemical Features of Phosphorus-Modified ZSM-5 Zeolite and Its Performance on
Catalytic Pyrolysis to Produce Ethylene

KE Ming^a; WANG Xieqing^b; ZHANG Fengmei^b

^a State Key Laboratory of Heavy Oil Processing, University of Petroleum,
Beijing,102249,China
^b Research Institute of Petroleum Processing SINOPEC, Beijing,100083, China

Received:1900-01-01 Revised:1900-01-01 Online:2003-12-28 Published:2003-12-28
Contact: KE Ming

摘要/Abstract

摘要： The physicochemical features of phosphorus-modified ZSM-5 zeolites (SiO2/Al2O3 molar ratio
is 25)were characterized by XRD(X-ray diffraction), BET(Brunauer, Emmett and Teller spcific
surface area measurement), NH3-TPD(ammonia temperature-programmed desorption) and MASNMR
(magic angle spinning nuclear magnetic resonance), and the performance on catalytic
pyrolysis to produce ethylene was investigated with a light hydrocarbon fixed bed micro-
reactor with n-octane as feed. The results show that the acid site density, acid intensity
and hydrothermal stability of ZSM-5 zeolite were improved by phosphorus modification. When
P2O5 content in ZSM-5 zeolite is higher than 2.5%, phosphorus modification can prevent ZSM
-5 zeolite crystal structure transformation from orthorhombic to monoclinic. In addition,
the dealumination of ZSM-5 zeolite framework was moderated by phosphorus modification under
high temperature hydrothermal treatment. The results of n-octane pyrolysis on phosphorus-
modified ZSM-5 zeolites show that ethylene yields of zeolites with different phosphorus
content are almost the same under the same n-octane conversion. However, the modified
zeolites with higher pyrolysis activity give lower yield of propene, butene and total
olefin than lower pyrolysis activity under the same n-octane conversion.

关键词: phosphorus-modified ZSM-5 zeolite;catalytic pyrolysis;ethylene;hydrothermal stability; magic angle spinning nuclear magnetic resonance

Abstract: The physicochemical features of phosphorus-modified ZSM-5 zeolites (SiO2/Al2O3 molar ratio
is 25)were characterized by XRD(X-ray diffraction), BET(Brunauer, Emmett and Teller spcific
surface area measurement), NH3-TPD(ammonia temperature-programmed desorption) and MASNMR
(magic angle spinning nuclear magnetic resonance), and the performance on catalytic
pyrolysis to produce ethylene was investigated with a light hydrocarbon fixed bed micro-
reactor with n-octane as feed. The results show that the acid site density, acid intensity
and hydrothermal stability of ZSM-5 zeolite were improved by phosphorus modification. When
P2O5 content in ZSM-5 zeolite is higher than 2.5%, phosphorus modification can prevent ZSM
-5 zeolite crystal structure transformation from orthorhombic to monoclinic. In addition,
the dealumination of ZSM-5 zeolite framework was moderated by phosphorus modification under
high temperature hydrothermal treatment. The results of n-octane pyrolysis on phosphorus-
modified ZSM-5 zeolites show that ethylene yields of zeolites with different phosphorus
content are almost the same under the same n-octane conversion. However, the modified
zeolites with higher pyrolysis activity give lower yield of propene, butene and total
olefin than lower pyrolysis activity under the same n-octane conversion.

Key words: phosphorus-modified ZSM-5 zeolite, catalytic pyrolysis, ethylene, hydrothermal stability, magic angle spinning nuclear magnetic resonance

柯明, 汪燮卿, 张凤美. 磷改性ZSM-5分子筛物化性质和裂解制乙烯性能的研究[J]. CIESC Journal.

KE Ming, WANG Xieqing, ZHANG Fengmei. Physicochemical Features of Phosphorus-Modified ZSM-5 Zeolite and Its Performance on
Catalytic Pyrolysis to Produce Ethylene [J]. .

参考文献

[1] Gao, C., He, M.Y., Dai, Y.Y., Zeolite Catalysis and Separation Technology, SINOPEC
Press, Beijing, 65-68 (1999).(in Chinese)
[2] Zhang, F.M., Shu, X.T., Shi, Zh. Ch., Wang, W.D., Qin,F.M., Wang, X.Q., "A pentasil-
type molecular sieve containing composition and its preparation method", CN 1211469A
(1998). (in Chinese)
[3] Zhang, F.M., Shu, X.T., Shi, Zh. Ch, Wang, W.D.,Qin, F.M., Wang, X.Q., "A pentasil-type
molecular sieve containing composition of more producing ethylene and propene", CN 1211470A
(1998). (in Chinese)
[4] He, M.Y., Yang, X.M., Shu, X.T., Luo, J.G., "Phosphorous containing zeolite having MFI
type structure", U S Pat.,5951963 (1999).
[5] Yang, X.M., Luo, J.G., "Effect of ZSM-5 zeolite modified with phosphorus oxide on
physicochemical features and shape selective catalytic performance", Petroleum Processing
and Petrochemicals, 32 (11), 48-51 (2001). (in Chinese)
[6] Wu, E.L., Lawton, S.H., Olson, D.H., Rohrman, A.C.Jr.,Kokotalilo, G.T., "ZSM-5-type
materials. Factors affecting crystal symmetry", J. Phys. Chem., 83 (21), 2777-2781(1979).
[7] Zhang, W.J., Yu, Q., Wei, G.X., Wang, Sh.J., Liu,Zh.Y., Lin, B.X., "Structural changes
of ZSM-5 molecular sieves after high temperature steam treatmeant", Acta Petrolei Sinica
(Petroleum Processing Section), 1 (1), 41-51 (1985). (in Chinese)
[8] Wang, Sh. Zh., Huang, N.G., "Study on phenomena of low pressure hysteresis in their
nitrogen adsorption of ZSM-5 zeolites", Petroleum Processing and Petrochemicals, 30 (4),50
-55 (1999). (in Chinese)
[9] Keading, W.W., Butter, S.A., "Production of chemical from methanol-Ⅰ. Low molecular
weight olefins", J. Catal., 61,155-164 (1980).
[10] Vinek, H., Rumplayr, G., Lercher, J.A., "Catalytic properties of postsynthesis
phosphorus-modified H-ZSM-5 zeolites", J. Catal., 115, 291-300 (1989).
[11] Vedrine, J.C., Auroux, A., Dejaifve, P., Ducarme, V.,Hoser, H., Zhou, S., "Catalytic
and physical properties of phosphorus-modified ZSM-5 zeolite", J. Catal., 73, 147-160
(1982).
[12] de Saldarriaga, L.S., Saldarriaga, C., Davis, M.E., "Investigations into the nature of
a silicoaluminophosphate with the faujasite structure", J. Am. Chem. Soc., 109, 2686-2691
(1987).
[13] Jahn, E., Muller, D., Becker, K., "Characterization of the local environment of Si
atoms incorporated into AlPO4-11by means of 27Al, 31p and 29Si MASn.m.r.
spectroscopy",Zeolites, 10 (3), 151-156 (1990).

磷改性ZSM-5分子筛物化性质和裂解制乙烯性能的研究

Physicochemical Features of Phosphorus-Modified ZSM-5 Zeolite and Its Performance on
Catalytic Pyrolysis to Produce Ethylene

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磷改性ZSM-5分子筛物化性质和裂解制乙烯性能的研究

Physicochemical Features of Phosphorus-Modified ZSM-5 Zeolite and Its Performance on Catalytic Pyrolysis to Produce Ethylene

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Physicochemical Features of Phosphorus-Modified ZSM-5 Zeolite and Its Performance on
Catalytic Pyrolysis to Produce Ethylene