The effect of doping and steam treatment on the catalytic activities of nano-scale H-ZSM-5 in the methanol to gasoline reaction

doi:10.1007/s11705-017-1654-y

Front. Chem. Sci. Eng.

2017, Vol. 11

Issue (4) : 564-574 https://doi.org/10.1007/s11705-017-1654-y

RESEARCH ARTICLE

The effect of doping and steam treatment on the catalytic activities of nano-scale H-ZSM-5 in the methanol to gasoline reaction

Baodong Song¹, Yongqiang Li¹, Gang Cao², Zhenhai Sun¹, Xu Han³(

)

¹. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
². Nankai University Catalyst Co. Ltd, Tianjin 300072, China
³. Key Lab of Indoor Air Environment Quality Control, School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China

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Abstract

In the transformation of methanol to gasoline (MTG), the selectivity to gasoline and the aromatic content in the produced gasoline are important factors. The catalytic activities of steam-treated and non-steam-treated nano-scale H-ZSM-5 (NHZ5) catalysts impregnated with Ag(I), Zn(II) or P(V) have been investigated in a continuous flow fixed bed reactor. The NH₃-TPD results showed that after impregnation, the Ag/NHZ5, Zn/NHZ5 and P/NHZ5 catalysts contained comparatively more strong, medium-strong and weak acid sites, respectively. Treatment with steam decreased the number of acid sites in all the catalysts, but the pore volumes in the catalysts were larger which improved carbon deposition resistance resulting in prolonged lifetimes. After 6 h of MTG reaction, the selectivity to gasoline for the steam-treated catalysts, $A g H 2 O / N H Z 5$ , $Z n H 2 O / N H Z 5$ and $P H 2 O / N H Z 5$ were 70.5, 68.4 and 68.7 wt-%, respectively, whereas their respective aromatic contents in the produced gasoline were 61.9, 55.4 and 39.0 wt-%. Thus $P H 2 O / N H Z 5$ is the most promising catalyst for MTG applications which can meet the China IV gasoline standard that the amount of aromatics in gasoline should be less than 48 wt-%.

Keywords MTG nano-scale H-ZSM-5 steam treatment gasoline selectivity to gasoline

Corresponding Author(s): Xu Han

Just Accepted Date: 14 April 2017 Online First Date: 19 July 2017 Issue Date: 06 November 2017

Cite this article:

Baodong Song,Yongqiang Li,Gang Cao, et al. The effect of doping and steam treatment on the catalytic activities of nano-scale H-ZSM-5 in the methanol to gasoline reaction[J]. Front. Chem. Sci. Eng., 2017, 11(4): 564-574.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1654-y
https://academic.hep.com.cn/fcse/EN/Y2017/V11/I4/564

Fig.1 Scheme 1MTG reaction unit 1, 2: Flow rate controller; 3: Temperature controller

Fig.2 SEM images of (a) HZSM-5, (b) Zn/NHZ5, (c) P/NHZ5 and (d) Ag/NHZ5, as well as EDX analysis of (e) Zn/NHZ5, (f) P/NHZ5 and (g) Ag/NHZ5

Fig.3 The XRD patterns of NHZ5 and the modified samples

Tab.1 Characterization of the pristine and the modified NHZ5

Fig.4 NH₃-TPD patterns of NHZ5 and modified samples

Fig.5 Methanol conversions over NHZ5 and the doped NHZ5 catalysts as a function of time. Reaction conditions: WHSV, 6.7 h^?¹; temperature, 673 K; reaction pressure, 0.1 MPa; catalyst loading, 10 g

Tab.2 Product distribution over the pristine and the modified NHZ5^a)

Fig.6 Scheme 2Reaction mechanism of MTG

Fig.7 The selectivity to aromatics with time over NHZ5 and the doped NHZ5. Reaction conditions: WHSV, 6.7 h^?¹; temperature, 673 K; reaction pressure, 0.1 MPa; catalyst loading 10 g

Fig.8 The selectivity to gasoline with time over NHZ5 and the doped NHZ5. Reaction conditions: WHSV, 6.7 h^?¹; temperature, 673 K; reaction pressure, 0.1 MPa; catalyst loading 10 g

Fig.9 Methanol conversion with time over the pristine and the steam modified NHZ5 catalyst. Reaction conditions: WHSV, 6.7 h^?¹; temperature, 673 K; reaction pressure, 0.1 MPa; catalyst loading, 10 g

Samples	Yields /%	SOA /wt-%	SOG /wt-%	COA /wt-%
Samples	CH₄	SOA /wt-%	SOG /wt-%	COA /wt-%	C₂-C₄	C₅₊	C₆H₆	C₇H₈	C₈H₁₀	C₉H₁₂	C₁₀H₁₄
NHZ5	2.1	38.0	28.4	0.4	3.9	13.5	9.4	5.6	32.8	61.2	50.7
$A g H 2 O / N H Z 5$	2.2	26.9	25.7	0.9	5.2	11.2	18.7	7.8	44.8	70.5	61.9
$Z n H 2 O / N H Z 5$	2.0	29.3	29.5	0.7	5.7	14.3	11.3	6.9	38.9	68.4	55.4
$P H 2 O / N H Z 5$	1.1	29.2	41.2	0.4	3.2	11.0	8.7	4.2	27.5	68.7	39.0

Tab.3 Product distribution over the pristine and the steam modified NHZ5^a)

Fig.10 The selectivity to aromatics with time over NHZ5 and the steamed NHZ5. Reaction conditions: WHSV, 6.7 h^?¹; temperature, 673 K; reaction pressure, 0.1 MPa; catalyst loading, 10 g

Fig.11 The selectivity to gasoline with time over NHZ5 and the steamed NHZ5. Reaction conditions: WHSV, 6.7 h^?¹; temperature, 673 K; reaction pressure, 0.1 MPa; catalyst loading, 10 g

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