Conversion of Methanol to Hydrocarbons over Phosphorus-modified ZSM-5/ZSM-11 Intergrowth Zeolites

Peng, Li; Zhang, Weiping; Han, Xiuwen; Bao, Xinhe

doi:10.1007/s10562-009-0214-6

Cited by 58 publications

(48 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Similar results were reported in the literature (Hodala et al, 2014;Takahashi et al, 2012;Lu and Liu, 2011;Song et al, 2010;Vu et al, 2010;Li et al, 2010;Ramesh et al, 2009;Zhao et al, 2007;Lercher and Rumplmayr, 1986). The addition of P up to 1.2 wt.…”

Section: Catalyst Characterizationsupporting

confidence: 91%

“…Phosphorus addition to HZSM-5 caused a decrease in the total acid site density. It also appears that the decrease in strong acid sites density was greater than that observed for weak acid sites, as reported previously (Takahashi et al, 2012;Lu and Liu, 2011;Ramesh et al, 2009;Song et al, 2010;Vu et al, 2010;Li et al, 2010;Zhao et al, 2007;Lercher and Rumplmayr, 1986).…”

Section: Catalyst Characterizationsupporting

confidence: 85%

See 1 more Smart Citation

Synthesis of Propylene From Ethanol Using Phosphorus-Modified HZSM-5

Costa

Silva

2016

Braz. J. Chem. Eng.

View full text Add to dashboard Cite

-Effects of phosphorus addition to HZSM-5 on ethanol conversion to propylene were evaluated. Catalysts were characterized by XRF, XRD, nitrogen adsorption, 27Al and 31 P MAS NMR, n-propylamine and ammonia TPD. Increasing P content decreased the strength and density of acid total sites. Ethanol dehydration was carried out in a fixed bed reactor operating at atmospheric pressure. Conversion was around 100% for all catalysts. 1.2 wt% of P catalyst showed the highest propylene yield, and was used to evaluate temperature and ethanol partial pressure effects on the product distribution. The highest propylene accumulated productivity was obtained for an ethanol partial pressure of 0.4 atm. Propylene formation was favored in the temperature range 475-500 °C. Significant changes in the product distribution as a function of time on stream were observed at higher temperatures, suggesting stronger catalyst deactivation. The ethylene yield decreased up to 500 °C, rising significantly at 550 °C, possibly due to heavier product cracking reactions.

show abstract

Section: Catalyst Characterizationsupporting

confidence: 91%

Section: Catalyst Characterizationsupporting

confidence: 85%

Synthesis of Propylene From Ethanol Using Phosphorus-Modified HZSM-5

Costa

Silva

2016

Braz. J. Chem. Eng.

View full text Add to dashboard Cite

show abstract

“…5,6 The selectivity towards propylene is increased even more with the introduction of phosphorus. [6][7][8][9][10] Usually, the improved selectivity towards propylene is attributed to the decrease in the acid site strength that is so often observed in phosphated H-ZSM-5, although steric factors have also been suggested to be responsible. [6][7][8][9][10][11][12] Even though there is still some debate on the effect of acid site strength on the MTO product distribution, the promoting effect of phosphorus on the hydrothermal stability of H-ZSM-5 is undisputed.…”

Section: Introductionmentioning

confidence: 99%

“…[6][7][8][9][10] Usually, the improved selectivity towards propylene is attributed to the decrease in the acid site strength that is so often observed in phosphated H-ZSM-5, although steric factors have also been suggested to be responsible. [6][7][8][9][10][11][12] Even though there is still some debate on the effect of acid site strength on the MTO product distribution, the promoting effect of phosphorus on the hydrothermal stability of H-ZSM-5 is undisputed. 4,9,[13][14][15][16][17][18][19][20][21][22][23][24][25] Zeolite H-ZSM-5 catalysts that contain phosphorus are more stable under hydrothermal conditions i.e.…”

Section: Introductionmentioning

confidence: 99%

Local silico-aluminophosphate interfaces within phosphated H-ZSM-5 zeolites

Bij

Weckhuysen

2014

Phys. Chem. Chem. Phys.

127

View full text Add to dashboard Cite

In order to elucidate phosphorus-zeolite H-ZSM-5 interactions, a variety of phosphorus-modified zeolite H-ZSM-5 materials were studied in a multi-spectroscopic manner. By deploying single pulse 27 Al, 31 P MAS NMR, 2D heteronuclear 27 Al-31 P correlation (HETCOR), 27 Al MQ MAS NMR spectroscopy, TPD of pyridine monitored by FT-IR spectroscopy, and Scanning Transmission X-ray Microscopy (STXM) the interplay and influence of acidity, thermal treatment and phosphorus on the structure and acidity of H-ZSM-5 were established. It was found that while acid treatment did not affect the zeolite structure, thermal treatment leads to the breaking of Si-OH-Al bonds, a decrease in the strong acid site number and the formation of terminal Al-OH groups. No extra-framework aluminium species was observed. Phosphorus precursors interact with the zeolitic framework through hydrogen bonds and physical coordination, as phosphorus species can be simply washed out with hot water. After phosphatation and thermal treatment two effects occur simultaneously, namely (i) phosphorus species transform into water insoluble condensed poly-phosphoric acid and (ii) phosphoric acid binds irreversibly to the terminal Al-OH groups of partially dislodged four-coordinated framework aluminium, forming local silico-aluminophosphate interfaces.These interfaces are potentially the promoters of hydrothermal stability in phosphated zeolite H-ZSM-5.

show abstract

“…The introduction of phosphorus to modify ZSM-5 is one of the ways to improve the propylene selectivity and reduce the aromatics product in the expense of the decrease of acidity [103][104][105][106], and with the washing of hot water, additional Brønsted acidity can be recovered [107,108]. Since it was firstly reported, the phosphorus modification of ZSM-5 has been applied to different reactions such as fluid catalytic cracking, toluene alkylation, and also methanol to hydrocarbons [108].…”

Section: 6phosphorus Modified Zsm-5mentioning

confidence: 99%

New micro and mesoporous materials for the reaction of methanol to olefins

Li¹

View full text Add to dashboard Cite

i ResumenLa transformación de metanol en olefinas empleando catalizadores ha atraí do el interés de la comunidad cientí fica debido a las amplias reservas de gas natural. El metanol se obtiene a partir del gas natural a través del gas de sí ntesis y también a partir de biomasa mediante gasificación, por lo que representa una alternativa frente a otras fuentes fósiles de energí a como el petróleo y el carbón. En esta tesis se han estudiado nuevos materiales catalí ticos para la reacción de metanol en olefinas optimizando las propiedades de los que actualmente se emplean de manera comercial y proponiendo nuevos materiales alternativos. Los catalizadores empleados actualmente están basados en zeolitas que son materiales microporosos de alta área especí fica pero presentan como limitaciones una vida corta antes de la desactivación por coque, o una baja estabilidad frente a la presencia de agua en el medio de reacción. El aumento del área especí fica a través de la disminución del tamaño de cristal o de la mesoporosidad mejorará las propiedades de difusión del catalizador.El silicoaluminofosfato SAPO-34 es empleado comercialmente en la actualidad.En esta tesis se ha optimizado la sí ntesis de este material disminuyendo drásticamente el tamaño de cristal y mejorando la estabilidad frente a la humedad ambiente. La disminución del tamaño de cristal ha aumentado la vida del catalizador frente a la deposición de coque y ha permitido relacionar la selectividad a productos con la distribución de silicio en la partí cula, distribución que es variable al contacto con la humedad ambiente. La estabilidad frente a la humedad ha sido mejorada mediante el tratamiento con vapor post-sí ntesis y también se ha estudiado el efecto de la eliminación del agente orgánico director de estructura en atmósfera reductora de hidrógeno y agua. De esta manera se han sintetizado muestras con mayor tiempo de vida en la reacción de metanol. El efecto de la reducción del tamaño de cristal se ha estudiado también para la zeolita SSZ-13, isomorfa con SAPO-34, mediante la adición de agentes surfactantes durante la sí ntesis y también se ha probado cómo esta reducción de tamaño produce el aumento el tiempo de vida del catalizador.ii Por último se ha optimizado el tiempo de vida y la estabilidad hidrotérmica de la zeolita ZSM-5, también usada comercialmente como componente activo del catalizador del proceso de metanol a propileno. Se ha estudiado el efecto del aumento de la mesoporosidad mediante tratamientos básicos/ácidos en las propiedades catalí ticas y se ha comprobado cómo la mesoporosidad aumenta el tiempo de vida pero afecta a la estabilidad hidrotérmica del catalizador. En la parte final se ha optimizado la estabilidad hidrotérmica de ZSM-5 mesoporosa mediante la adición de fósforo. El estudio ha permitido comprobar que la actividad del catalizador basado el ZSM-5 mesoporosa se puede preservar mediante la mejora de la estabilidad hidrotérmica, incluyendo fósforo en la composición del catalizador.iii Resum La transformació de metanol en olefines ...

show abstract

Conversion of Methanol to Hydrocarbons over Phosphorus-modified ZSM-5/ZSM-11 Intergrowth Zeolites

Cited by 58 publications

References 58 publications

Synthesis of Propylene From Ethanol Using Phosphorus-Modified HZSM-5

Synthesis of Propylene From Ethanol Using Phosphorus-Modified HZSM-5

Local silico-aluminophosphate interfaces within phosphated H-ZSM-5 zeolites

New micro and mesoporous materials for the reaction of methanol to olefins

Contact Info

Product

Resources

About