hydroprocessing heterogeneous catalysts for aviation grade

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Hydroprocessing Heterogeneous Catalysts for Aviation Grade Green Diesel: Preparation & Characterization Abstract: Green diesel is mostly produced by a process to transform vegetable oil into biofuel through hydrocracking and hydrogenation. For the aviation grade biofuel, several requirements are needed, such as low freezing point and low viscosity, etc. The catalysts we study on are NiMo/g-Al 2 O 3 2,3 , Pd/C, and NiAg/SAPO-11 1,4,5 respectively. The fresh and spent catalysts were characterized by FT-IR, powder X-ray diffraction (XRD) and Scanning Electron Microscope (SEM) to understand the change of the catalyst after hydroprocessing. The NiAg/SAPO- 11 catalyst for hydrocracking and hydroisomerization is prepared by two different temperature subsequently after co-impregnation. From XRD patterns of fresh NiAg/SAPO-11 catalysts, we found that nickel presents in different forms. One is Ni(OH) 2 the other is NiO. We infer the reason that made NiAg/SAPO-11 invalid after catalyzed might be the leaching of nickel and the alkane remaining on the catalyst. Consider of that, we found a possibility of regeneration by reimpregnation after calcined the spent catalyst. Catalysts after Hydroprocessing: Preparation of NiAg/SAPO-11 Catalyst: Regenerate the Catalysts: Pd/C NiMo/g-Al 2 O 3 NiAg/SAPO-11 Scheme NiMo/g-Al 2 O 3 NiAg/SAPO-11 Ni and Ag precursors SAPO-11 180Dried 500Calcined 75% yield co-impregnation Different Ni XRD pattern 180 dried shows Ni(OH) 2 pattern 500 calcined shows NiO pattern 1. Calcine: burn the impurity off 2. Reimpregnation: reload the Ni 1.Liu, S.; Zhu, Q.; Guan, Q.; He, L.; Li, W. Bioresour. Technol. 2015, 183, 93. 2.Palcheva,R.; Kaluža, L.; Spojakina, A.; Jirátová, K.; Tyuliev,G. Chin. J. Catal. 2012, 33, 952. 3.Wang, Y.; Lin, H.; Zheng, Y. Catal. Sci. Technol. 2014, 4,109. 4.Chellappa, T.; José Fonseca Costa, M.; Nascimento, W.A.; Ferreira de Lima, L.; Almeida Bassan, Í.; Tavares, M.; Fernandes JR., V.J.; Menezes, A.; Guilherme Meira, L.; Telésforo Nóbrega de Medeiros, J.; Maribondo do Nascimento, R. Bull. Pol. Ac.: Tech. 2014, 62, 481. 5.Liu, Q.; Zuo, H.; Zhang, Q.; Wang, T.; Ma, L. Chin. J. Catal. 2014, 35, 748. Vegetable Oil Hydroprocessing by Catalysts Pd/C NiMo/g-Al 2 O 3 NiAg/SAPO-11 Green Diesel E-mail: [email protected] Chih-Chieh Chen, Chung-Hung Hsieh* Department of Chemistry, Tamkang University, Tamsui, New Taipei City, Taiwan Acknowledgments Referance Before and After catalyze IR XRD SEM IR XRD SEM SEM IR XRD Chung-Hung Hsieh Research Group Wei-Cheng Wang Research Group a lkane remained a lkane remained p attern of substrate: g-Al 2 O 3 a lkane remained a bsence of Ni pattern 180 dried NiAg /SAPO - 11 was chosen for the catalyze experiments almost identical pattern The color has changed after calcined Spent catalyst Fresh catalyst Black calcine Miller indices d(Å ) 2 q ( o ) (111) 2.34 38.4 (200) 2.03 44.6 (220) 1.43 64.9 (311) 1.22 78.0 Al pattern become sharp !

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Page 1: Hydroprocessing Heterogeneous Catalysts for Aviation Grade

Hydroprocessing Heterogeneous Catalysts for Aviation Grade Green Diesel: Preparation & Characterization

Abstract:Green diesel is mostly produced by a process to transform vegetable oil into biofuel through hydrocracking and hydrogenation. For the aviation grade biofuel, several requirements are needed, such as low freezing point and low viscosity, etc.The catalysts we study on are NiMo/g-Al2O3

2,3, Pd/C, and NiAg/SAPO-111,4,5 respectively. The fresh and spent catalysts were characterized by FT-IR, powder X-ray diffraction (XRD) and Scanning Electron Microscope (SEM) to understand the change of the catalyst after hydroprocessing. The NiAg/SAPO-11 catalyst for hydrocracking and hydroisomerization is prepared by two different temperature subsequently after co-impregnation. From XRD patterns of fresh NiAg/SAPO-11 catalysts, we found that nickel presents in different forms. One is Ni(OH)2 the other is NiO. We infer the reason that made NiAg/SAPO-11 invalid after catalyzed might be the leaching of nickel and the alkane remaining on the catalyst. Consider of that, we found a possibility of regeneration by reimpregnation after calcined the spent catalyst.

․Catalysts after Hydroprocessing:

․Preparation of NiAg/SAPO-11 Catalyst:

․Regenerate the Catalysts:

。Pd/C

。NiMo/g-Al2O3

。NiAg/SAPO-11

。Scheme

。NiMo/g-Al2O3

。NiAg/SAPO-11

Ni and Agprecursors

SAPO-11

180℃

Dried

500℃

Calcined

75% yield

co-impregnation

Different Ni XRD pattern

180 ℃ dried shows Ni(OH)2 pattern

500 ℃ calcined shows NiO pattern

1.Calcine: burn the impurity off2.Reimpregnation: reload the Ni

1.Liu, S.; Zhu, Q.; Guan, Q.; He, L.; Li, W. Bioresour. Technol. 2015, 183, 93.2.Palcheva,R.; Kaluža, L.; Spojakina, A.; Jirátová, K.; Tyuliev,G. Chin. J. Catal. 2012, 33, 952.3.Wang, Y.; Lin, H.; Zheng, Y. Catal. Sci. Technol. 2014, 4,109.4.Chellappa, T.; José Fonseca Costa, M.; Nascimento, W.A.; Ferreira de Lima, L.; Almeida Bassan, Í.; Tavares, M.; Fernandes JR., V.J.; Menezes, A.; Guilherme Meira, L.; Telésforo Nóbrega de Medeiros, J.; Maribondo do Nascimento, R. Bull. Pol. Ac.: Tech. 2014, 62, 481.5.Liu, Q.; Zuo, H.; Zhang, Q.; Wang, T.; Ma, L. Chin. J. Catal. 2014, 35, 748.

Vegetable Oil Hydroprocessing by Catalysts

Pd/C

NiMo/g-Al2O3

NiAg/SAPO-11

Green Diesel

E-mail: [email protected] Chen, Chung-Hung Hsieh*

Department of Chemistry, Tamkang University, Tamsui, New Taipei City, Taiwan

AcknowledgmentsReferance

Before and After catalyze

IR XRD SEM

IR XRD SEM

SEMIR XRD

․Chung-Hung Hsieh Research Group

․ Wei-Cheng Wang Research Group

alkane remained

alkane remained

pattern of substrate: g-Al2O3

alkane remained

absence of Ni pattern

→ 180 ℃ dried NiAg/SAPO-11 was chosen for the catalyze experiments

almost identical pattern

The color has changed after calcined

Spent catalyst

Fresh catalyst

Blackcalcine

Miller indices d(Å) 2q (o)

(111) 2.34 38.4

(200) 2.03 44.6

(220) 1.43 64.9

(311) 1.22 78.0

Al pattern become sharp !