Preparation of pyridine and 3-picoline from acrolein and ammonia with HF/MgZSM-5 catalyst

Zhang, Xian; Wu, Zhen; Liu, Wei; Chao, Zi‐Sheng

doi:10.1016/j.catcom.2016.02.011

Cited by 17 publications

(15 citation statements)

References 16 publications

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“…38 In addition, the reduction of midstrength acid sites was more obvious than that of weak acid sites, mainly because the OH − group of Z5 was partly occupied by F − ions which led to Brønsted acid sites converting to Lewis acid sites. 39 Furthermore, the Pt-incorporated catalysts (Pt-Z5/FZ5) exhibited the NH 3 desorption at a high-temperature region (600−700 °C) compared with the parent Z5/FZ5, which should be attributed to the introduction of Pt species sites. Overall, the original acidic sites on catalysts were well preserved after loading Pt because the Pt loading (<0.5 wt %) was much lower than that of Ni (>1 wt %).…”

Section: T H I S C O N T E N T Imentioning

confidence: 99%

In Situ Upgrading of Cellulose Pyrolysis Volatiles Using Hydrofluorinated and Platinum-Loaded HZSM-5 for High Selectivity Production of Light Aromatics

Wang

Cao

Zhao

et al. 2019

Ind. Eng. Chem. Res.

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The ZSM-5(Z5) was synergistically modified by leaching agent HF (0.5 mol/L) and metallic Pt (0.1, 0.2, 0.5, and 1 wt %) to prepare the bifunctional hierarchical Pt-FZ5 for enhancing light aromatic products by catalytic reforming of volatiles from cellulose pyrolysis. The results show that HF reduced the acidity and significantly increased the mesopores through the original pore enlargement, promoting uniform dispersion of metal Pt (outer and inner channels) and mass transfer of reactants with products. In addition, the metal Pt was mainly combined with Brønsted acid sites which promoted the cleavage of initial volatiles to produce more light aromatics rather than coke deposition. The Pt-FZ5 exhibited the highest aromatic yield of 30.3% with a high aromatic selectivity in bio-oil of 80.5% when the Pt loading is 0.2 wt % owing to its rich mesoporous (2−9 nm) and appropriate acidity. Meanwhile, the coke deposition of Pt-FZ5 was significantly inhibited.

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Section: T H I S C O N T E N T Imentioning

confidence: 99%

In Situ Upgrading of Cellulose Pyrolysis Volatiles Using Hydrofluorinated and Platinum-Loaded HZSM-5 for High Selectivity Production of Light Aromatics

Wang

Cao

Zhao

et al. 2019

Ind. Eng. Chem. Res.

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“…In the Chichibabin synthesis mechanism, pyridine can be produced from formaldehyde and acetaldehyde in a ratio of 1:2, with ammonia acting as a nitrogen source. , First, acrolein can be formed through aldol condensation from acetaldehyde and formaldehyde. Then, the acrolein is condensed with aminated acetaldehyde through Michael addition reactions and ring closure to form a dihydropyridine, which can be subsequently transformed to a pyridine through a dehydrogenation reaction. , Zhang et al prepared pyridine from acrolein and ammonia using HF/MgZSM-5 . They pointed out that the pyridine should be formed on a strong acid site.…”

Section: Resultsmentioning

confidence: 99%

“…After the production of 2-propen-1-imine and vinylamine through amination, these molecules can undergo a Diels-Alder reaction to form cyclic compounds. Meanwhile, it is more likely to produce disubstituted tetrahydropyridine (Supporting Information, Figure S3) through single-component polymerization of 2-propen-1-imine. , Since the pyridine synthesis reaction is carried out in the catalyst, the mass transfer effect of the reactive intermediate in the pyridine synthesis process needs to be considered together with the pore size of the glycerol molecule, which is limited to ∼0.55 nm . Therefore, the catalysis of ZSM-5 is not conducive to the formation or diffusion of multisubstituted pyridine products.…”

Section: Resultsmentioning

confidence: 99%

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Insight into the Mechanism of Glycerol Dehydration and Subsequent Pyridine Synthesis

Jiang

Wang

et al. 2021

ACS Sustainable Chem. Eng.

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In the present study, glycerol was exploited as the feedstock to synthesize pyridine with ammonia gas as a carrier and reactant through thermal conversion. A density functional theory (DFT) at the M06-2X method was applied to understand the mechanism of glycerol dehydration, the ammonization of oxygenated compounds, and the condensation of imines. The results confirmed that glycerol could be directly converted into pyridine in ammonia atmosphere at 550 °C. The overall view of the thermal conversion mechanism of glycerol was compared with the previous experimental data and the proposed mechanisms, which indicated that the neutral glycerol dehydration process should mainly produce acrolein, acetaldehyde, formaldehyde, and acetol. The produced oxygenated compounds (acrolein and acetaldehyde) can react with ammonia to form imine, which would further undergo Michael addition, a Diels-Alder reaction, deammonization, and dehydrogenation to form pyridine. In a catalytic condition, ZSM-5 not only plays a shape-selective effect on the conversion of glycerol to pyridine but also changes the path of the reaction. The structure of ZSM-5 limits the formation of multisubstituted pyridine products, which is beneficial to the formation of pyridine and monosubstituted pyridine. Protonated vinylamine intermediates may be a critical step limiting pyridine yield and selectivity. The kinetic analysis that is based on transition state theory was consistent with product contribution in experiments. The present study confirmed the selectivity and the conversion route of glycerol to pyridine.

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“…In this sense, zeolite-based catalysts (e.g., HZSM-5) have unique shape selectivity, high surface area, and remarkable thermal stability. They are highly active to produce pyridines by promoting C-N condensation and Michael addition when their pore size and acidity are accurately tailored [244][245][246][247][248]. Interestingly, a neater approach starts directly from glycerol by carrying out in-situ dehydration, which is possible to accomplish with the same catalysts [249][250][251][252].…”

Section: N-heterocyclesmentioning

confidence: 99%

Catalytic transformations of glycerol via hydroxyacetone into nitrogen heterocycles of industrial interest

Santa-Pau¹

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A lo largo de la lectura de la presente tesis, se le hará evidente al lector el hecho de que este trabajo se sustenta en el esfuerzo, dedicación y apoyo que otras muchas personas le han brindado al autor del mismo para que pudiera llevarlo a cabo de forma exitosa. Por ello, en estas líneas, me gustaría agradecer a todos aquellos que, de una u otra manera me han brindado a mí o a la presente tesis doctoral cualquier tipo de ayuda, personal o profesional, que haya quedado reflejada en mayor o menor medida en cualquiera de las líneas expuestas en el documento que se presenta a continuación. Pido disculpas de antemano por los muchos nombres que se me olvidarán, pero a todos, sabed que os estoy infinitamente agradecido.En primer lugar, debo dar las gracias a mi director de Tesis el Dr. Marcelo E. Domine por su apoyo y confianza desde nuestra primera reunión en septiembre de 2015, por haber visto en mí alguien en que merecía la pena apostar, y por seguir considerándolo así hasta el día de hoy. Por sus consejos, enseñanzas y, en especial, su paciencia conmigo durante todos estos años.En segundo lugar, a la Profesora Patricia Concepción y al doctor Yannick Mathieu.Gracias por toda vuestra ayuda y por todo el conocimiento que habéis volcado en mí.Siempre os voy a considerar referentes y espero teneros siempre cerca, para seguir aprendiendo y, lo más importante, disfrutando de vuestras opiniones, de vuestros consejos y de nuestras discusiones.A los doctores Pascual Oña-Burgos, Daniel Delgado y Luis Miguel Martínez-Prieto (aquí también debo incluir a Yannick). A lo largo de estos años son incontables los momentos que hemos compartido. Vuestro entusiasmo, vuestra pasión a la hora de entender esta profesión han sido, en muchos momentos, la verdadera fuerza motriz de esta Tesis Doctoral. Cada ratito con vosotros ha alimentado mi motivación, gracias además por vuestro cariño y apoyo. He tenido mucha suerte de encontrarme unos amigos tan buenos.A Silvia, una amiga excepcional, siempre dispuesta a escucharme, a apoyarme y a ayudarme. Uno de los grandes tesoros producidos, mejor dicho, descubiertos, en estos años.

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Preparation of pyridine and 3-picoline from acrolein and ammonia with HF/MgZSM-5 catalyst

Cited by 17 publications

References 16 publications

In Situ Upgrading of Cellulose Pyrolysis Volatiles Using Hydrofluorinated and Platinum-Loaded HZSM-5 for High Selectivity Production of Light Aromatics

In Situ Upgrading of Cellulose Pyrolysis Volatiles Using Hydrofluorinated and Platinum-Loaded HZSM-5 for High Selectivity Production of Light Aromatics

Insight into the Mechanism of Glycerol Dehydration and Subsequent Pyridine Synthesis

Catalytic transformations of glycerol via hydroxyacetone into nitrogen heterocycles of industrial interest

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