Integration of catalytic cracking and hydrotreating technology for triglyceride deoxygenation

Lin

et al. 2019

Catalysts

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The roles of catalyst acidity and basicity playing in catalytic conversion of oleic acid were studied in a fixed-bed micro-reactor at atmospheric pressure. The chemical compositions of the petroleum-like products were obtained and the reaction pathways of different catalysts are discussed. The metal oxides are suitable for upgrading oleic acid into organic liquid products (OLPs). Over 98% oxygen was removed when CaO, MgO, and TiO 2 were implemented, whereas a minimum oxygen removal lower than 20% was obtained by using quartz. The oxygen removal was 73% by alumina; however, the light oil yield (to feed) and the valuable product yield received were the highest in all investigated catalysts. The hydrocarbons in OLPs, overwhelmingly presenting in the product, were found to be alkenes and cycloalkenes, followed by saturated hydrocarbons, and then aromatics lower than 4%. For Lewis acidic catalysts, higher acidity of the catalyst is beneficial to deoxygenation but also secondary cracking. CaO has higher dehydrogenation capability than MgO does.Catalysts 2019, 9, 1063 2 of 13 catalysts [6]. The early acidic and basic cracking catalysts for biofuels upgrading dated back to the 1980s [8]. At 300~500 • C, Both acid and base metal oxide catalysts were found to be effective catalysts in the deoxygenation of fatty acids or triglycerides to a mixture of oxygen containing products and hydrocarbons [4,[9][10][11][12]. The various impacts of oxygenates upgraded by both acid and base catalysts were also compared [13][14][15][16]. The Al 2 O 3 was able to remove 94 wt.% of oxygen from waste cooking oil at the temperature of 470 • C [4]. The basic sites in a catalyst were found to be capable of strongly inhibiting secondary cracking, which resulted in high residual oil yields and low gas yields. Xu et al. found that the amounts of carboxylic acids and aldehydes, as well as the high acid value of liquid products, were significantly decreased by using base catalysts, and that the catalysts were modified by using base catalysts such as CaO rather than Al 2 O 3 . Furthermore, at low temperature, the product of the formers showed good solubility in diesel, good cold flow properties, and high heat value [14][15][16]. This is contributed to by the neutralization reactions taking place between the basic sites on catalysts and acidic intermediates in liquid products. The produced neutral hydrocarbons had more similar molecular structure to diesel fuels and better properties than acidic oxygenate intermediates.Some literature reported the reaction processes of the catalytic cracking oxygenates to petroleum-like products over metal oxide catalysts; however, most of the catalytic cracking work has been performed using acid catalysts, and the effect of the basic sites on catalyst performance and reaction mechanisms have not been sufficiently discussed. In this study, the specific roles that the acidity and basicity, and the types of acidic sites of the catalyst, played in the product distribution of oleic acid were investigated.

Section: Thermal Treatmentmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Catalytic Decomposition of Oleic Acid to Fuels and Chemicals: Roles of Catalyst Acidity and Basicity on Product Distribution and Reaction Pathways

Lin

et al. 2019

Catalysts

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“…Sodium bromide finally moves into the aqueous phase because it is an inorganic salt only dissolving in the aqueous. The unconverted 1-bromobutane and the resultant-butyl adipate were quantitatively tested by GC (FID) (SHIMADZU, Nakagyo-ku, Kyoto, Japan), and the detailed testing information is the same as the previous publication [33]. The conversion and the selectivity were calculated by the amount of unconverted 1-bromobutane and that of the resultant-butyl adipate, respectively.…”

Section: Supplementarymentioning

confidence: 99%

Application of Phase Transfer Catalysis in the Esterification of Organic Acids: The Primary Products from Ring Hydrocarbon Oxidation Processes

Lin

et al. 2019

Catalysts

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For enhancing the cetane number (CN) of diesel fraction, the selective oxidative ring opening method was applied to upgrade ring hydrocarbons. Organic acids, one of the main products from this oxidative reaction, being esterified by the phase transfer catalysis (PTC) approach were studied. Adipic acid, benzoic acid, and phthalic acid were used as model compounds. Reaction time, reaction temperature, the amount of water, and the amount of catalyst in the esterification process were investigated and optimized using orthogonal experimental design method. The kinetics of esterification process was then conducted under the optimal condition. The types of catalysts and organic acids, the amount of catalyst and water were also investigated. The PTC esterification was one rate controlling reaction on the interface between the aqueous phase and the oil phase. Hydrophobicity is a key factor for converting benzoic acid, adipic acid, and phthalic acid to the corresponding esters. It was found that around 5–8% water is the optimal quantity for the given reaction system. Two cases of esterification processes of PTC were proposed.

“…In our previous work, it was found that SiO 2 –Al 2 O 3 –TiO 2 (SAT) supported catalyst had efficient hydrodeoxygenation (HDO) capability [ 21 – 24 ]. In this study, a trinary porous SAT was synthesized using sol–gel method.…”

Section: Introductionmentioning

confidence: 99%

Hydro‐upgrading of light cycle oil‐synthesis of NiMo/SiO2-Al2O3-TiO2 porous catalyst

Zhang

et al. 2021

J Porous Mater

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The demand for transportation diesel fuels has been increasing in most countries for the last decade. As is one of the primary sources for diesel distillates, light cycle oil (LCO), having the advantages of inheriting similar density and boiling point range to diesel fuels, but high contents of aromatics, sulfur, and nitrogen, needs to be upgraded before being utilized. This work reports a trinary porous SiO 2 –Al 2 O 3 –TiO 2 (SAT) synthesized by sol–gel method and used as the NiMo catalyst support for the LCO hydro-upgrading. NiMo/Al 2 O 3 -zeolite (AZ) was used as a reference to evaluate the performances of the NiMo/SAT. The catalysts were characterized by XRD, BET, Pyridine-FTIR, and TEM; and evaluated in a 20-mL fixed-bed microreactor using a Fluid Catalytic Cracking LCO as feedstock. It was found that the SAT support possessed a high surface area, high pore volume, and good acid properties. The NiMo/SAT catalyst exhibited even better hydrodesulfurization, hydrodenitrogenation, and hydrodearomatization performances than NiMo/AZ when the reaction was performed at 375 °C and 1100 psi. Compared with the zeolite addition catalyst, the SAT catalyst has the advantages of simple synthesis procedures and low input cost.