Improved THETA-1 for Light Olefins Oligomerization to Diesel: Influence of Textural and Acidic Properties

Abstract

Martínez, C.; Corma Canós, A. (2014). Improved THETA-1 for light olefins oligomerization to diesel: Influence of textural and acidic properties. Topics in Catalysis. 57(6-9):668-682. doi:10.1007/s1124. Abstract.The increase in diesel demand, especially in Europe, and the need for high fuel quality requirements, is forcing refiners to move into additional processes for production of high cetane diesel in order to meet the present market trends. Oligomerization of light olefins into middle distillate range products is a viable option. The fuel produced through this technology is environmentally friendly, free of sulfur and aromatics, and the adequate choice of the heterogeneous catalyst will direct the selectivity towards low branched oligomers, which will result in a high quality product. In this work we show the benefits of combining basic desilication treatments for generation of additional mesoporosity in mono-directional Theta-1 zeolite, with selective acid dealumination steps that restore not only the microporosity to values close to those of the parent samples, but also the total and strong Brønsted acidity. These modified Theta-1 zeolites present an outstanding catalytic behavior for oligomerization of propene, with a largely increased initial activity, a much higher resistance to deactivation with time on stream, and an improved selectivity to products in the diesel fraction, as compared to the original microporous Theta-1.

Mesostructured Catalysts Based on the BEA Topology for Olefin Oligomerisation

“…[26,69,73] These analyses were validated using the ASTM D2887 Reference Gas Oil no. The fractions corresponding to the 170 8C( C 6 -C 10 )c ut characteristic of naphtha products (NCut), and to the 170-390 8Cc ut characteristic of diesel products (DCut, corresponding approximately to the C 10 -C 24 n-paraffinic range) were determined according to the ASTM D2887 method (standard test method for boiling range distribution of petroleum fractions by gas chromatography).…”

“…solid phosphoric acid, [9,24,25] zeolites, [6,[26][27][28][29][30] amorphous silicaalumina [31,32] and other metal oxide catalysts. [33,34] Zeolites and zeotypesa re particularly promising versatile, crystalline, microporousm aterials which may withstand the catalytic reaction conditions and catalystr egeneration treatments (e.g.,t ob urn off coke).…”

Catalytic Conversion of 1‐butene over Modified Versions of Commercial ZSM‐5 to Produce Clean Fuels and Chemicals

“…The fractions corresponding to the 170°C cut characteristic of naphtha products (NCut), and to the 170-390°C cut characteristic of diesel products (DCut, corresponding approximately to the C 10 À C 24 n-paraffinic range) were determined according to the ASTM D2887 method (Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography). [39,50,98] These analyses were validated using the ASTM D2887 Reference Gas Oil no 1 (Supelco, sample 1, Batch 2) and the results agreed, within the allowable difference ranges, with the ASTM D2887 consensus boiling point values. The C 10 type products (corresponding to the temperature cut point) may be distributed between DCut and NCut fractions.…”

“…[39,[42][43][44][45] The top-down strategies are advantageously cheaper, relatively easy to reproduce and scale-up for larger production. [23,28,46] Zeotypes based on the MFI, [39,43,47] MOR, [24,48] FAU [49] and TON [50] topologies were prepared via topdown strategies. MFI versions were reported as effective catalysts, for example, for selective catalytic cracking of 1butene, [51][52][53] and 2-methyl-2-butene [54] to light olefins.…”

Spielt die Zeolithkatalyse in Bioraffinerien der Zukunft eine ähnlich große Rolle wie in der Erdölraffination?

“…Ebenfalls sollte er kleine Mengen Mineralsäuren vertragen. Mit der Herstellung hierarchischer Zeolithe befasst sich eine Übersicht, [50] und auch die Definition des Hierarchiefaktors, [51] der bereits auf Materialien mit 10-Ring-Porentopologie [52] und sogar auf hydrophile Zeolithe mit hohem Aluminiumoxidanteil angewendet wurde, [53] ist aufgeführt. Je nach Grad der Behandlungen kann migrierendes Siliciumdioxid die entstandenen Gitterfehlstellen und die gebündelten Silanol-Endgruppen mehr oder weniger stark ausgleichen.…”