Abstract
Oil-derived middle distillates (straight-run gas oil and mixture with light cycle oil and coker gas oil) for Ultra-Low Sulfur Diesel (ULSD) production by HyDroTreating (HDT) were pretreated by selective Nitrogen Organic Compounds (NOC) adsorption. Highly crystalline Metal-Organic Framework (MOF) MIL-101(Cr) prepared with propylene oxide (proton scavenger) as textural improver was used to that end. MOF was characterized by N2 physisorption, X-ray diffraction, thermal analysis, infrared, Raman and UV-vis spectroscopies, and electron microscopy (SEM and HR-TEM). NOC removal was carried out at room temperature and atmospheric pressure, the adsorbent being easily regenerable under mild conditions. Extruded MOF efficiently removed NOC from real feedstocks to concentrations ~ 80 ppm which allowed ULSD production at much milder conditions to those used during pristine feedstocks HDT. Operating temperature could be significantly diminished (from 350 to 330 °C, at 56 kg cm−2 (5.77 MPa), LHSV = 1.5 h−1, H2/oil = 2500 ft3 bbl−1 (445 m3 m−3)) which could notably prolong cycle life of NiMo/Al2O3 formulation used.
Highlights
Ever stricter environmental regulations demand for UltraLow Sulfur Diesel (ULSD, 10–15 ppm S) from oil-derived middle distillates HyDroTreating (HDT)
Weak bases as epoxides react with protons from H2O in coordination sphere of hydrated metal complexes [52] forming capability of our MIL-101 (Cr)(OH)x clusters
During Propylene Oxide (PO)-modified Metal-Organic Framework (MOF) synthesis Cr(OH)x clusters react with dicarboxylic acid moieties [50]
Summary
Ever stricter environmental regulations demand for UltraLow Sulfur Diesel (ULSD, 10–15 ppm S) from oil-derived middle distillates HyDroTreating (HDT). By increasing HDT severity (operating at higher pressure, over 70 kg cmÀ2 (7.19 MPa), for example) could enable integration of other more difficult low-priced feedstocks available in refineries In this context, Light Cycle Oil (LCO) [9] and/or coker gas oil CGO [10] could be utilized improving ULSD production and leading to enhanced revenues. Extra ~9 Â 106 barrels (1.431 Â 106 m3) ULSD produced before costly catalyst change In this contribution a detailed study using MIL-101(Cr) during pre-treatment of Straight-Run Gas Oil (SRGO) and mixture with Light Cycle Oil (LCO) and Coker Gas Oil (CGO) aimed to ULSD production by HyDroTreating (HDT) at commercially relevant conditions was carried out. Obtained extrudates (Fig. 1a) were dried at 120 °C (24 h), cut to 2–3 mm length (Fig. 1b)
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