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Asphaltenes-free vacuum resid derived deasphalted oils (DAOs) from Chinese Liaohe (LDAO) and Venezuela Orinoco (VDAO) were subjected to catalytic hydrotreating. Electrospray ionization (ESI) Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses were performed on LDAO and VDAO before and after hydrotreating to determine the structural composition transformation of nitrogen-containing compounds as a result of hydrotreating. The results showed that the basic nitrogen contents of the two DAO before and after hydrotreating were relatively constant. However, the neutral nitrogen contents of hydrotreated LDAO and VDAO were dramatically reduced. The LDAO had a higher neutral nitrogen conversion than VDAO, even though LDAO had a higher neutral nitrogen content than VDAO prior to hydrotreating. The significant difference in nitrogen removal for the DAOs was due to the structural variation of the neutral nitrogen compounds. By plotting the double bond equivalent (DBE) value as a function of carbon number for N1 class species, the hydrodenitrogenation reactivities of nitrogen compounds could be classified as easy- and hard-to-convert nitrogen compounds. The easy-to-convert nitrogen compounds have more unsaturated cores and have less and/or shorter alkyl side chains than the hard-to-convert nitrogen compounds which have long alkyl side chains.

Mesoporous MY-xGa zeolites exhibiting both crystallized pore walls and narrowly dispersed mesopores with different Ga content were successfully synthesized. The synthesized samples were characterized by XRD, N 2 adsorption desorption isotherms, SEM, TEM, XPS, FTIR, 29 Si MAS NMR, 71 Ga MAS NMR, and Py-FTIR methods. The results show that the synthesized samples exhibit unique open channel like mesopore systems and outstanding crystallite natures; no nonframework Ga species were observed over the MY-xGa series samples, and their acidic properties can be modulated by varying the Ga/Al ratio in the initial synthesis gel. The corresponding NiMo/HMY-xGa catalysts were prepared via the incipient wetness coimpregnation method; the morphologies of the sulfide catalysts were characterized by HRTEM, and the covalent states of the active metals were characterized by XPS. The catalytic activities of the investigated catalysts for the 4,6-DMDBT HDS reaction were assessed, and the collected products were analyzed by GC and GC-MS methods. The catalyst NiMo/HMY-0.5Ga showed the highest catalytic activity due to the synergistic effect of modulated acidic properties, excellent morphology, highest sulfidation degree, and proper proportion of NiMoS phase. More importantly, 4-MDBT, DBT, and BP were observed and identified as the products of the 4,6-DMDBT HDS reaction, designated as the demethylation pathway (DM) for the 4,6-DMDBT HDS reaction. Finally, a reaction network including DDS, HYD, ISO, and DM pathways for the 4,6-DMDBT HDS reaction over catalyst NiMo/HMY-0.5Ga was proposed.

The distribution of vanadium (V) compounds in the petroleum vacuum residuum (VR) and their transformations in hydrodemetallization (HDM) were investigated. V compounds in the VR and its hydrotreated products were extracted by different solvents in sequence to obtain methanol, dimethylformamide (DMF), and toluene extract fractions. The extracts were further separated into several subfractions using silica gel chromatography with various polar solvents. Positive-ion electrospray ionization (ESI) Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses was used to characterize V compounds before and after HDM. The contents of V compounds in the methanol, DMF, and toluene extracts were 9.04, 22.19, and 62.58%, respectively. The V compounds in the methanol extract were mainly porphyrin with a molecular formula of C n H m N 4 V 1 O 1 , which were found undergoing side-chain cracking and could be removed through hydrotreating. C n H m N 5 V 1 O 2 species were found in the DMF extracts, which can be easily converted or removed under severe reaction conditions. The V compounds in the toluene extracts were most resistant for hydrotreating, which were speculated as vanadyl porphyrins with complex substituent groups attached to the core porphyrin structures. The results indicated that a highly active HDM catalyst should possess a highly active hydrogenesis property and macropore size distribution for the different V compounds removed.

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