Zhao Suoqi

Separation and characterization of petroleum asphaltene fractions by ESI FT-ICR MS and UV-vis spectrometer

Using heptane, toluene, and tetrahydrofuran (THF) as eluant, asphaltenes were fractionated into five fractions based on their polarity and solubility. The molecular composition of polar heteroatom species in both asphaltene and its fractions were analyzed by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The application of UV-vis spectrometer in characterizing asphaltene composition and measuring asphaltene concentration was discussed. About 11.9 wt% asphaltene components adsorbed permanently on silica gel in the extrography column after excessive elution with various solvents. In negative FT-ICR MS, the mass spectra show that acidic and neutral nitrogen-containing compounds such as N1 and N1S1 mainly existe in the first three less polar fractions, while oxygen-containing compounds such as O2, O2S, O2S2, O3, and O4 show high relative abundance in more polar fractions. These results suggest oxygen-containing compounds have stronger adsorption ability with silica gel. It was observed that the double bond equivalence (DBE) distribution of N1 class species in the fractions shifted to higher values while the carbon number shifted to smaller numbers as polarity of fractions increased. This indicates that acidic and neutral N1 compounds with longer carbon chain and less aromaticity have less polarity compared with those with shorter carbon chain and stronger aromaticity. UV-vis absorbance indicats that fractions containing the most aromatic and most polar asphaltene have better absorbance at long wavelength, while the fractions that consist of least aromatic and least polar asphatlenes show high absorbance at short wavelength.

Thermal transformation of acid compounds in high TAN crude oil

The Liaohe crude oil with high total acid number (TAN) was subjected to thermal reaction at 300 °C to 500 °C. Reaction products were collected and analyzed by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to determine acid compounds in the crude oil. The double-bond equivalence (DBE) versus carbon number was used to characterize the oxygenated components in the feed and reaction products. The O2 class which mainly corresponds to naphthenic acids decarboxylated at 350–400 °C, resulting in a sharply decrease in TAN. Phenols (O1 class) are more thermally stable than carboxylic acids. Carboxylic acids were also thermally cracked into smaller molecular size acids, evidenced by the presence of acetic acid, propanoic acid, and butyric acid in the liquid product. These small acid species are strong acids likely responsible for corrosion problems in refineries.

Effects of experimental conditions on the molecular composition of maltenes and asphaltenes derived from oilsands bitumen: Characterized by negative-ion ESI FT-ICR MS

A vacuum topped Canadian oilsands bitumen (VTB) was subjected to solvent precipitation and subsequently characterized by elemental analysis, gel permeation chromatograph (GPC), 1H-NMR spectroscopy and negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Effects of experimental conditions such as solvent types (n-C5, n-C6, and n-C7), solvent purity, and solvent washing time on asphaltenes yields, bulk composition, and molecular composition of detectable heteroatom compounds in ESI source were determined. Elemental nitrogen and sulfur were enriched in asphaltenes while elemental oxygen had comparable content in maltenes and asphaltenes. Molecular composition of asphaltenes varies with separation conditions. The N1 and O1 species identified by ESI FT-ICR MS were enriched in maltenes. The O2 species exhibited two different double bond equivalents (DBE) distributions and solubility in normal paraffin solvents, indicating two types of molecular structures. Multi oxygen atom containing compounds mainly detected in asphaltenes. Compound class distributions are similar for maltenes derived from n-C5, n-C6, and n-C7, as well as for asphaltenes. The cyclic paraffin impurities in normal paraffin solvents had a significant influence on asphaltenes yields and heteroatom molecular composition. A portion of neutral N1 species and acidic O2 species adsorbed on asphaltenes could be dissolved by increasing washing time. Cautions should be exercised when interpreting the properties and composition of asphaltenes obtained with different experimental conditions.

Alkylation mechanism of benzene with 1-dodecene catalyzed by Et3NHCl-AlCl3

The isotope exchange method was employed to investigate the catalytic mechanism of ionic liquid in alkylation of benzenes with olefins. It is proposed that alkylation was induced by the Lewis acid AlCl3 which attracted π electrons of 1-dodecene to shift toward 1-carbon, thus forming a carbonium ion. The carbonium ion further reacted with benzenes to form a complex. Due to unstabilit of the complex, a deuterated ring proton was transferred into an electronegative 1-carbon of the side chain to substitute for the AlCl3, accordingly 2-phenyldodecane was generated.

Alkylation of benzene with propylene catalyzed by FeCl3-chloropyridine ionic liquid

Alkylation of benzene with propylene was carried out with FeCl3-chloro-butyl-pyridine (FeCl3-[bpc]) ionic liquid as catalyst to obtain cumene. Significant improvements in propylene conversion and cumene selectivity under mild reaction conditions were attained by modification of the catalyst with HCl. Under 20°C, 0.1 MPa, reaction time 5 min, mole ratio of benzene to propylene 10:1 and mass ratio of FeCl3-[bpc] to benzene 1:100, conversion of propylene can increase from 83.60% to 100.00% and selectivity of cumene can increase from 90.86% to 98.47%. If reaction is carried out in following two stages, the result will be very good. At the initial stage of the reaction, alkylation is the main reaction and a higher conversion of propylene is obtained at a lower temperature. At the later stage of the reaction, transalkylation is the main reaction and selectivity to cumene can be increased by appropriately raising the reaction temperature.

Properties, compositions and structure characteristics of Kazakhstan and Russian Vacuum Residua

Kazakhstan vacuum residue (KAZVR) and Russia vacuum residue (RUSVR) were respectively cut into a number of narrow cuts and non-extractable end-cut by supercritical fluid extraction and fractionation (SFEF). The properties distribution and SARA compositions of the fractions were analyzed, structure parameters and structure configurations were determined by means of the modified BL method based on 13C-NMR and 1H-NMR data. The results show uneven enriching of contaminants in heavier fractions and much complex structure for end-cuts and removing end-cuts from residua will greatly favor further upgrading. The results would help detailed understanding of KAZVR and RUSVR and their processing adaptability.

The chemical fundamentals for heavy oil supercritical fluid extraction and multi-stage separation technology

The supercritical fluid extraction and fractionation method (SFEF) can realize deep cut and separation for heavy oils, which have provided a powerful tool for heavy oil chemistry research. This work summarizes recent research progress on aspects include the association and aggregation, the diffusion phenomena of SFEF cuts, the association and interaction between trace metal species and asphaltene in liquid solvent and supercritical conditions. The molecular level composition changes in supercritical extraction, thermal reaction and hydrotreating processes will also be discussed. The inspiration of the relevant chemical fundamentals to the development of heavy oil multi-stage separation by supercritical fluid processing technologies will be introduced as well.

Development of petroleum refining molecular management modeling platform

In order to maximize the petroleum resource utilization in modern refineries, the molecular management of refining process becomes more and more popular. Molecular management model is built based on the molecular-level characterization, compositional modeling, phase behavior prediction and kinetic models development. The review discusses the concept of refining molecular management and the related research subjects. Our group has been working on developing practical molecular management technologies in the recent years and has built a software platform for the molecular-level model construction. The basic framework, modules and functions of the developed petroleum refining molecular management modeling platform are shown. The platform covers all aspects of molecular-level modeling of petroleum refining processes, including individual molecule generation, property prediction, composition model construction, automatic reaction network and kinetic model building.