Changes of Petroleum Acid Distribution Characterized by FT-ICR MS in Heavy Acidic Crude Oil after True Boiling Point Distillation

The molecular transformations of carboxylic acids in heavy acidic SL crude before and after true boiling point distillation were examined by ultra-high resolution negative-ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The acid class(heteroatom number), type(z numbers) and carbon number distributions were positively characterized. It was found out that the total acid number(TAN) of SL crude decreased after true boiling point distillation, and the abundance of O2 class in mass spectra was also found to be reduced from 67.6% to 34.5% in SL TBP mixed crude as measured by MS spectra, indicating to a potential carboxylic acid decomposition. However, it was interesting that the carboxylic acids type distribution in both oils was almost the same although their relative abundance in SL TBP mixed crude turned to be much lower, suggesting that various petroleum carboxylic acid types have the similar thermal decomposition reaction behavior. Furthermore, for each O2 type of acids in SL TBP mixed crude, the abundance of carboxylic acids with carbon number higher than 35 was reduced greatly, especially for those with carbon number higher than 60, the mass peaks of which were nearly totally removed, indicating that the large carboxylic acid molecules in heavy fractions decomposed more significantly because of longer heating time during the true boiling point distillation process. As a result, the reduction of TAN may be caused by the thermal decomposition of carboxylic acids especially those with high carbon number, suggesting that quick distillation or much lower pressure is required to avoid the thermal decomposition.

Application of Molecular Distillation Process to Extend the True Boiling Point Curve of Petroleum Residues 400 ℃ ＋

True Boiling Point （TBP） distillation is one of the most common experimental techniques for determination of petroleum properties. The methods for performing TBP distillation experiments are described by ASTM D2892 and by ASTM D5236. However, these methods are established for petroleum fractions that reach temperatures up to 565 ~C. In this work, two petroleum residues were distilled in a falling film molecular distillation prototype and the data were used to obtain the extension of the TBP curve above a temperature of 565 ~C. It was possible to extend the TBP curve of both petroleum up to temperatures close to 700 ~C with consistency and continuity in comparison to the standard curve. In addition, an amount of raw material that was been treated as residue could be reused.

A simulation of diesel hydrotreating process with real component method

Computer simulation is a good guide and reference for development and research on petroleum refining processes. Traditionally, pseudo-components are used in the simulation, in which their physical properties are estimated by empirical relations and cannot be associated with actual chemical reactions, as no molecular structure is available for pseudo-components. This limitation can be overcome if real components are used. In this paper, a real component based method is proposed for the simulation of a diesel hydrotreating process by using the software of Unisim Design. This process includes reaction units and distillation units. The chemical reaction network is established by analyzing the feedstock. The feedstock is characterized by real components, which are obtained based on true boiling point curve. Simulation results are consistent with actual data.