Development of semi-synthetic catalyst based on clay and their use in catalytic cracking of petroleum residue

Two semi-synthetic clay-based catalysts were prepared. These catalysts were obtained by incorporating lanthanum oxide (Cat1) and chromium oxide (Cat2). They were then tested for catalytic cracking of a heavy petroleum residue (fuel). The two formulations were carried out in the presence of silica to improve their acidity then underwent an acid activation. The catalysts obtained were characterized by various methods (XRD, FTIR, ICP-OES, SEM). The results showed that the incorporation of oxides and the addition of silica improves the structural characteristics of the final products. The support used was a kaolinite rich clay, having a specific surface area of 15.26 m2/g and acidity of 14 meq/g. These values increase, respectively, to 456.14 m2/g and 50 meq/g for Cat1 and to 475.12 m2/g and 57 meq/g for Cat2. The influence of the type of oxide incorporated, the specific surface area, the porosity and the acidity of the catalysts on their catalytic activity was studied. The nature of the oxide used proved to be decisive on the quality of the catalyst. Thus Cat1, prepared with lanthanum oxide, showed the best performance in cracking the petroleum residue achieving a conversion rate of 74.13% compared to 66.53% for cat2.

Comparison of coking additives obtained from different types of oil stock

Coke producers often face a shortage of valuable grades of coals, i.e. coking coals. This paper examines the possibility to obtain a coking additive by applying delayed coking to various types of heavy petroleum residues. The paper also gives a comparative description. Five types of heavy petroleum residue from the KINEF oil refinery were used in the experiments that aimed to produce carbon material. They included vacuum residue ELOU-AVT-6, vacuum residue S-1000 resultant from the hydrocracking process, visbreaker bottoms from the S-3000 unit, and two mixtures of the ELOU-AVT-6 unit products: a mixture of vacuum residue and third vacuum cut; and a mixture of vacuum residue, third vacuum cut and atmospheric residue. The carbon material obtained from all the above types of raw materials was analyzed for quality; an X-ray diffraction analysis was carried out; and the interplanar spacings d002 and d110 were calculated, as well as the linear sizes of Lc and La crystallites. The coking additive obtained instead of the typical petroleum coke was found to meet the specification. Thus, the volatile matter content in it is within the range from 15 to 25 wt%. This additive can be used in steel production instead of coking coal. The coking additive from a mixture of vacuum residue, third vacuum cut and atmospheric residue has the highest content of volatile matter (19.30%), while the coking additive from the visbreaking residue from the S-3000 has the lowest volatile matter content (16.15%). The latter is due to the fact that the primary petroleum material was subjected to light thermal cracking. It is shown that as the composition of the heavy petroleum residue changes, so do the properties of the resultant coking additive: a higher fraction of the low-boiling components in the feedstock is associated with a higher volatile matter content; the carbon materials produced from vacuum residue have a higher microhardness; the coking product produced from the visbreaker bottoms has a lower porosity compared with the product obtained from the vacuum residue. This research was carried out as part of a governmental assignment of the Ministry of Education and Science of the Russian Federation in the framework of the following research project: 0792-2020-0010 “Fundamentals of innovative processing techniques to obtain environmentally-friendly motor fuels and innovative carbon materials with variable macro- and microstructure of the mesophase from heavy hydrocarbon materials”. The research was carried out at the laboratory of the Shared Knowledge Centre of the Saint Petersburg Mining University.

Obtaining Pure Vanadyl Porphyrins from Heavy Petroleum Residue to Create Catalysts for Various Processes

Asphaltenes and resins from petroleum vacuum residue were shown to be the promising raw materials for obtaining pure vanadyl porphyrins. Vanadyl porphyrins are recovered from petroleum objects via the extraction of dimethyl formamide (DMFA) followed by purification on a chromatographic column using silica gel and sulfocationite. The composition of the obtained vanadyl porphyrins was studied by means of mass spectrometry with matrix assisted laser desorption/ionization (MALDI) and high performance liquid chromatography (HPLC). Thus obtained metalloporphyrins can be used as a basis to create catalysts for various chemical processes, which may serve as an alternative to their synthesis.

Combined Cracking Residue and Mechanical Activation Oil Shale

The joint cracking of mechanically activated oil shale and petroleum residue was studied. The introduction of oil shale allowed to intensify the process of destruction of high-molecular components of the petroleum residue. In the obtained liquid thermolysis products, oils predominate from 40,2 to 81,1% wt. With an increase in the share of oil shale in the cracking products, the proportion of asphaltenes decreases from 4,2 to 2,8% wt, and of tar from 6,7 to 4,8% wt. In gaseous products, the proportion of carbon dioxide and carbon monoxide increases markedly. The introduction of mechanically activated oil shale also affects the fractional composition of thermolysis products; the proportion of gasoline (IPB – 200 °С) and diesel fractions (200–360 °С) changes

Ex-Situ Synthesis and Study of Nanosized Mo-Containing Catalyst for Petroleum Residue Hydro-Conversion

This study represents the results of ex-situ synthesis and research of the properties of concentrated suspensions with new catalysts for petroleum residue hydro-conversion. Suspensions were prepared and stabilized in a petroleum residue medium through reverse emulsions containing water-soluble Mo-precursor and S-containing agents (elemental sulfur, thiocarbamide) in the absence of a solid carrier. The resulting ex-situ catalyst dispersions had Mo content of 6–10 wt % and contained nanosized and submicron catalyst particles stabilized in a petroleum residue medium. The effects of S-containing agents on the properties of catalytic particles (sulfidation level, dispersity, structural and morphological features) were studied. The synthesis conditions for the optimal ex-situ catalyst providing the lowest coke yield (0.2 wt %) and the highest conversion (55.5 wt %) during petroleum residue hydro-conversion in a single pass mode have been determined.