Search Results (7)

This review is devoted to the occurrence, extraction, structural characterization and catalytic applications of vanadyl porphyrins present in heavy crude oils and petroleum residues. Vanadyl porphyrins represent the major vanadium-containing compounds in petroleum systems and play a dual role as both catalyst poisons during refining processes and valuable precursors for functional catalytic materials. Particular attention is devoted to recent advances in extraction technologies, including solvent extraction, ionic liquids, deep eutectic solvents, functionalized adsorbents and chelating agents. Process intensification approaches such as ultrasound- and microwave-assisted extraction, are also discussed as promising strategies for improving extraction efficiency and selectivity. Furthermore, recent developments in petroleum characterization using FTICR-MS, EPR, HYSCORE and LA-ICP-MS techniques are reviewed, providing insights into metalloporphyrin speciation, oxidation states, and distribution within complex petroleum matrices. Beyond their traditional role in catalyst deactivation, vanadyl porphyrins have emerged as attractive precursors for catalytic materials applied in oxidation reactions, photocatalysis, oxidative desulfurization, wastewater treatment and selective organic synthesis. The development of hybrid catalytic systems based on mesoporous silica, graphene oxide, carbon nanotubes, polymer matrices, and metal–organic frameworks has significantly improved catalyst stability, activity and recyclability. Current challenges related to the selective extraction, preservation of metalloporphyrin structure and catalytic performance evaluation are also discussed. Overall, this review provides an integrated perspective on the recovery, characterization and valorization of vanadyl porphyrins for sustainable petroleum upgrading and environmental applications. Full article

The presence of vanadium compounds in heavy oils poses a significant challenge by poisoning and deactivating refining catalysts, making their removal an essential processing step. However, this process is challenged by the competitive adsorption of abundant polycyclic aromatic hydrocarbons (PAHs) in heavy oils, due to the similar conjugated π-electron structure of PAHs and vanadyl porphyrins. In the presented study, the adsorption behaviors of vanadyl octaethylporphyrin (VOOEP) and 1-methylpyrene (1-MP) on various solid adsorbents were investigated. Among the adsorbents studied, the primary secondary amine adsorbent (PSA) demonstrated superior performance, achieving high VOOEP adsorption capacity and exceptional selectivity, even in the presence of a large excess of 1-MP. The adsorption kinetics, isotherms, and thermodynamics of VOOEP and 1-MP onto PSA were studied. Four common kinetic models (pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion) were used for data fitting. The adsorption isotherms were modeled using Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherms. The adsorption kinetics for both VOOEP and 1-MP on PSA were best described by the pseudo-second-order model, while equilibrium data were well fitted by the Freundlich isotherm. Thermodynamic analysis confirmed that the adsorption of VOOEP and 1-MP on PSA is a spontaneous and exothermic process. The practical applicability of PSA was confirmed with a heavy deasphalted oil (HDAO), where it efficiently removed vanadium with high selectivity, with lower co-adsorption of desirable oil components. The results indicate that PSA is a promising adsorbent for effectively removing vanadium compounds from heavy oils. Full article

Titanium nitride and vanadium nitride–carbon-based composite systems, TiN/C and VN/C, were prepared using a new synthesis method based on the thermal decomposition of titanyl tetraphenyl porphyrin (TiOTPP) and vanadyl tetraphenyl porphyrin (VOTPP), respectively. The structure of the TiN/C and VN/C composite materials, as well as their precursors, were characterized using Fourier Transformed Infrared Spectroscopy, X-Ray diffraction (XRD), X-Ray energy dispersive (EDS) and X-Ray photoelectron spectroscopy (XPS). Morphologies of the TiN/C and VN/C composites were examined by means of scanning electron (SEM) and transmission electron (TEM) microscopy. The synthesis of the non-metalated tetraphenyl porphyrin, the titanium, and vanadium tetraphenyl porphyrin complexes were confirmed using FTIR. The thermal decomposition of the titanium and vanadium tetraphenyl porphyrin complexes produced the respective metal nitride encapsulated in a carbon matrix; this was confirmed by XRD, SEM, TEM, and XPS. From the XRD patterns, it was determined that the TiN and VN were presented in cubic form with expected space group FM-3M and 1:1 (metal:N) stoichiometry. The XPS results confirmed the presence of both TiN and VN in the carbon matrix without metal carbides. The SEM and TEM results showed that both TiN and VN nanoparticles formed small clusters throughout the carbon matrix; the EDS results revealed a uniform composition. The synthesis method presented in this work is novel and serves as an effective means to produce TiN and VN NPs with good structure and morphology embedded in a carbon matrix. Full article

Metalloporphyrin-containing mesoporous materials, named VTPP@SBA, were prepared via a simple anchoring of vanadyl porphyrin (5,10,15,20-Tetraphenyl-21H,23H-porphine vanadium(IV) oxide) through a SBA-15-type mesoporous material. For comparison, vanadyl porphyrin was also impregnated on SiO₂ (VTPP/SiO₂). The characterization results of catalysts by XRD, FTIR, DR-UV-vis, and EPR confirm the incorporation of vanadyl porphyrin within the mesoporous SBA-15. These catalysts have also been studied using electrochemical and photoelectrochemical methods. Impedance measurements confirmed that supporting the porphyrin in silica improved the electrical conductivity of samples. In fact, when using mesoporous silica, current densities associated with oxidation/reduction processes appreciably increased, implying an enhancement in charge transfer processes and, therefore, in electrochemical performance. All samples presented n-type semiconductivity and provided an interesting photoelectrocatalytic response upon illumination, especially silica-supported porphyrins. This is the first time that V-porphyrin-derived materials have been tested for photoelectrochemical applications, showing good potential for this use. Full article

The purpose of this work is to analyze the electron–nuclear interactions of the vanadyl-porphyrin (VP) complexes in oil asphaltenes. Asphaltenes from the Athabasca oil sands were studied by HYperfine Sublevel CORrelation Spectroscopy (HYSCORE) electron paramagnetic resonance (EPR). It makes it possible to resolve and interpret complex hyperfine spectra of intrinsic VP with strong and weak hyperfine interactions between the electron magnetic moment and various nuclear spins (¹H, ¹⁴N, ⁵¹V). The main parameters of spin-Hamiltonian for the VP spin system are determined. The axially symmetric structure of the VP complexes is revealed, and the local nuclear environment of the paramagnetic center is investigated. The results can be used for the study of asphaltene electron–nuclear structure and asphaltene aggregates with the aim of elucidating asphaltenes’ transformation(s) under the influence of external treatment. Full article

The composition of purified vanadyl porphyrins recovered from the resins of heavy oils possessing high and low vanadium contents was investigated. Vanadium content in the resins of the heavy oils under study differs by a factor of ca. 15. To recover and purify vanadyl porphyrins from the resins, extraction by N,N–dimethylformamide (DMF) with subsequent two-stage column chromatography on silica gel and sulfocationite were employed. The change of structural-group composition and content of vanadyl porphyrins in the products obtained at each stage was evaluated using Fourier IR and UV-Vis spectroscopy. Analysis of the purified vanadyl porphyrins using MALDI mass spectrometry determined distribution of their most abundant types (etio- and DPEP) and identified C₂₇–C₃₉ homologs for the resins possessing high vanadium content and C₂₈–C₃₉ homologs for the resins with low vanadium content. Full article

In the present work, the first data on the catalytic activity of d-metal complexes of petroleum porphyrins obtained via two-stage re-metallization (acid demetallization with subsequent metalation) of high-purity petroleum vanadyl porphyrins are presented. During acid demetallization of petroleum vanadyl porphyrins, the highest yield (49%) and spectral purity of free petroporphyrin bases were achieved with concentrated sulfuric acid and a diluted solution of vanadyl porphyrins in chloroform. In the series of divalent cations of Mn, Fe, Co, Ni, Cu, and Zn, only the last four metals are complexed with demetallated petroporphyrins without significant changes in their component composition, whereas the interaction with Mn and Fe cations causes an evident structural transformation or even full degradation of petroporphyrin macrocycles, respectively. The composition and spectral purity of petroleum porphyrin-containing reactants and products were analyzed by FT-IR, UV-Vis, NMR, and MALDI-TOF mass spectroscopic methods. The obtained petroporphyrin-based d-metal complexes were assayed by the reaction of 2-mercaptoethanol oxidative dimerization, in which the copper porphyrins exhibited the highest catalytic activity. Full article