Transfer Hydrogenation of Biomass-Like Phenolic Compounds and 2-PrOH over Ni-Based Catalysts Prepared Using Supercritical Antisolvent Coprecipitation

Transfer hydrogenation (TH) is considered as one of the most promising ways to convert biomass into valuable products. This study aims to demonstrate the performance of high-loaded Ni-based catalysts in the TH of phenolic compounds such as guaiacol and dimethoxybenzenes. The experiments were carried out under supercritical conditions at 250 °C using 2-PrOH as the only hydrogen donor. Ni-SiO2 and NiCu-SiO2 were synthesized using the eco-friendly original method based on supercritical antisolvent coprecipitation. It has been found that guaiacol is rapidly converted into 2-methoxycyclohexanol and cyclohexanol, while the presence of Cu impedes the formation of the latter product. Transformations of dimethoxybenzene position isomers are slower and result in different products. Thus, 1,3-dimethoxybenzene loses oxygen atoms transform into methoxycyclohexane and cyclohexanol, whereas the saturation of the aromatic ring is more typical for other isomers. The Cu addition increases specific catalytic activity in the TH of 1,2-and 1,3-dimethoxybenzene compared to the Cu-free catalyst

Advanced High-Loaded Ni–Cu Catalysts in Transfer Hydrogenation of Anisole: Unexpected Effect of Cu Addition

Binary Ni–Cu heterogeneous catalysts are known to demonstrate excellent activity in conventional hydrogenation of phenolic compounds, and Cu addition facilitates hydrodeoxygenation (HDO). In this study, we aimed to show the effect of Cu on the specific catalytic activity and selectivity of Ni–Cu catalysts in transfer hydrogenation, in which 2-PrOH was used as a solvent and an H donor. Catalytic transformations of anisole were studied in sub- and supercritical alcohol at 150 and 250 °C. The catalysts were prepared using an environmentally friendly supercritical antisolvent coprecipitation method, which makes it possible to obtain well-dispersed particles (less than 7 nm) at high metal loading (up to 50 wt.%). When copper is added, deactivation of the catalyst in transformations of anisole, including HDO, is observed. The experimental data and the appropriate kinetic analysis demonstrate that there is a decrease in the rate of anisole conversion accompanied by an increase in the concentration of acetone formed during the dehydrogenation of 2-PrOH

Correlation between Asphaltene Stability in n-Heptane and Crude Oil Composition Revealed with Chemical Imaging

Five crude oil samples with different physical properties have been studied with respect to asphaltene stability. The attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopic imaging approach of n-heptane-induced precipitation has been used to monitor crude oil behaviour under dilution with a flocculation agent. For each sample, the dynamics of asphaltene precipitation has been observed by applying this chemical imaging method. Based on these data, the stability of crude oil samples has been compared and the correlation between asphaltene stability and crude oil properties has been proposed

Transformation of Petroleum Asphaltenes in Supercritical Alcohols Studied via FTIR and NMR Techniques

The aliphatic alcohols (methanol, ethanol, and 1- and 2-propanols) were used for the first time as a reaction media for the upgrading of crude oil asphaltenes. The process was realized in a batch reactor under supercritical conditions (at 350 °C). The three main fractions of the products (hexane- and benzene-soluble fractions, HSF and BSF, and insoluble residue, IR) were analyzed using attenuated total reflection Fourier tranform infrared (ATR-FTIR) and ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy to characterize structural changes of the initial asphaltenes (IA). According to NMR data, the aliphatics are the main part of the hexane-soluble fraction (HSF) and benzene-soluble fraction (BSF). The alcohols were appeared to influence the content of both aliphatics and aromatics in the products. The content of aliphatics in the HSF increases in the line from “lighter” to “heavier” alcohols used but reduces in the BSF. However, the content of aromatics in the HSF increases from “heavier” to “lighter” alcohols, while this order is reversed for the BSF. According to the ATR-FTIR spectroscopy data, the aromatics-to-aliphatics ratios observed for the insoluble residues are 2–3 times higher as compared with the initial asphaltenes but 2 times lower for the HSF. The BSF are composed of less-condensed aromatics than those of the IA. It is shown that the alcohols used as a reaction media are incorporated in the product molecules as alkoxy substituents in aromatic ethers Ar–OAlk. According to NMR and ATR-FTIR data obtained, the alkylation–dealkylation and alkoxylation reactions make a crucial contribution to the chemical transformations of the asphaltenes

Synthesis of Co-Ni Alloy Particles with the Structure of a Solid Substitution Solution by Precipitation in a Supercritical Carbon Dioxide

Mixed Co-Ni bimetallic systems with the structure of a solid substitution solution have been synthesized using the supercritical antisolvent precipitation (SAS) method, which uses supercritical CO2 as an antisolvent. The systems obtained have been characterized in detail using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Fourier-transform infrared (FTIR) spectroscopy, and magnetostatic measurements. It has been found that Co-enriched systems have a defective hexagonal close-packed (hcp) structure, which was described by a model which embedded cubic fragments of packaging into a hexagonal close-packed (hcp) structure. It has been shown that an increase in water content at the precipitation stage leads to a decrease in the size of cubic fragments and a more uniform distribution of them in Co-enriched systems. It has also been shown that mixed systems have the greatest coercivity in the line of samples. Ni-enriched bimetallic systems have a cubic close-packed (ccp) structure with modified crystal lattice parameters

Synthesis of Catalytic Precursors Based on Mixed Ni-Al Oxides by Supercritical Antisolvent Co-Precipitation

Mixed Ni-Al oxide catalytic precursors with different elemental ratios (20, 50, and 80 wt.% Ni0) were synthesized using green supercritical antisolvent co-precipitation (SAS). The obtained oxide precursors and metal catalysts were characterized in detail by X-ray diffraction (XRD) analysis, atomic pair distribution function (PDF) analysis, CO adsorption, and high-resolution transmission electron microscopy (HRTEM). It was found that the composition and structure of the Ni-Al precursors are related to the Ni content. The mixed Ni1−xAlxO oxide with NiO-based crystal structure was formed in the Ni-enriched sample, whereas the highly dispersed NiAl2O4 spinel was observed in the Al-enriched sample. The obtained metal catalysts were tested in the process of anisole H2-free hydrogenation. 2-PrOH was used as a hydrogen donor. The catalyst with 50 wt.% Ni0 demonstrated the highest activity in the hydrogenation process

CVD synthesis of multi-layered polycrystalline diamond films with reduced roughness using time-limited injections of N2 gas

Multi-layered polycrystalline diamond (PCD) films were synthesized using microwave plasma-assisted chemical vapor deposition (CVD) with periodical addition (injections) of N2 gas to the standard CH4-H2 gas mixture. The aim of such an approach was to reduce the roughness of the films while preserving the overall high quality and phase purity of the PCD material. The thicknesses of the films were in the range of 5 to 51 μm, while the number of layers was from 1 to 15. The introduction of even the smallest amount of nitrogen leads to a significant (more than 2-fold) increase in the growth rate of PCD films. Optimized injection regimes allowed the reduction of the relative roughness (Sq/thickness) of the PCD films by more than 3 times in comparison with standard microcrystalline diamond film grown under similar conditions without N2 addition. The proposed method of periodic injection of N2 during growth restricted the formation of continuous NCD layers, which improved the overall sp3/sp2 ratio in comparison with standard multi-layered MCD/NCD materials. The obtained multi-layered PCD materials with reduced roughness may be used for the formation of protective and hard covers, optical coatings, electrochemical and thermal management applications. Prime novelty statement The multi-layered PCD films were synthesized in a microwave plasma CVD in regimes with short-term periodic N2 injections in CH4-H2 process gas; the average growth rate is doubled owing to the pulsed nitrogen injection, while the surface roughness is reduced by more than 3 times in comparison with a standard (no N2 injection) microcrystalline film