M. P. Boronoev

Platinum and palladium nanoparticles in modified mesoporous phenol—formaldehyde polymers as hydrogenation catalysts

Mesoporous polymeric supports modified with sulfo groups and PPI dendrimers have been prepared. Catalysts containing palladium and platinum nanoparticles have been synthesized on their basis. The resulting catalysts have been studied by transmission electron microscopy and X-ray photoelectron spectroscopy. It has been shown that the metal deposition procedure has an effect on the morphology of the resulting catalyst. Catalytic activity has been studied using the example of the hydrogenation of phenylacetylene and naphthalene at temperatures of 80 and 400°C, and pressures of 1.0 and 5.0 MPa, respectively.

Hydroprocessing of Aromatics Using Sulfide Catalysts Supported on Ordered Mesoporous Phenol–Formaldehyde Polymers

Ni–W sulfide catalysts for the hydroprocessing of aromatic hydrocarbons were synthesized by the in situ decomposition of tetrabutylammonium nickel thiotungstate complex supported on ordered mesoporous phenol–formaldehyde polymer. Catalysts obtained with and without additional sulfidation with dimethyl disulfide were characterized by X-ray photoelectron spectroscopy and transmission electron microscopy. The catalytic activity has been studied using naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, and anthracene as examples. It is shown that the system used in this study proved to be active in hydrogenation and hydrocracking of polyaromatic hydrocarbons.

Hybrid catalysts based on platinum and palladium nanoparticles for the hydrogenation of terpenes under slurry conditions

Catalysts based on platinum and palladium nanoparticles immobilized in mesoporous phenolformaldehyde polymers modified with sulfo groups have been used for the hydrogenation of a number of terpenes, such as (S)-(–)-limonene, α-terpinene, γ-terpinene, and terpinolene. It has been found that Pd-containing catalysts exhibit higher activity in the exhaustive hydrogenation of terpenes, whereas Pt-containing catalysts have high selectivity for p-menthene.

Nickel–molybdenum sulfide catalysts supported on an ordered mesoporous polymer for hydrogenating–hydrocracking of model biaromatic petroleum compounds

Nickel–molybdenum sulfide catalysts have been synthesized in situ in a hydrocarbon medium by the decomposition of the [(n-Bu)4N]2Ni(MoS4)2 precursor complex supported on an ordered mesoporous phenol–formaldehyde polymer in the presence of a sulfiding agent (dimethyl disulfide). The catalytic properties of the samples have been studied in a batch reactor at 380°C and a hydrogen pressure of 5.0 MPa using the example of naphthalene, 1-methylnaphthalene, and 2-methylnaphthalene. The tests have shown that the conversion of biaromatic substrates is close to quantitative and the use of dimethyl disulfide as a sulfiding agent leads to an increase in the amount of complete hydrogenation products, as evidenced by the high content of the active phase in this case.

Bimetallic sulfide catalysts based on mesoporous organic supports in the hydrofining of light cycle oil

Bimetallic sulfide hydrodearomatization–hydrodesulfurization catalysts based on mesoporous organic supports made of phenol-formaldehyde resins (MPF) and porous aromatic frameworks (PAFs) have been synthesized. The catalysts exhibit high activity in the hydroconversion of light cycle oil: the sulfur content decreases from 3500 to 390 ppm within 8 h of reaction at a hydrogen pressure of 5 MPa and a temperature of 380°C.

Hydroconversion of Naphthalene in the Presence of NiMoS/NiWS-AlCl 3 Catalyst Systems Derived from Mesoporous Aromatic Frameworks

A catalyst containing aluminum chloride supported on a mesoporous aromatic framework (PAF) was synthesized. The effect of the PAF-AlCl3 catalyst on the products of the hydrogenation-hydrocracking of naphthalene in the presence of PAF-NiMoS and PAF-NiWS bimetallic catalysts was studied. The addition of PAF-AlCl3 markedly enhances the yield of reaction products and the best naphthalene conversion results were obtained by adding sulfur to the reaction mixture. Thus, naphthalene can be hydroconverted quantitatively to reaction products, 70% of which are the result of hydrogenation and 30% the result of cracking, using the PAF-NiMoS/PAF-AlCl3 (1:3.3 wt. ratio) catalyst system.

Mesoporous organo-inorganic hybrid materials as hydrogenation catalysts

Abstract The paper concerns application of two types of organic materials – porous aromatic frameworks (PAFs) with diamond-like structure and the ordered mesoporous phenol-formaldehyde polymers (MPFs) – as supports for metal and metal sulfide nanoparticles. The obtained hybrid materials were tested in hydrogenation of various unsaturated and aromatic compounds. Ruthenium catalyst, based on PAF (Ru-PAF-30), possessed high activity in exhaustive hydrogenation of phenol into cyclohexanol with TOF value of 2700 h−1. Platinum catalyst, based on modified with sulfo-groups MPF (MPF-SO3H-Pt), was selective in semi-hydrogenation of terpenes, [α-terpinene, γ-terpinene, terpinolene, (s)-limonene]. Bimetallic Ni–W sulfide catalysts, prepared by in situ decomposition of [(n-Bu)4N]2Ni(WS4)2 within the pores of MPFs and PAFs, possessed high efficiency in hydrogenation-hydrocracking of naphthalenes as model substrates.

Guaiacol Hydrogenation in an Aqueous Medium in the Presence of a Palladium Catalyst Supported on a Mesoporous Dendrimer-Containing Polymer

Guaiacol hydrogenation in an aqueous medium in the presence of a palladium catalyst supported on a mesoporous dendrimer-containing polymer and the effect of addition of sulfuric acid to the catalyst system have been studied. It has been found that the main hydrogenation product is 2-methoxycyclohexanol. After the addition of sulfuric acid to the catalyst system, the reaction mechanism significantly changes and cyclohexanol becomes the main hydrogenation product.

Alkylation of Aromatic Compounds in the Presence of Catalysts Based on Mesoporous Phenol–Formaldehyde Polymers

A catalyst based on a mesoporous phenol–formaldehyde polymer (MPF) as an organic support modified with the IMHSO4 ionic liquid has been synthesized. The catalytic activity of the sample has been studied in the alkylation of aromatic compounds with octene-1. It has been found that the use of the catalyst in phenol alkylation leads to the formation of both alkylphenols (C-alkylates) and alkyl phenyl ethers (O-alkylates) with a total yield of up to 60%. In the case of alkylation of benzene and benzene derivatives, significant conversion values (45–50%) are achieved only for toluene and anisole.

Hydrogenation of Unsaturated Hydrocarbons on Platinum and Palladium Catalysts Encapsulated in Mesoporous Bakelites

Syntheses are reported for catalysts derived from platinum and palladium nanoparticles supported on a mesoporous phenol formaldehyde polymer modified by an ionic liquid. These catalysts are used for the hydrogenation of unsaturated compounds, specifically, acyclic and cyclic isoprenoids: isoprene, 2,5 – dimethyl–2,4–hexadiene, limonene, α –terpinene, γ –terpinene, as well as phenylacetylene, transstilbene, and 1,4–diphenyl–1,3–butadiene. High activity was found for these catalysts in hydrogenation reactions. The palladium catalysts were more active than their platinum analogs. The products of complete hydrogenation predominate in the hydrogenation of isoprenoids on the palladium catalysts, while monoene products predominate in the reactions on platinum catalysts.