Renewable fuels have been widely developed in recent decades. Products derived from the processing of biological feedstocks have a lower carbon footprint than conventional petroleum products due to the absorption of carbon dioxide during the cultivation phase. Technologies for co-processing petroleum and renewable feedstocks are of particular interest due to their ease of integration into refineries. However, renewable feedstocks are not necessarily allocated to products according to the material balance of processing products separately. There is a problem in determining which part of the renewable carbon has gone into which fractions. This paper provides a comparative description of the methods for determining bioorganic carbon in petroleum products. The article considers the accuracy, technical and technical-economic parameters of both standardized and experimental methods for determining the biocarbon content. The Alpha Magnetic Spectrometer (AMS) method is characterized by high accuracy and a shorter analysis time. However, the cost of the necessary equipment is significantly higher than that of other methods. The Liquid-Solid Chromatography (LSC) method is less precise and more cost-effective but requires a longer analysis time. The Isotope-Ratio Mass Spectrometry (IRMS) method offers a combination of the advantages, yet it is constrained by notable limitations in terms of the identified feedstocks. An assessment of the possibility of introducing such methods at enterprises engaged in co-processing is given, as a result of which the most optimal method for determining biocarbon is the direct LSC method.

The influence of microwave treatment on the structural characteristics of MCM-41 silica-based supports and properties of Ru-containing catalysts prepared thereon was investigated. The 800 W and 20 min mode of microwave treatment inevitably destroyed MCM-41 silica structure during the deposition of ruthenium particles. When moderate irradiation power to 400 W and duration time to 10 min, the destruction of the support was partially prevented, but the ruthenium loading reduces, simultaneously. To reinforce MCM-41 silica halloysite nanotubes (Hal) were introduced as a matrix for templated self-assembly of mesoporous silica, thereby forming ordered hierarchical MCM-41/Hal composite. The beneficial effect of Hal on the structural properties and stability of MCM-41 support under microwave-assisted Ru impregnation was demonstrated. MCM-41/Halsupported catalysts revealed enhanced textural properties and characteristics of active component (high metal loading, narrow particle size distribution, high dispersion) compared to the analogous based on pure MCM-41. The catalytic properties were estimated in hydrogenation of multi-component aromatics-containing model feed, and Ru/MCM-41/Hal catalyst reveals 100 % benzene and ca. 89-90 % ethylbenzene and toluene conversion at the temperature range of 100-150 degrees & Scy; for 3 h.

Hierarchical composite with halloysite nanotubular core and MCM-41 shell was synthesized and applied as a support for the CoMoS catalyst. This clay-based aluminosilicate combines the advantages of ordered silica with high specific surface and halloysite nanotubes (HNTs) having transport hollow cavity and acting as reinforcing component for mesoporous arrays. The properties of the supports and catalysts were investigated by XRD, TPDNH3, TPR-H2, FTIR Py, TEM, XPS and N2 adsorption methods. The composite-supported sulfide catalyst reveals a hierarchical pore arrangement with a high dispersion of active particles provided by the confinement effect of MCM-41 silica and HNTs. The catalyst has an enhanced activity in hydrotreating, and at 340 C the content of sulfur and polyaromatics was reduced to 14 ppm and 0.69 wt%, respectively. The reaction rate constant over CoMoS/MCM-41/HNT catalyst is 20.5 (gS)-0.4/g (l-0.4h), whereas activation energy of 114 kJ*mol-1 is close to that for alumina-supported reference sample, indicating the efficiency of mass transfer.

Heterogeneous catalysts play a crucial role in the petrochemical synthesis and oil refining industries [...]

One of the steps in scaling the technology for the synthesis of zeolite-containing catalysts from the laboratory to commercial level is support forming. In this study, halloysite nanotubes and aluminum oxide were used as binders for preparing a support based on MFI (ZSM-5) zeolite. The Pt catalysts (Pt/ZSM-5/Al2O3 and Pt/ZSM-5/Hall) were tested in isomerization of the aromatic C8 fraction. The forming of supports influenced not only mechanical but also physicochemical properties of the catalysts. On introducing binders into the catalytic system, the fraction of mesopores in the total pore volume of the supports increased, the acidity of the samples decreased, and the ratio of the amounts of the weak and strong acid sites changed. The use of aluminum oxide and halloysite as binders leads to different pathways of the transformation of the aromatic feedstock. The main side reactions observed in the presence of Pt/ZSM-5/Al2O3 and Pt/ZSM-5/Hall catalysts are hydrocracking of alkylaromatic hydrocarbons and their transalkylation/disproportionation, respectively. The best results were obtained at 380°C and feed space velocity of 6 h–1 with Pt/ZSM-5/Hall: p-/о-xylene ratio 1.05, loss of xylenes 4.31

The development of active and stable catalysts for liquid-phase hydrodeoxygenation (HDO) of bio-oil derived from lignocellulose is challenging. We have proposed a strategy for the design of Ni- and Pt-containing catalysts supported on halloysite nanotubes hydrophobized with organic silanes. The hydrophobization of aluminosilicate nanotubes promotes the fixation of active nanoparticles on the inner surface of the halloysite, providing stability to the obtained catalytic systems under HDO conditions. The activity of the catalysts obtained was studied in the HDO of model bio-oil compounds in batch reactors at temperatures of 120-180 degrees C, a hydrogen pressure of 3 MPa and a molar ratio of reagent to metal of 200, using water as the solvent. A Pt/HNT-S16 catalyst, based on the hexadecyltriethoxysilane-modified halloysite, showed a high activity (TOF = 905 h-1) and increased stability (TON = 522) in an aqueous environment in the HDO of anisole (10 wt% aqueous solution). Waterproof catalysts supported on hydrophobized halloysite nanotubes for hydrodeoxygenation of bio-oil aromatics compounds derived from lignocellulose.

The quality and durability of road surfaces have long been an area of interest for researchers all over the world, who are trying to prolong life of service of roads and cut the additional expenses. The quality of bitumen, one of the most important parts of road building materials, can be improved with various modifiers, lots of which have been introduced and used commercially for a long time. This paper studies bio-oil obtained in the process of slow pyrolysis of sawdust as a sustainable modifier for bitumen production. Adhesive properties of bitumen produced by different methods of bio-oil introduction into the material are studied, as well as some of the no-harm characteristics. It was found that introducing both bio-oil and its fraction boiling above 350 degrees & Scy; directly into bitumen leads to a rise in adhesion rate (up to 91.52 % for unfractionated bio-oil and 79.98 % for bio-oil >350 degrees & Scy; fraction vs. 62.88 % for base bitumen). However, adding >350 degrees & Scy; fraction of bio-oil proved to deteriorate the bitumen's rheological characteristics, such as ductility and penetration, while adding bio-oil made bitumen fail the ageing test (mass change). The addition of bio-oil in the amount of 1 wt% into vacuum, residue showed to have a limited effect on the adhesion properties of the resulting oxidized bitumen, while passing both no-harm and ageing tests. The results reported that the optimal concentration of bio-oil added to bitumen in the case of the current study was 2-3 wt%, since it is at this share of the modifier that the binder shows peak adhesion indicators of the adhesion with the mineral surface.

High quality synthetic fuels could be obtained using the Fischer-Tropsch process. Development of new catalysts for this process is very important for the selective formation of fuel fractions. RuCo catalysts prepared by modifying the support with ethylenediaminetetraacetic acid, urea, acetone azine, or citric acid was investigated for the first time in order to see the effect of the ligand on the catalytic properties of the bimetallic system. The catalysts were characterized by TEM, STEM, XRF, H2-TPR, NH3-TPD, and XPS. It was assumed that total acidity, reducibility, dispersion and atomic surface composition of the catalysts are dependent on the ligands used. The catalyst obtained after modification of Al2O3 with citric acid was characterized by low activity and the predominant formation of solid paraffins. The use of EDTA resulted in a highly active catalyst with highest selectivity to gasoline. Catalyst modified with acetone azine showed a high alpha (0.898) as well as a selectivity to the diesel fraction of 64.1 %, but average CO conversion of 23.3 %. The optimal catalytic system among those studied was Ru/Co/Al2O3-urea. This system had a high conversion rate of 37.3 % and a selectivity towards C5+ hydrocarbons of 79.4 %. The diesel fraction was also produced in high yield.

–CoMo sulfide catalysts supported on aluminosilicate halloysite nanotubes (CoMoS/HNT) and on dealuminated halloysite nanotubes (CoMoS/HNT(deAl)) were synthesized by incipient wetness impregnation using pseudoboehmite as a binder. Both the supports and related catalysts were characterized by low-temperature nitrogen adsorption, energy dispersive X-ray fluorescence analysis, temperature-programmed reduction by hydrogen, FTIR spectroscopy of adsorbed pyridine, transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalyst samples were further tested in hydrotreating of diesel feedstocks. Dealumination of halloysite was found to increase the area of Si-enriched surface segments, thus weakening interaction between the sulfide phase and the support and, hence, increasing the content of highly active sulfide particles. In the case of a mixed feedstock, CoMoS/HNT(deAl) + Al2O3 achieved a reaction rate constant of 0.605 ppm S–0.4/g(L–0.4 h) compared to 0.429 ppm S–0.4/g(L–0.4 h) for an alumina-supported sample.

This review discusses recent advances in catalytic hydrodeoxygenation of lignocellulosic biomass. Lignocellulosic biomass is the most promising plant-based raw material for the production of liquid engine fuels or individual petrochemical monomers. Among the several existing techniques for biomass processing, pyrolysis offers superior efficiency. Given that the bio-oil produced by biomass pyrolysis has unsatisfactory performance characteristics caused by the presence of oxygenates, this bio-oil cannot be used directly as a fuel. Hydrodeoxygenation using selective catalysts is able to reduce the oxygen content in bio-oil and to improve its performance characteristics. To this end, bifunctional catalysts that contain active metal sites on an acid support hold promise. Noble metals (e.g., Pt, Pd, and Ru) and/or transition metals (e.g., Ni, Co, and Mo), as well as sulfides and phosphides of transition metals, can be used as an active catalytic phase. Metal oxides (e.g., ZrO 2 , CeO 2 , Al 2 O 3 , and TiO 2 ), carbon, zeolites (e.g., ZSM-5, Y, Beta, and SAPO-11), and mesoporous silica-based materials (e.g., SBA-15 and MCM-41) have been most often used as supports in hydrodeoxygenation catalysts. However, the implementation and upscaling of the hydrodeoxygenation of biomass pyrolytic bio-oil is limited because of the rapid deactivation of the catalyst in the presence of water, due to sintering and leaching the active phase with acidic components of bio-oil. Therefore, the development of catalysts that would provide high activity and stability under bio-oil hydrodeoxygenation conditions has become one of the most pressing issues for the petrochemical industry.

The present study investigates a series of gallium-based catalysts supported on natural and composite aluminosilicate mesoporous supports in the CO2-assisted oxidative dehydrogenation of propane. The catalyst supports were prepared by mixing a functional material with a boehmite binder, the functional materials being derived from natural halloysite nanotubes (HNTs). Three different supports were used: pristine HNTs; HNTs with MCM-41 synthesized around halloysite; and HNTs with MCM-41 synthesized inside the halloysite lumen. The CO2-assisted oxidative propane dehydrogenation was tested in the range of 550–700°C at a CO2/C3H8 molar ratio of 2.0. All the catalysts showed comparable propane conversion (from 10–13

Halloysite nanotubes (HNTs) is a promising support for liquid-phase hydrodeoxygenation (HDO) catalysts due to a wide abundance, low cost and tunable properties. Acid etching of halloysite by sulfuric acid was found to enlarge lumen diameter (24.3 nm), enhance specific surface area (154 m2/g) and acidity (0.343 mmol/g). Based on pristine and dealuminated HNTs, Ru-containing catalysts were synthesized via impregnation under micro-wave irradiation. The catalytic properties of synthesized catalysts in HDO of guaiacol were studied in batch reactors at 120-180 degrees C, under hydrogen pressure of 3 MPa, with guaiacol/Ru molar ratio of 200 in water as a solvent. Comparing the results of catalytic tests, we have concluded that the catalysts based on etched halloysite enhanced greater activity (TOF - 211 h-1) in the HDO of guaiacol compared their analogue supported on pristine HNTs. Moreover, the Ru-catalyst based on etched HNTs contributed to an increase selectivity to hydrogenolysis with effective oxygen removal.

Carvone belongs to the chemical family of terpenoids and is the main component of various plant oils. Carvone and its hydrogenated products are used in the flavouring and food industries. A quantitative thermodynamic analysis of the general network of carvone hydrogenation reactions was performed based on the thermochemical properties of the starting carvone and all possible intermediates and end products. The enthalpies of vaporisation, enthalpies of formation, entropies and heat capacities of the reactants were determined by complementary measurements and a combination of empirical, theoretical and quantum chemical methods. The energetics and entropy change in the hydrogenation and isomerisation reactions that take place during the conversion of carvone were derived, and the Gibbs energies of the reactions were estimated. It was shown that negative Gibbs energies are recorded for all reactions that may occur during the hydrogenation of carvone, although these differ significantly in magnitude. This means that all these reactions are thermodynamically feasible in a wide range from ambient temperature to elevated temperatures. Therefore, all these reactions definitely take place under kinetic and not thermodynamic control. Nevertheless, the numerical Gibbs energy values can help to establish the chemoselectivity of catalysts used to convert carvone to either carvacarol or to dihydro- and terahydrocarvone, either in carvotanacetone or carveol.

Selective hydrogenation of vinyl groups (C = C) and carbonyl groups (C = O) is of significance to effectively convert low-value organic compounds into high-value target chemicals, while a challenge remains on the hydrogenation of C = C bond that is in π-bond conjugation with the C = O bond. Herein, we address this challenge based on a synergetic modulation strategy on electronic structure and adsorption configurations to achieve a highly selective hydrogenation of the C = C bond, achieved by laser-assisted embedding of PdxCu bimetals in the ZIF-8 bulk phase (x represents the Pd/Cu molar ratio in PdCu nanoparticles). It is revealed that laser assisted synthesis of PdxCu bimetals not only inhibits the hydrogenation of C = O and promotes the hydrogenation of C = C, but also results in an arched absorption configuration for substrate molecules that facilitates the selective hydrogenation of vinyl groups. Exemplified by cinnamaldehyde (CAL), the present work achieves 98.03 % conversion of CAL and 100 % selectivity of the hydrocinnamaldehyde (HCAL) (70 °C, 1 MPa H2, 1 h), indicating the potential of laser-matter interaction to tackle the trade-off between conversion efficiency and selectivity in thermal catalysis.

Selective hydrogenation of vinyl groups (C = C) and carbonyl groups (C = O) is of significance to effectively convert low-value organic compounds into high-value target chemicals, while a challenge remains on the hydrogenation of C = C bond that is in it-bond conjugation with the C = O bond. Herein, we address this challenge based on a synergetic modulation strategy on electronic structure and adsorption configurations to achieve a highly selective hydrogenation of the C = C bond, achieved by laser-assisted embedding of PdxCu bimetals in the ZIF-8 bulk phase (x represents the Pd/Cu molar ratio in PdCu nanoparticles). It is revealed that laser assisted synthesis of PdxCu bimetals not only inhibits the hydrogenation of C = O and promotes the hydrogenation of C = C, but also results in an arched absorption configuration for substrate molecules that facilitates the selective hydrogenation of vinyl groups. Exemplified by cinnamaldehyde (CAL), the present work achieves 98.03 % conversion of CAL and 100 % selectivity of the hydrocinnamaldehyde (HCAL) (70 degrees C, 1 MPa H2, 1 h), indicating the potential of laser-matter interaction to tackle the trade-off between conversion efficiency and selectivity in thermal catalysis.

Silanized aluminosilicate halloysite nanotubes were investigated as a support for Pd–Ag catalysts. The samples were characterized by low-temperature nitrogen adsorption, ammonia temperature-programmed desorption, and transmission electron microscopy, and tested in selective hydrogenation of acetylene. The Pd–Ag/halloysite catalysts synthesized from [Pd(NH3)4]Cl2 as a palladium precursor proved to be the most selective towards ethylene: the selectivity reached about 85

Effective and low-cost gram-scale Ru-containing catalysts for removal of aromatics from the gasoline fraction while retaining the octane number.

The MOR-type zeolite was synthesized by a template-free method using natural aluminosilicate halloysite nanotubes (HNT) as a hard template and a source of aluminum and silicon. Samples were studied using a complex of physicochemical methods of analysis: XRD, TEM, N2 physisorption, NH3-TPD and XRF. Specific BET surface area of MOR prepared using HNT is 306 m2/g, mesopores in the MOR:HNT accounted for 30 % of the total pore volume. Based on the synthesized materials (MOR, MOR:HNT and MOR + HNT), Pt-containing catalysts were prepared. The catalysts were investigated in the gas-phase isomerization of C-8 aromatic fraction in a temperature range of 360-420 degrees C, varying LHSV from 2 to 6 h-1, at H2 pressure of 1 MPa and hydrogen/ feedstock volume ratio of 900 nl/l. The prepared catalysts demonstrated strong activity in ethylbenzene trans-formation (more than 95 %), while providing a high yield of p-xylene (more than 95 % of thermodynamic value).

Pd nanoparticles are widely applied in catalysis. In this work, the deposition of Pd nanoparticles onto halloysite (Hal) nanotubes from different Pd precursors and solvents has been investigated. The prepared Pd/Hal catalysts have been characterized by low-temperature N2 adsorption, transmission electron microscopy, zeta potential measurement, and tested in the hydrogenation of acetylene. On calcined Hal, the largest nanoparticles are formed in acid media, and the smallest are formed in non-aqueous one. Silanization of halloysite decreases absolute values of its zeta potential significantly and drops PdNPs size twice. Catalytic tests have shown that acetylene conversion and selectivity to ethylene depend on the deposition method, and the most active catalysts were prepared from Pd acetate dissolved in acetone. The lowest activity and highest selectivity to ethylene were demonstrated by the azine-modified halloysite, that could be related to Pd poisoning with nitrogen.