Propene Formation Research Articles

Regularities of the formation of cool-flame oxidation products of rich propane-oxygen mixtures in a two-section reactor

The effect of the ratio of the reagents on a stabilized cool flame of rich propane-oxygen mixtures is investigated. It was found that with an increase in the initial concentration of propane in the mixture, its consumption, as well as the concentration of propylene, has a maximum a ratio of C3H8 : O2 = 1 : 1. In this case, the selectivity of propylene formation reaches a maximum a ratio of C3H8 : O2 = 4 : 1. It is shown that an increase in the initial propane concentration in the mixture increases the yield of methane, but reduces the yield of propylene, ethylene, hydrogen, CO, CO2, methanol, formaldehyde and acetaldehyde. At a ratio of C3H8 : O2 = 6 : 1, ethane was also found in the reaction products. The possibility of ethanol formation in the reactions of ethoxyl and hydroxyethyl radicals with acetaldehyde has been analyzed using the CBS-QB3 quantum-chemical method.

Synthesis and Photoelectrochemical Properties of Copper Titanate for Pollutant Removal

Copper species are considered one of the materials capable of converting pollutants in add-products values. However, its stability is a challenge when applied in photoelectrocatalytic (PEC) processes. A promissory alternative is to couple copper species with other materials improving their chemical stability, such as TiO2, an p-type semiconductor with excellent charge transfer. The insertion of Cu atoms into the titanium crystal lattice can promote the formation of stable binary copper oxides and/or the production of ternary/quaternary oxides by sharing oxygen between the species1,2. In addition, the presence of TiO2 on CO2 conversion may lead to the reactions for methanol and ethanol formation due to its property to favor the generation of hydroxyl radicals (OH•) and H+ from the oxidation of water. Then, in the present work carried out the preparation of n-type ternary oxide semiconductor based in copper and titanium oxides. Cu–O–Ti was synthesized by a time-efficient, arc-melting method from TiO2 and Cu2O. The particulate product showed in its composition mixture between TiCu2O3 / TiCu3O5 and high crystalline phase. These ternary oxides presented a broad-band absorption in the UV−visible spectral region with absorbance coefficient located at 675 nm. Also, the material showed thermal stability up to ∼475 °C, and cathodic photoelectrochemical activity. Controlled thermal oxidation of copper from the Cu (I) to Cu (II) oxidation state showed that the crystal lattice could accommodate Cu2+ cations up to ∼475 °C, beyond which the compound was converted to CuO and TiCuO3. This process was monitored by powder X-ray diffraction and X-ray photoelectron spectroscopy. The mott-Schottky plots for this ternary oxide exhibited a decrease of capacitance indicating an increase of CO2 absorbing active sites. The efficiency of photocatalyst was evaluated by PEC experiments to CO2 conversion into alcohols. The experiments were carried out bubbling CO2 in 1.0 Mol L-1 NaHCaO3. The ternary oxide favored the ethanol and propane formation, as the final product, exhibiting high selectivity and concentration. Keywords: ternary copper oxide, copper titanate, arc synthesis, p-type semiconductor, photoelectrochemistry, CO2 conversion, C2 products formation.

Progressive Fabrication of a Pt‐Based High‐Entropy‐Alloy Catalyst toward Highly Efficient Propane Dehydrogenation

AbstractHigh‐entropy alloys (HEAs) have emerged as burgeoning heterogeneous catalysts due to their vast material space, unique structure, and superior stability. However, the dominant trial‐and‐error approaches hamper the exploration of efficient catalysts, necessitating the development of rational design strategies. Here, we report a progressive approach to the design and fabrication of HEA catalysts guided by alloying effects toward propane dehydrogenation. Cu, Sn, Au, and Pd are selected and demonstrated to induce dilution, encapsulation, surface enrichment, and inhomogeneity effects on Pt. The fabricated HEA, PtCuSnAuPd/SiO2, exhibits excellent activity, selectivity, and stability. The propylene formation rates reach 256 and 390 molC3H6 gPt−1 h−1 at 550 and 600 °C, respectively. Systematic characterizations reveal that the random elemental mixing, structural stability, and high Pt exposure promote the exposure of abundant stable isolated Pt sites. This work comprehensively explores the rational design and fabrication of HEA catalysts from a unique perspective, offering opportunities for developing advanced catalysts.

Progressive Fabrication of a Pt-Based High-Entropy-Alloy Catalyst toward Highly Efficient Propane Dehydrogenation.

High-entropy alloys (HEAs) have emerged as burgeoning heterogeneous catalysts due to their vast material space, unique structure, and superior stability. However, the dominant trial-and-error approaches hamper the exploration of efficient catalysts, necessitating the development of rational design strategies. Here, we report a progressive approach to the design and fabrication of HEA catalysts guided by alloying effects toward propane dehydrogenation. Cu, Sn, Au, and Pd are selected and demonstrated to induce dilution, encapsulation, surface enrichment, and inhomogeneity effects on Pt. The fabricated HEA, PtCuSnAuPd/SiO2, exhibits excellent activity, selectivity, and stability. The propylene formation rates reach 256 and 390 molC3H6 gPt-1 h-1 at 550 and 600 °C, respectively. Systematic characterizations reveal that the random elemental mixing, structural stability, and high Pt exposure promote the exposure of abundant stable isolated Pt sites. This work comprehensively explores the rational design and fabrication of HEA catalysts from a unique perspective, offering opportunities for developing advanced catalysts.

Hydrodeoxygenation of Glycerol to Propene Over Molybdenum and Niobium Phosphate Catalysts

AbstractIn single‐step conversion of glycerol to propene, the intricate catalytic pathways with molybdenum and niobium catalysts remain elusive. While these catalysts can effectively accelerate the hydrogenolytic cleavage of the glycerol CO bonds, resulting in a high selectivity to propene, the routes have not been thoroughly studied. This study explores the reaction routes and the role hydrogen plays in determining the product distribution. The hydrodeoxygenation (HDO) of glycerol was investigated using various glycerol purities in both batch and continuous reaction modes. Remarkably, Mo(PO4)x and Nb(PO4)x demonstrated catalytic performance with raw glycerol, indicating that impurities had no detrimental effect on the catalyst's activity. In batch mode, a propene selectivity of 53% was achieved over Mo(PO4)x as the catalyst, highlighting the catalyst's stability under these conditions. In continuous operation, the highest product selectivity to propene (12%) was observed at low temperatures (573 K), while more C2 to C6 alkanes were formed at increased temperatures (623 and 673 K). Whereas a hydrogen atmosphere promotes formation of 2‐propenol, as primary precursor to propene, an inert atmosphere leads to increased formation of propanal and dissociation products. Our work has elucidated new routes to upcycle biorenewable glycerol to propene over Mo(PO4)x and Nb(PO4)x catalysts.

Revealing mechanisms for the formation of acetone and propanal in the acetoxylation of propylene on PdCu catalysts combined DFT with kMC analysis

1,4-butanediol has attracted much attention and Lyondell method is a competitive production technology due to its wide range of feedstock sources, in which the acetoxylation of propylene to allyl acetate on PdCu catalysts is an essential step. By combining Density Functional Theory and kinetic Monte Carlo simulations, the formation mechanisms and pathways of byproducts acetone and propanal in the acetoxylation of propylene to allyl acetate on PdCu catalysts were systematically investigated. Most species tend to be adsorbed on Pd atoms, which is consistent with that Pd atoms are main active sites. Acetone is obtained by the hydrogenation of CH3COCH2*, which comes from the oxidation and then dehydrogenation of propylene. Propanal is produced by the hydrogenation of CH3CHCHO*, which can be formed by the dehydrogenation and then oxidation of propylene or the oxidation and then dehydrogenation of propylene. Compared with acetone, propanal is more difficult to form and its formation reactions have higher Gibbs activation energy. This work provides theoretical guidance for the better modification of catalysts and the reduction of byproducts acetone and propanal on microscopic and mesoscopic scales.

High stable PtZnLa/Beta catalyst with low Pt loading for propane dehydrogenation

A high stable and active Pt-Zn-La/Beta catalyst with 0.1 wt% Pt loading was studied for catalyzing propane dehydrogenation (PDH) in this work, which is constructed by anchoring La and Zn species onto silanol nests of Beta zeolite at first and then loading Pt on the resultant material after calcination. It is found that the Beta zeolite with the Si/Al ratio of 9.75 is more appropriate than the one with higher Si/Al ratio to be used as the support after the dealumination. And that anchoring La and Zn species prior to Pt onto the silanol nests are quite important. In Pt0.1Zn0.4La0.4/Beta catalyst, La significantly dispersed and stabilized Pt1Zn1 ensembles on the zeolite surface while Zn isolated the Pt atoms and therefore the catalyst is much active, highly selective and catalytic stable. With this catalytic structure, the catalyst provided a high initial propylene formation rate of 113.8 molC3H6·gPt−1·h−1 with extremely low deactivation constant of 0.0149 h−1 and a high propylene selectivity of 98 % at 600 °C.

Effects of adding metals to Beta zeolite on ethanol conversion to hydrocarbons

This study investigated the effects of Beta zeolite ion exchange with Fe, Zn, and Co on ethanol conversion to hydrocarbons. Various characterization techniques such as X-ray fluorescence (XRF), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray diffraction (XRD), magic angle rotation nuclear magnetic resonance spectrometry (MAS NMR) of 29Si and 27Al, scanning electron microscopy (SEM), nitrogen physisorption, ammonia temperature-programmed desorption (NH3-TPD) and Fourier transform infrared spectroscopy (FTIR) were employed. Catalytic tests were performed at temperatures from 475 to 550 °C under ambient pressure. The metal addition to Beta zeolite reduced micropore area and volume, decreased the concentration of the extra-framework aluminum, and increased total acid site density and Lewis acid sites, except for Fe. For all catalysts, ethylene was identified as the primary product. However, catalysts containing Zn and Co displayed the formation of propylene and C1 to C3 paraffins. The catalyst with Fe exhibited the highest deactivation and a significant decrease in acidity, attributed to the formation of extra-framework aluminum, resulting in exclusive ethylene production.

Stabilizing ultra-small bimetallic PtSn clusters within S-1 crystals for effective propane dehydrogenation with low Pt loading

It’s a great challenge for enhancing the stability over Pt-based catalysts with low Pt loading during propane dehydrogenation based upon the manipulation of ultra-small PtSn clusters and their compositions. Here, we developed a novel strategy to produce and stabilize sub-nanometer PtSn clusters even atomical dispersion within Silicalite-1 crystals via tailoring calcination atmosphere from air to argon, which could achieve a stable performance of propane dehydrogenation with only 0.15 wt% Pt loading. Argon calcination atmosphere of PtSn@Silicalite-1 significantly decreased the size of PtSn clusters, which further presented a strikingly catalytic performance with the high formation of propylene over 8.0 mol[C3H6]·g[Pt]−1·h−1 even after 3840 min at 600 °C (WHSV=760 g[C3H8]·g[Pt]−1·h−1). Hardly any deactivation was obtained over PtSn8@S-1-Ar-50 after long-term runs for 3840 min with an extremely low deactivation constant of 0.0001 h−1 so far, which was mainly derived from the outstanding stability of PtSn sub-nanometers within S-1 crystals through appropriate flow rate of argon calcination atmosphere.

Mechanistic investigation of methanol-to-olefins conversion catalyzed by H-ZSM-5 zeolite: a DFT study.

The mechanisms for the formation of the first C - C bond and lower olefins on methanol to olefins (MTO) conversion on H-ZSM-5 had been focused in dispute. In this paper, density functional theory has been used to study the reaction mechanisms of methanol to olefins on ZSM-5. The configurations of reactants, intermediates, products and transition state of the numerous reactions involved in such a process have been optimized, as well as the elementary reactions related to these configurations were determined by the calculation of corresponding activation energy barriers and reaction heats. Here, two different kinds of the mechanisms were proposed for the formation of dimethylether (DME), one involving an associative interaction of two methanol molecules with the zeolite Brønsted acid sites and the other occurring via a surface methoxy species and a methanol molecule. A critical intermediate of the methoxy methyl cation was theoretically verified by the reaction of the methoxy species and dimethylether. Besides, it was found that the first intermediates containing a C - C bond were 1,2-dimethoxyethane and 2-methoxy-ethanolare, in which the former was formed from methoxy species with dimethyl ether and the latter was formed from methanol by onium ions((CH3)2O+CH2CH2OCH3), respectively. For the whole reaction mechanism, the results in this paper indicated that the ethene formation is more favorable than propylene formation due to the low activation energy barrier for ethene formation (123.49 vs. 162.09kJ.mol-1). From these calculations, it would be concluded that ethene is the first alkene product that induces the occurrence of the hydrocarbon pool mechanism. All the periodic density function theory (DFT) calculations were performed by the Vienna Ab Initio Simulation package (VASP). The interaction between nucleus and valence electron was described using the pseudopotentials found in the projector augmented wave (PAW) method. PBE-D3 was used in the whole DFT calculations and CI-NEB was used to locate transition state.

Design of ZnFeAlO4/Zn-SAPO-34 composite catalyst for selective hydrogenation of CO2 to propane

Catalytic hydrogenation of CO2 into a single product provides a promising strategy for recycling and utilizing this greenhouse gas, but it remains challenge. Herein, a ZnFeAlO4/Zn-SAPO-34 composite catalyst has been designed, which exhibits a space-time yield of propane of 4.21 mmol g−1 h−1, along with a long-term stability of over 180 h. It was found that the Fe sites in ZnFeAlO4 spinel are conductive to accelerate CO2 hydrogenation into CH3OH, which are stable enough to prevent reduction and carbonization. Characterization results proved that more Brønsted acid sites of SAPO-34 and the addition of Zn species into SAPO-34 zeolite are favorable to form active methylbenzenes with four or five methyl groups, preferentially leading to the formation of propylene via the aromatics-based cycle, which could be hydrogenated to propane. This work presents a feasible strategy in designing an efficient composite catalyst for the synthesis of specific single products from CO2 hydrogenation.

Kinetic modeling of the effect of the conditions of conjugate oxidation of propane and ethylene on the yield of propylene

The study of the oxidation of propane-ethylene mixtures by numerical kinetic modeling allowed us to establish that in the range of 400–600 oC with an increase in the conversion of propane with an increase in temperature, the selectivity of propylene formation passes through a maximum, the position of which depends on the concentration of ethylene in the initial mixture. The addition of ethylene to the initial mixture leads to a reduction in propane consumption and an increase in the selectivity of propylene formation. The conditions under which ethylene introduced into the initial mixture is not consumed during the process are determined, so formally it can be considered as a catalyst, and the process of propane oxidation as proceeding in a pseudo-catalytic regime.

On the role of hydrogen inhibition in gas-phase methane pyrolysis for carbon capture and hydrogen production in a tubular flow reactor

The thermal pyrolysis of methane enables economically competitive hydrogen production without direct CO2 emissions. Although several mechanisms for the process have already been proposed, especially the inhibitory effect of hydrogen as well as the process operation at increased pressure have not yet been fully clarified. In this context, the present work investigates the influence of hydrogen and argon as inert gas on product composition, methane conversion, and hydrogen selectivity as a function of temperature (1000 °C to 1600 °C), residence time (1 s to 7 s), molar dilution ratio (1:1–4:1), and pressure (1 bar to 4 bar) in a high-temperature reactor. Within the scope of this work, total differences in CH4 conversion of up to 50 % could be observed at equal process parameters between an argon and hydrogen dilution, underlining the potential impact of diluents on the overall process. Moreover, increasing the pressure from 1 bar to 4 bar reduces the formation of byproducts significantly for both H2 and Ar as diluent, however, with different mechanistic characteristics. The most remarkable difference is the formation of propylene that exclusively takes place in argon-diluted reaction gas mixtures. This occurrence persists unabated, even under elevated pressures and temperatures reaching as high as 1600 °C. We ascribe this phenomenon to the interaction of methyl and ethyl radicals, establishing it as an impasse to further reactions leading to the formation of solid products. Herewith, the study provides novel insights from a reaction engineering perspective as well as from a process development perspective and clarifies the role of the dilution gases hydrogen and argon on the methane pyrolysis reaction.

Mechanistic and kinetic insights of the formation of allene and propyne from the C3H3 reaction with water.

Allene (H2C = C = CH2) and propyne (CH3-C≡CH) are important compounds in the combustion chemistry. They can be created from the reaction of proparyl radicals with water. In this study, therefore, a computational study into the C3H3 + H2O potential energy landscape has been carefully conducted. The computed results indicate that the reaction paths forming the products (allene: CH2CCH2 + •OH) and (propyne: HCCCH3 + •OH) prevail under the 300-2000K temperature range, where the latter is much more predominant compared to the former. However, these two products are not easily formed under ambient conditions due to the high energy barriers. In the 300 - 2000K temperature range, the branching ratio for the propyne + •OH product declines from 100 to 86%, whereas the allene + •OH product shows an increase, reaching 14% at 2000K. The overall bimolecular rate constant of the title reaction can be presented by the modified Arrhenius expression of ktotal = 1.94 × 10-12 T0.14 exp[(-30.55kcal.mol-1)/RT] cm3 molecule-1s-1. The total rate constant at the ambient conditions in this work, 2.37 × 10-34 cm3 molecule-1s-1, was found to be over five orders of magnitude lower than the total rate constant of the C3H3 + NH3 reaction, 7.98 × 10-29 cm3 molecule-1s-1, calculated by Hue et al. (Int. J. Chem. Kinet. 2020, 4(2), 84-91). The results in this study contribute to elucidating the mechanism of allene and propylene formation from the C3H3 + H2O reaction, and they can be used for modeling C3H3-related systems under atmospheric and combustion conditions. All the geometric structures of the C3H3 + H2O system were optimized by the B3LYP method in conjunction with the 6-311 + + G(3df,2p) basis set. Single-point energies of these species were calculated at the CCSD(T)/6-311 + + G(3df,2p) level of theory. The CCSD(T)/CBS level has also been used to compute single-point energies for the two major reaction channels (C3H3 + H2O → allene + •OH and C3H3 + H2O → propyne + •OH). Rate constants and branching ratios of the key reaction channels were calculated in the 300-2000K temperature interval using the Chemrate software based on the transition state theory (TST) with Eckart tunneling corrections.

Origin of extra-stable multinuclear zinc species riveted into siliceous zeolite for efficient propane dehydrogenation

Zn-based catalysts are promising for direct propane dehydrogenation (PDH) to propylene owing to their cheaper and environment-friendly features but are subjected to serious depletion of active Zn component under working conditions. Herein, we successfully open a “black box” for the origin of active Zn speciations confined within the silicalite-1 (S-1) zeolite by thermogravimetric-mass spectrometry analysis and in-situ Fourier transform infrared spectroscopy. Guided by this, single-site, multinuclear and nanometer hydroxylated ZnOx species are separately encapsulated into the channels of S-1 zeolite by the controllable transformation of intermediate Zn(OH)x with assistant of vicinal- and nest-silanols. Delightfully, synthetic m-ZnOx@S-1 catalyst enables enviable propylene formation rate (50.8 mmol∙gcat−1∙h−1) and propylene selectivity (>96 %) in the PDH reaction. Most importantly, initial activity revives as before and without Zn loss after 7 regeneration cycles. This exceptional PDH performance is benefited from low-coordination and extra-stable multinuclear ZnOx species that can greatly lower the dehydrogenation barrier, favoring the PDH pathway to further produce propylene and hydrogen. These findings elucidate the potential of Zn-based zeolite catalysts for the development of PDH reaction and afford value-filled opportunities in alternative PDH catalyst optimization.

Propane dehydrogenation performance of titanosilicate-1 supported CoOx catalysts by adjusting the acidity and reducibility

The development of low-cost and toxicity-free cobalt oxide-based catalysts for propane dehydrogenation to propylene (PDH) has gained momentum. In this paper, titanosilicate-1 (TS-1) supported CoOx catalysts doped with different alkali and alkaline earth metal ions (M = Na, K, Mg, Ca and Ba) were prepared by adjusting the acidity, reducibility and oxidation state to increase the activity and stability during the PDH reaction. It was found that the decrease in the number of Lewis acid sites and lack of Co2+Ox species with the addition of K ions led to an almost complete loss of the activity of the Co-K catalyst. However, Co-Ca catalyst exhibited moderate acidity, more Lewis acid sites, a larger amount of the in-situ formed highly-dispersed metallic Co0 nanoparticles (∼5 nm) and Co2+Ox species strongly interacting with the support, all of which were responsible for its highest space-time yield (STY) of propylene formation (0.88 kg h−1 kgcat.−1). Though Co3O4 particles were more active for the side reactions, they could be readily reduced to metallic Co0 nanoparticles during the PDH process, and increased the selectivity to propylene with time on stream. Specifically, it was demonstrated that the highly-dispersed metallic Co0 nanoparticles were also active for the PDH activity, but was lower than Co2+Ox species that were strongly interacted with TS-1 support. The deposited coke on the catalysts was related to the catalyst deactivation. The Co0 species could not completely return to the oxidation states after burning off the deposited coke, which seemed to be related to the incomplete recovery of catalytic activity after regeneration.

PH-dependent growth of alumina nanorods with a high aspect ratio for enhanced propane dehydrogenation performance

Controllable synthesis of porous alumina is always challenging due to the diversity of precursors and the complexity of the growth process. In this work, alumina nanorods with adjustable aspect ratios were synthesized by precipitation to investigate the morphology evolution mechanism related to aging pH, and the structure–activity relationship of alumina. The evolution path of precursors ammonium aluminum carbonate hydroxide (NH4Al(OH)2CO3, AACH) was established by tracking the variation in electrical charges and nitrate concentration during the growth process. It was revealed that the anisotropic adsorption of ions on the AACH crystal facets can modulate the axial and radial growth rates of the microcrystalline rods, regulating the one-dimensional oriented assembly of AACH. Alumina synthesized at pH 9.5 exhibited more exposition of (100) facets due to its higher aspect ratio, resulting in an aluminum content of up to 30% in the five-coordinated state. Due to the presence of strong metal-support interactions, the corresponding PtSn/Al2O3 catalyst demonstrated good propane dehydrogenation activity and stability, with propylene formation with 99% selectivity within 30 h of reaction. This study highlighted the significance of pH regulation in the growth environment of AACH, enabling the selective exposure of crystal facets in the alumina support, and providing an effective pathway to obtain highly active and stable catalysts.

In Situ Formation of Platinum-Carbon Catalysts in Propane Dehydrogenation.

The catalytic production of propylene via propane dehydrogenation (PDH) is a key reaction in the chemical industry. By combining operando transmission electron microscopy with density functional theory analysis, we show that the intercalation and ordering of carbon on Pt interstitials to form Pt-C solid solutions is relevant for increasing propylene production. More specifically, we found that at the point of enhanced propylene formation, the structure of platinum nanoparticles is transformed into a transient caesium chloride-type Pt-C polymorph. At more elevated temperatures, the zincblende and rock salt polymorphs seemingly coexist. When propylene production was highest, multiple crystal structures consisting of Pt and carbon were occasionally found to coexist in one individual nanoparticle, distorting the Pt lattice. Catalyst coking was detected at all stages of the reaction, but did initially not affect all particles. These findings could lead to the development of novel synthesis strategies towards tailoring highly efficient PDH catalysts.

In Situ Formation of Platinum‐Carbon Catalysts in Propane Dehydrogenation

AbstractThe catalytic production of propylene via propane dehydrogenation (PDH) is a key reaction in the chemical industry. By combining operando transmission electron microscopy with density functional theory analysis, we show that the intercalation and ordering of carbon on Pt interstitials to form Pt−C solid solutions is relevant for increasing propylene production. More specifically, we found that at the point of enhanced propylene formation, the structure of platinum nanoparticles is transformed into a transient caesium chloride‐type Pt−C polymorph. At more elevated temperatures, the zincblende and rock salt polymorphs seemingly coexist. When propylene production was highest, multiple crystal structures consisting of Pt and carbon were occasionally found to coexist in one individual nanoparticle, distorting the Pt lattice. Catalyst coking was detected at all stages of the reaction, but did initially not affect all particles. These findings could lead to the development of novel synthesis strategies towards tailoring highly efficient PDH catalysts.

Kinetic analysis of monomolecular cracking of normal Alkanes (C4[sbnd]C6) over Brønsted Acid site of Zeolitic type catalyst with energetic evaluation of transition states using Quantum-Chemical modeling

The work aims to determine the kinetic parameters of reactions for production of light olefins via catalytic cracking reactions of C4–C6 n-alkanes based on the energy characteristics of the transition state using quantum chemical calculations. Cracking reactions of C4–C6 n-alkanes proceed via protolytic mechanism on the Brønsted acid sites of zeolite-containing catalysts. For kinetic studies in this work, the thermochemical parameters of the intermediate stages, including hydrocarbon adsorption and transition state were determined, then the activation energies and rate constants were determined over the temperature range of catalytic cracking process from 773 to 903 K (500–630 °C).The results showed that DFT method in combination with B3LYP and ωB97X-D functionals, and 3–21 G basis demonstrated quite high accuracy in determining thermochemical parameters, including enthalpy, entropy and Gibbs free energy at both energetic levels of adsorption and transition state. Then, modeling continued by calculations of activation energies and rate constants of reactions. Obtained kinetic parameters made it possible to determine the reactivity of hydrocarbons with different chain length. It was obtained that the rate constants of butane cracking reactions with the formation of ethylene are 54–90 times higher than the formation of propylene. The rate constants of pentane cracking reactions with the formation of butylene are on average 5 times higher than the formation of propylene. The rate constants for hexane cracking reactions with the formation of butylene are 2.9–3.7 times higher compared to the formation of propylene.