Research Advances on Cyclohexane Catalytic Cracking

This article elaborates on the research achievements of domestic and foreign researchers in exploring the conversion pathways and reaction mechanisms of cyclohexane catalytic cracking in recent years.It analyzes the effects of different catalysts and process conditions on the conversion laws of cyclohexane,summarizes the conversion pathways of cyclohexane,and discusses the chemical mechanisms of several main reactions of cyclohexane in catalytic cracking,such as cracking,isomerization,hydrogen transfer,dehydrogenation,and alkylation;Several advanced characterization methods and common research methods were listed,and prospects for future development in this field were proposed based on existing research.

A comparative single-pulse shock tube experiment and kinetic modeling study on pyrolysis of cyclohexane,methylcyclohexane and ethylcyclohexane

The pyrolysis of cyclohexane,methylcyclohexane,and ethylcyclohexane have been studied behind reflected shock waves at pressures of 5 and10 bar and at temperatures of 930-1550 K for 0.05%fuel diluted by Argon.A single-pulse shock tube(SPST)is used to perform the pyrolysis experiments at reaction times varying from 1.65 to 1.74 ms.Major products are obtained and quantified using gas chromatography analysis.A flame ionization detector and a thermal conductivity detector are used for species identification and quantification.Kinetic modeling has been performed using several detailed and lumped chemical kinetic mechanisms.Differences in modeling results among the kinetic models are described.Reaction path analysis and sensitivity analysis are performed to determine the important reactions controlling fuel pyrolysis and their influence on the predicted concentrations of reactant and product species profiles.The present work provides new fundamental knowledge in understating pyrolysis characteristics of cyclohexane compounds and additional data set for detailed kinetic mechanism development.

Investigation of cyclohexane catalytic degradation driven by N atoms from N_(2)discharges

The effect of N_(2)discharge products on cyclohexane degradation over a MnO_(2)/γ-Al_(2)O_(3)catalyst has been evaluated by feeding N_(2)discharge products to the catalyst using a specially designed dielectric barrier discharge reactor.At a reaction temperature of 100℃,the cyclohexane conversion increased from 2.46%(without N_(2)discharge products)to 26.3%(with N_(2)discharge products).N-and O-containing by-product(3,4-dehydroproline)was found on the catalyst surface using gas chromatograph-mass spectrometry identification,in which C=N–C and C=N–H bonds were also confirmed from x-ray photoelectron spectroscopy analysis results.Operando analysis results using diffuse reflectance infrared Fourier transform spectroscopy revealed that N atoms can react with surface H_(2)O possibly to NH and OH reactive species that have reactivities to promote CO oxidation to CO_(2).The mechanism of N-atom-driven cyclohexane degradation to CO and CO_(2)is proposed.

Synthesis of cerium-doped MCM-48 molecular sieves and its catalytic performance for selective oxidation of cyclohexane

Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Raman spectroscopy. The results showed that all the samples held the structure of MCM-48, and Ce could enter the framework of MCM-48. However, when Ce/Si molar ratio in the sampies was high （0.04 or 0.059）, there were CeO2 crystallites as secondary phase in the extraframework of MCM-48. Ce-doped MCM-48 was a very efficient catalyst for the oxidation of cyclohexane in a solvent-free system with oxygen as an oxidant. In the conditions of 0.5 MPa 02 and 413 K for 5 h, the conversion of cyclohexane was 8.1% over Ce-MCM-48-0.02, the total selectivity of cyclohexanol and cyclohaxnone was 98.7%. With an increase of Ce content, the conversion of cyclohexane and the selectivity to cyclohexanol decreased somewhat, but the selectivity to cyclohexanone increased.

New insights for the catalytic oxidation of cyclohexane to K-A oil

Au-based catalysts have been reported to be active in the cyclohexane oxidation to K-A oil, but they showed some limitiations in terms of productivity, selectivity and required reaction conditions. The possibility to overcome some of these limits has been explored coupling Au with Cu, which can be suitable for undergoing the electron-switch in the initial step of the cyclohexane oxidation. Hence, a bimetallic 2 wt% Au Cu/Al_(2)O_(3) catalyst was tested in the oxidation of cyclohexane, working at mild conditions of 120 ℃ and 4 bar of O_(2). The combination of the catalyst with a very small amount of benzaldehyde used as cheaper and non-toxic radical initiator allowed to obtain a very high productivity of cyclohexanol and cyclohexanone(45 mmol*m L/mgmet*h) with a selectivity of 94%. Moreover, comparing the catalysed reaction with the non-catalysed one, the role of the catalyst has been disclosed.

Study on Catalytic Cracking of Cyclohexane to Produce Light Olefins

Catalytic cracking of cyclohexane(CHA) over ZSM-5, Beta, and USY zeolite catalysts was examined in a fixed fluidized bed reactor(ACE) at 773 K. The adsorption of cyclohexane in ZSM-5, Beta, and USY catalysts was investigated by IR spectroscopy. The IR results demonstrated that the zeolite structure has a remarkable influence on adsorption. Beta zeolite has stronger adsorption of cyclohexane than ZSM-5 and USY zeolites. During the cracking of cyclohexane, path Ⅰ(cyclohexane →methycyclopentane →light olefins) and path Ⅱ(cyclohexane → cyclohexene → light olefins) were found as two important reaction pathways to produce light olefins. A mixture of ZSM-5 and Beta zeolites is better suited for path Ⅰ, and a combination of ZSM-5 and USY zeolites is suitable for path Ⅱ. When pathway Ⅰ and pathway Ⅱ had the same proportion in cyclohexane conversion, pathway Ⅱ would be a better choice for light olefins production.

One-step Synthesis of ε-Caprolactam by the Liquid Phase Nitrosation of Cyclohexane over the Catalysts Containing CH_3COO^- or —COOH

ε-Caprolactam（CL or CPL） is one of the most important intermediates used in polymer industry for the production of several million tons of nylon-6 every year^[1]. All current commercial processes for the production of caprolactam are based on either benzene or tolueneI21. Caprolactam is synthesized by the Beckmann rearrangement of cyclohexanone oxime with fuming sulfuric acid or sulfuric acid as the reaction medium, and cyclohexanone oxime is produced by the reaction between cyclohexanone and hydro- xylamine（only one exception is the Toray PNC process）.

Quantitative interpretation to the chain mechanism of free radical reactions in cyclohexane pyrolysis

Pyrolysis of cyclohexane was conducted with a plug flow tube reactor in the temperature range of 873-973 K. Based on the experimental data, the mechanism and kinetic model of cyclohexane pyrolysis reaction were proposed. The kinetic analysis shows that overall conversion of cyclohexane is a first order reaction, of which the rate constant increased from 0.0086 to 0.0225 to 0.0623 s-1 with the increase of temperature from 873 to 923 to 973 K, and the apparent activation energy was determined to be 155.0±1.0 kJ mol-1. The mechanism suggests that the cyclohexane is consumed by four processes：the homolysis of C-C bond （Path I）, the homolysis of C-H bond （Path II） in reaction chain initia- tion, the H-abstraction of various radicals from the feed molecules in reaction chain propagation （Path III）, and the process associated with coke formation （Path IV）. The reaction path probability （RPP） ratio of XPath I：XPath II ： XPath III ： XPath IV was 0.5420：0.0045：0.3897：0.0638 at 873 K, and 0.4336 ： 0.0061 ： 0.4885 ： 0.0718 at 973 K, respectively.

Highly efficient cobalt-doped carbon nitride polymers for solvent-free selective oxidation of cyclohexane

Selective oxidation of saturated hydrocarbons with molecular oxygen has been of great interest in catalysis, and the development of highly efficient catalysts for this process is a crucial challenge. A new kind of heterogeneous catalyst, cobalt-doped carbon nitride polymer(g-C_3N_4),was harnessed for the selective oxidation of cyclohexane. X-ray diffraction, Fourier transform infrared spectra and high resolution transmission electron microscope revealed that Co species were highly dispersed in g-C_3N_4 matrix and the characteristic structure of polymeric g-C_3N_4 can be retained after Co-doping, although Co-doping caused the incomplete polymerization to some extent. Ultraviolet-visible, Raman and X-ray photoelectron spectroscopy further proved the successful Co doping in g-C_3N_4 matrix as the form of Co(Ⅱ)-N bonds. For the selective oxidation of cyclohexane, Co-doping can markedly promote the catalytic performance of g-C_3N_4 catalyst due to the synergistic effect of Co species and gC_3N_4 hybrid. Furthermore, the content of Co largely affected the activity of Co-doped g-C_3N_4 catalysts, among which the catalyst with 9.0 wt%Co content exhibited the highest yield(9.0%) of cyclohexanone and cyclohexanol, as well as a high stability. Meanwhile, the reaction mechanism over Co-doped g-C_3N_4 catalysts was elaborated.

Theoretic heat sink simulation and experimental investigation of the pyrolysis of substituted cyclohexanes

Reaxgen program for the pyrolysis mechanism of cycloalkanes was adopted to simulate the heat sink of substituted cyclohexanes. Thermal cracking of cyclohexanes was performed to examine the cracking performance, wherein the substituent effects were detailedly discussed under supercritical condition. It was found that Reaxgen program played a good part in the screening and optimization of cyclohexanes. A good agreement with the experimental data for the mono-substituted and bi-substituted cyclohexanes was demonstrated, however, some deviation for the tri-substituted cyclohexanes were observed. The experiment results indicated that the gaseous product yield increased sharply for mono- substituted cyclohexanes with short substituents containing no more than two carbons. Nevertheless, continuous increase in the alkyl chain depressed the gaseous product yield smoothly. The cyclic substituent dramatically inhibited the pyrolysis of cyclohexanes. All the substituents but cyclohexyl had no obvious effect on the yield of hydrogen and olefins （≤C4）. For bi-substituted cyclohexanes, the more close the distance between the two substituents, the higher the gaseous product yield was obtained. However, opposite result on the selectivity to hydrogen and olefins （≤C4） was generally obtained except 1,3-dimethylcyclohexane. The position of tri-substituents acted little significance on the gaseous product yield, as well as the selectivity to hydrogen and olefins （≤C4）.

Diffusion Characteristics and Removal of Cyclohexane in Polyolefin Elastomer Melt

The diffusion coefficient of volatiles in polymer solutions is a crucial parameter to describe the mass transfer efficiency and ability of volatiles.In this research,polyolefin elastomer(POE)was used as a polymer,and cyclohexane was used as a volatile.A gravimetric analysis was applied to measure the diffusion coefficient of cyclohexane in POE.The devolatilization rate of the POE-cyclohexane system under different conditions was measured.The effects of temperature,film sample thickness,and initial concentration of volatiles on the devolatilization rate were discussed.Based on the devolatilization rate data,the average diffusion coefficient of cyclohexane in POE was obtained by fitting with a mathematical model.The experimental results indicate that the devolatilization rate increased with increasing temperature and initial concentration of volatiles,but it decreased with increasing sample thickness.As the thickness increased,the overall diffusion resistance increased.As the temperature increased,the molecular movement increased,resulting in the increase of average diffusion coefficient.The relationship between the diffusion coefficient of the POE-cyclohexane system and temperature follows the Arrhenius law.The diffusion activation energy E=6201.73 J/mol,and the pre-exponential factor of the diffusion coefficient D0=2.64×10^(-10) m^(2)/s.This work can provide basic data for exploring the devolatilization of POE polymers and serves as a useful reference for enhancing the effect of devolatilization.

Structural Effect on Electron Impact Decomposition of 1,3-and 1,4-Cyclohexane Dinitrites

Alkyl dinitrites have at-tracted attention as an im-portant type of nitrosating agent and a pollution source in atmosphere.The reac-tivity and chemistry of alkyl dinitrites induced by the two ONO functional groups are relatively unknown.In this work,decompositions of 1,3-cyclohexane dinitrite and 1,4-cyclohexane dinitrite are studied by electron impact ionization mass spectroscopy(EI-MS).Apart from NO^(+)(m=z=30),fragment ions m=z=43 and 71 are the most abundant for the 1,3-isomer.On the other hand,fragments m=z=29,57,85,and 97 stand out in the EI-MS spectrum of 1,4-isomer.Possible dissociation mechanisms of the two dinitrites are proposed by theoretical calculations.The results reveal that the ring-opening of 1,3-cyclohexane dinitrite mainly starts from the intermediate ion(M-NO)^(+)by cleavage of twoαC-βC bonds.For 1,4-cyclohexane dinitrite,in addition to the decomposition via intermediate(M-NO)^(+),cleavage ofβC-βC bonds can occur directly from the parent cation(M)^(+).The results will help to understand the structural related chemistry of alkyl dinitrites in atmosphere and in NO transfer process.

Solution-combustion Synthesized Nano-pellet α-Al_(2)O_(3) and Catalytic Oxidation of Cyclohexane by Its Supported Cobalt Acetate

Nano-pelletα-Al_(2)O_(3) was prepared using aluminum nitrate as precursor and urea as fuel by a fast method of solution combustion synthesis.The formation of the nano material was dependent on the molar ratio of fuel/oxidant,calcination temperature,and foreign metallic ions.The prerequisite conditions of the formation were a suitable fuel/oxidant molar ratio larger than two and calcination temperature higher than 673 K.Foreign ions,Ce^(4+) or Co^(2+),hindered this formation via promoting the generation of stable penta-coordinated Al^(3+) ions due to strong interaction with alumina,were revealed by ^(27)Al NMR spectra.Such Al^(3+) ions were recognized as a critical intermediate state for the phase transformation of alumina and their presence deterred the transformation.The nano-pellet morphology of the product demonstrated a specific surface area of 69 m^(2)/g,of which the external surface area occupied 59 m^(2)/g.It was found that the supported cobalt acetate on such nano-pellets existed as nanoparticles attached to the external surface,evidenced by the TEM characterization.The prepared catalyst could efficiently catalyze the selective oxidation of cyclohexane under the reaction condition of pressure under 0.8 MPa,temperature at 373 K,and time for 4 hours.The conversion of the reaction achieved up to 7.9%;while the cyclohexanone selectivity was 42.7%and the cyclohexanone and cyclohexanol selectivity was 91.6%.This catalytic performance recommends the supported cobalt acetate on the inert nano-pellet a-Al_(2)O_(3) as a promising catalyst for the selective oxidation of cyclohexane.

Solvent-free partial oxidation of cyclohexane to KA oil over hydrotalcitederived Cu-MgAlO mixed metal oxides

A highly efficient and stable hydrotalcite-derived Cu-MgAlO catalyst was developed for the partial oxidation of cyclohexane with molecular oxygen.The physical–chemical properties of Cu-MgAlO catalysts were studied,and the results indicated that the copper component had been successfully introduced into the hydrotalcite unit layer structure.The catalytic reaction results showed that copper as the active species could activate CAH bond and effectively promote the decomposition of cyclohexyl hydroperoxide(CHHP)to the mixture of cyclohexanol and cyclohexanone(KA oil).8.3%of cyclohexane conversion and 82.9%of selectivity for KA oil were obtained over 9%Cu-MgAlO catalyst at 150℃with 0.6 MPa of oxygen pressure for 2 h.Especially,its catalytic performance was still stable after five runs.

Mechanistic Insights into the Catalytic Cracking of Cyclohexane

Although naphthenes have long been identified as important feedstock components for the production of light olefins and aromatics in fluid catalytic cracking units,their cacking mechanism and microscopic reaction networks,such as activation modes,ring-opening paths,and the production of aromatics,remain debated.In this context,we reported experimental and computational work aimed at elucidating the reaction network of naphthenes in fluid catalytic cracking using cyclohexane as the model naphthene.First,the main reactions for the formation of highly selective and value-added products such as light olefins and aromatics were discussed.Then,the proportions of cyclohexane activation via(i)the non-classical carbonium mechanism and(ii)the classical carbenium mechanism were analyzed by data fitting methods,which revealed that around 32.6%of cyclohexane was initiated by path(i),and the remaining naphthene was activated by path(ii).Moreover,our DFT results showed that the ring opening of cyclohexane through pathway(i)was more difficult than that through path(ii),and ring opening followed by the ring contraction of cyclohexane carbenium ions was the most energetically favorable route among the different ring-opening ways.

Studies on the Biomimetic Oxidation Catalyzed by the Model Compound of Cytochrome P-450 (Ⅶ) The Influence of the Axial Ligand X in TPPFe(Ⅲ)X on Its Catalytic Properties for the Oxygenation of Cyclohexane

In the study of cyclohexane monoxygenation with PhIO catalyzed by TPPFe( Ⅲ )X, we found the Influence of different axial ionic ligands X (X = F, Cl, Br, I, SCN, OR, R, CH,3, C2H6, (CH3)2CH, (CH2)3C)in TPPFe( Ⅲ )X on the oxidation products distribution and the yields of cyclohexanol. This paper deals with the linear relationship between the catalytic activity of TPPFe(Ⅲ)X and both the electronic or/ and steric effects of the axial ligands OR in TPPFe(Ⅲ)OR on its catalytic activity.

Studies on Biomlmetic Oxidation for the Model Compound of Cytochrome P-450(IV)——Studies on Oxygenation of Cyclohexane Catalyzed by μ-Oxo-bis(5,10, 15,20-tetraphenylporphinato)iron(Ⅲ)

Chloro-（5,10,15,20-tetraphenylporphinato）iron（Ⅲ）(TPPFeCl)（A） used as a model compound of cytochrome P-450 to catalyze the monooxyenation of alkane is known, but the oxygenation of alkane catalyzed by μ-oxo-bis（5,10,15,20-tetraphenylporphinato）-iron（Ⅲ）(（TPPFe）;O)（B） has not been reported. The catalytic characteristics of B for the oxygenation of cyclohexane with PhIO in CH;Cl;and cyclohexane medium were studied. We found that B had a fairly good

Highly dispersive tetrahedral vanadium species on pure silica ZSM-12 zeolite boosting the selective oxidation of cyclohexane into cyclohexanone

The selective oxidation of cyclohexane is a promising green route for the production of KA oil(cyclohexanol and cyclohexanone),but remains a huge challenge to design high-performing heterogeneous catalysts under mild conditions.Herein,a pure silica ZSM-12(MTW topology)zeolite was applied as the support to immobilize highly dispersive tetrahedrally coordinated vanadium(V)species and the constructed catalyst 1%V/SZ-12 exhibited high efficiency in the fast and selective oxidation of cyclohexane into cyclohexanone with H_(2)O_(2).The reaction completed within 30 s,affording the selectivity of 99%towards cyclohexanone and the extremely high turnover frequency(TOF)of 5,891 h^(-1).1%V/SZ-12 was facilely reused with stable activity and feasibly extended to the oxidation of various cyclohexane derivatives.The one-dimensional 12-membered ring microchannels contributed to the formation and accessibility of tetrahedrally coordinated high valent V5+species as the robust active centers,which activated H_(2)O_(2) to generate V–O–O·,the active oxygen species for the electrophilic attack on cyclohexane to produce cyclohexanone as the sole product.