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.

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.

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.

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.

SYNTHESIS AND STRUCTURE DETERMINATION OF NEODYMIUM COMPLEXES WITH CYCLOHEXANECARBOXYLIC ACID

Two complexes,NdL3·2C2H5OH and NdL3·2H2O where L=cyclohexane-carboxylate anion,weresynthesized and the structure of the former was determined by the single-crystal X-ray diffration method.The crystal is triclinic,Pspace group with the cell parameters:a=1.2385（6）,b=1.2385（6）,c=0.9421（5）nm.α=91.69（4）°,β=98.49（4）°,γ=99.16（5）°,Z=2,V=1.436 nm3.The structure was refined to Rvalue of 0.0866.Each Nd atom is connected with other two Nd atoms by two bidentate and two tridentatecarboxyl groups to form a linear polymer.The Nd atom is further coordinated by a chelating carboxyl andtwo ethanol molecules.So the central atom is nine-coordinated with a distorted monocappedsquare-antiprism geometry.The infrared spectra and the thermal analysis of the complexes were alsostudied.

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.

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.

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.

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.

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 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）2O）（B） has not been reported. The catalytic characteristics of B for the oxygenation of cyclohexane with PhIO in CH2Cl2 and cyclohexane medium were studied. We found that B had a fairly

One-Pot Synthesis of Substituted Cyclohexanes from Condensation of Aldehyde and Methylketone

Three asymmetrically substituted cyclohexanes were prepared from one-pot reactions of aldehydes and methylketones, and the products were characterized by single crystal structure analysis, NMR spectroscopy and microanalysis.

Cobalt-nitrogen co-doped porous carbon sphere as highly efficient catalyst for liquid-phase cyclohexane oxidation with molecular oxygen and the active sites investigation

The selective oxidation of cyclohexane to cyclohexanone and cyclohexanol(KA oil)is a challenging issue in the chemical industry.At present the industrial conversion of cyclohexane to cyclohexanone and cyclohexanol is normally controlled at less than 5%selectivity.Thus,the development of highly active and stable catalysts for the aerobic oxidation of cyclohexane is necessary to overcome this low-efficiency process.Therefore,we have developed a cobalt-nitrogen co-doped porous sphere catalyst,Co-NC-x(x is the Zn/Co molar ratio,where x=0,0.5,1,2,and 4)by pyrolyzing resorcinol-formaldehyde resin microspheres.It achieved 88.28%cyclohexanone and cyclohexanol selectivity and a cyclohexane conversion of 8.88%under Co-NC-2.The results showed that the introduction of zinc effectively alleviated the aggregation of Co nanoparticles and optimized the structural properties of the material.In addition,Co0 and pyridinic-N are proposed to be the possible active species,and their proportion efficiently increased in the presence of Zn^(2+)species.In this study,we developed a novel strategy to design highly active catalysts for cyclohexane oxidation.

Highly efficient separation of benzene+cyclohexane mixtures by extraction combined extractive distillation using imidazolium-based dicationic ionic liquids

Benzene(BEN)and cyclohexane(CYH),which have very close boiling points and a binary azeotrope,are the most difficult binary components in the separation of aromatic and non-aromatic hydrocarbons.This study further explored the separation mechanism and industrial application prospects of BEN+CYH mixtures separated by a dicationic ionic liquid(DIL)[C_(5)(MIM)_(2)][NTf_(2)]_(2) based on experimental research.The calculation results of the Conductor-like Screening model Segment Activity Coefficient(COSMO-SAC)model show that selectivity and solvent capacity of the DIL are significantly improved.The effects of different anions and cations on the micro-structure distribution and diffusion behavior of BEN+CYH system were investigated by quantum chemistry(QC)calculations and molecular dynamics(MD)simulations.The results indicate that the anion[NTf_(2)]_(2)has low polarity,uniform charge distribution,and a dual role of hydrogen bonding andπ-πbonding,and the cation[C_(5)(MIM)_(2)]^(2+) has stronger interaction with BEN and higher selectivity than conventional cations.The liquid-liquid extraction and extractive distillation(LLE-ED)process using an optimized 65 mol/mol DIL+35 mol/mol H_(2)O mixed solution as the extractant was proposed,which solved the problem of low product purity in the LLE process and high energy consumption in the ED process.Under the best operating conditions,the purity of CYH product was 99.9%,the purity of BEN product was 99.6%,the recovery rate of BEN reached 99.9%,and the recovery rate of DIL reached 99.9%.The heat-integrated LLE-ED process reduced total annual cost by 21.6%,and reduced CO_(2) emissions by 48.0%,which has broad industrial application prospects.

Selective liquid phase oxidation of cyclohexane over Pt/CeO_(2)-ZrO_(2)-SnO_(2)/SiO_(2)catalysts with molecular oxygen

Partial oxidation of cyclohexane into cyclohexanone and cyclohexanol(KA-oil)is an industrially significant reaction for producing precursors for the synthesis ofε-caprolactam and adipic acid,which are the building blocks of nylon.However,to date,the cyclohexane conversion ratio has usually been limited to less than 6%to prevent further oxidation of the cyclohexanol and cyclohexanone targets.In this study,we report that Pt/CeO_(2)-ZrO_(2)-SnO_(2)/SiO_(2),in which CeO2-ZrO2-SnO2 provide reactive oxygen molecules from inside the bulk,can act as efficient catalysts.Optimization of the catalyst composition and reaction conditions provided a cyclohexane conversion ratio of 24.1%and a total selectivity for cyclohexanol and cyclohexanone of 83.4%at 130℃in 0.5 MPa(4.9 atm)air for 7 h over a 5wt%Pt/16wt%Ce_(0.68)Zr_(0.17)Sn_(0.15)O_(2.0)/SiO_(2)catalyst.This catalyst has significant advantages over conventional catalysts because the reaction proceeds at a lower pressure,and there is no need for toxic radical initiators or free-radical scavengers.

Chitosan-mediated synthesis of mesoporous α-Fe_(2)O_(3)nanoparticles and their applications in catalyzing selective oxidation of cyclohexane

This paper reports the chitosan-mediated synthesis of porous hematite nanoparticles with FeCl3 as the precursor via a hydrothermal approach at 160℃.A series of porous chitosan/iron oxide hybrid nanoparticles were obtained via changing the ratio of chitosan to FeCl3,FeCl3 concentration and pH value of the reaction solution,and producing porous iron oxide nanoparticles after calcination.The as-prepared samples were characterized by means of X-ray diffraction,transmission electron microscopy,thermal gravimetric analysis,Fourier transform infrared,and N2 sorption.The particle sizes of these metal oxides were less than 100 nm,and the pore sizes were in the range of 2-16 nm.It was demonstrated that chitosan played a key role in the formation of the porous structures.The resultant α-Fe2O3 nanoparticles were used as the support to immobilize Au or Pd nanoparticles,producing Au/α-Fe2O3 or Pd/α-Fe2O3 nanoparticles.The as-prepared α-Fe2O3 nanocatalyst exhibited high selectivity towards cyclohexanone and cyclohexanol for catalyzing cyclohexane oxidation with O2 at 150℃.

The selective deposition of Fe species inside ZSM-5 for the oxidation of cyclohexane to cyclohexanone

The design of efficient iron-based catalysts remains a great challenge for selective cyclohexane oxidation to cyclohexanone under mild conditions.Because of the complex distribution of iron location on the support,the selectivity is always low.Here,we report a general strategy to selectively deposit highly-dispersed FeO_(x) into the micropore of ZSM-5 by atomic layer deposition(ALD).The framework of ZSM-5 and the Bronsted acid sites are intact during ALD,and the Fe species are selectively deposited onto the defect and Lewis acid sites of ZSM-5.Besides,more Fe–O–Si bonds are formed over FeO_(x)/ZSM-5 with a low loading of Fe,while FeO_(x) nanoparticles are generated at high Fe loading.They cannot be realized by the traditional solution method.The obtained FeO_(x)/ZSM-5 catalysts perform high selectivity of cyclohexanone(92%–97%),and ALD cycle numbers of FeO_(x) control the activity.Compared with the Fe nanoparticles,the Fe–O–Si species performs higher turnover frequency and stability in the oxidation reaction.

Ti^(3+) self-doped TiO_(2) as a photocatalyst for cyclohexane oxidation under visible light irradiation

Most of TiO_(2) particles can be used as a photocatalyst for the selective oxidation of cyclohexane under ultraviolet light illumination.In this paper,Ti^(3+) self-doped TiO_(2) submicron-sized particles(i.e.,Ti^(3+)/TiO_(2) SMP)were used as a catalyst for visible-light driven photocatalytic cyclohexane oxidation.The microstructure and properties of the Ti^(3+)/TiO_(2) SMP were characterized by X-ray diffraction(XRD),UVevisible diffuse reflection(UVeVis DRS),scanning electron microscopy(SEM),electron paramagnetic resonance(EPR),solid-state photoluminescence spectroscopy(PLS)and X-ray photoelectron spectroscopy(XPS).The Ti^(3+)/TiO_(2) SMP exhibits good visible-light driven photocatalytic performances for cyclohexane oxidation with cyclohexanone as a dominate product.Effects of solvent,reaction temperature,reaction time and oxygen pressure on the formation of cyclohexanone were investigated.The cyclohexane oxidation over the Ti^(3+)/TiO_(2) SMP photocatalyst using carbon tetrachloride as a solvent under the optimal conditions presents a greater selectivity to cyclohexane(i.e.,95.1%).Based on the controlled experimental results with different radical scavengers,the hole(h^(+))is critical for the activation of cyclohexane.