N-Hexane Isomerization on Ni-Pt/Catalysts Supported on Mordenite

The aim of this work was to evaluate the catalytic properties for n-hexane isomerization of bifunctional monometallic (Ni or Pt) and bimetallic catalysts (Pt-Ni), using HMOR zeolite as support. The method used for metal dispersion in the zeolite was competitive ion exchange using ammine complexes [Ni(NH3)6]Cl2 and [Pt(NH3)4]Cl2 as precursors. The catalysts were characterized by X-Ray diffraction, X-Ray energy dispersion spectroscopy, temperature-programmed reduction and transmission electron microscopy. The n-hexane isomerization reaction using the catalysts was carried out to evaluate the catalyst activity. The reaction was carried out in a fixed bed reactor operating at 250?C, 1 atm, H2/C6 = 9 molar ratio. The profiles obtained from TPR suggest that, for bimetallic catalysts, the presence of platinum facilitates the reduction of Ni2+ cations. The bimetallic catalysts presented a higher activity in the isomerization of n-hexane when compared to the monometallic ones, as well better stability as the Pt content in the solid increases.

Measurement and Correlation of Liquid-liquid Equilibria for 1-Hexene-n-Hexane-3-Methysulfolane

Utilizing solvent extraction to separate alkanes and olefins from catalytic light gasoline is an effective method for maximizing the utility of gasoline fractions.This study presents the determination of liquid-liquid equilibrium data for the ternary system of 1-hexene-n-hexane-3-methylsulfolane at 30℃,40℃,and 50℃under atmospheric pressure.The obtained data facilitated the construction of a ternary phase diagram for the system.The results showed that the extraction selectivity of 1-hexene/n-hexane exceeded 1.5 when using 3-methylsulfolane as the extraction solvent.Furthermore,the thermodynamic consistency of the experimental data was examined using Hand’s equation and the Othmer-Tobias method.The correlation coefficient,R^(2)≥0.9578,indicated the acceptable reliability of the phase equilibrium data.Subsequently,the NRTL(non-random two liquid)model was used to correlate the liquid-liquid phase equilibrium data and derive the binary interaction parameter.Notably,the results demonstrated that the root mean square deviation of the NRTL model correlation values from the experimental values did not exceed 2.5%.

Critical approaches in the catalytic transformation of sugar isomerization and epimerization after Fischer-History,challenges,and prospects

The transformation of aldose to ketose or common sugars into rare saccharides,including rare ketoses and aldoses,is of great value and interest to the food industry and for saccharidic biomass utilization,medicine,and the synthesis of drugs.Nowadays,high-fructose corn syrup(HFCS)is industrially produced in more than 10 million tons annually using immobilized glucose isomerase.Some low-calorie saccharides such as tagatose and psicose,which are becoming popular sweeteners,have also been produced on a pilot scale in order to replace sucrose and HFCS.However,current catalysts and catalytic processes are still difficult to utilize in biomass conversion and also have strong substrate dependence in producing high-value,rare sugars.Considering the specific reaction properties of saccharides and catalysts,since the pioneering discovery by Fischer,various catalysts and catalytic systems have been discovered or developed in attempts to extend the reaction pathways,improve the reaction efficiency,and to potentially produce commercial products.In this review,we trace the history of sugar isomerization/epimerization reactions and summarize the important breakthroughs for each reaction as well as the difficulties that remain unresolved to date.

Towards understanding the mechanism of n-hexane tolerance in Synechocystis sp.PCC 6803

Synthetic biology efforts have also led to the development of photosynthetic cyanobacteria as"autotrophic cell factories"for biosynthesis of various biofuels directly from CO_(2).However,the low tolerance to toxicity of biofuels has restricted the economic application of cyanobacterial hosts.In this study,RNAseq transcriptomics was employed to reveal stress responses to exogenous n-hexane in Synechocystis sp.PCC 6803.Functional enrichment analysis of the transcriptomic data showed that signal transduction systems were induced significantly.To further identify regulatory genes related to n-hexane tolerance,a library of transcriptional regulators(TRs)deletion mutants was then screened for their roles in nhexane tolerance.The results showed that a knockout mutant of slr0724 that encodes an Hta R suppressor protein was more tolerant to n-hexane than the wild type,indicating the involvement of slr0724 in nhexane tolerance.This study provides the foundation for better understanding the cellular responses to n-hexane in Synechocystis sp.PCC 6803,which could contribute to the further engineering of nhexane tolerance in cyanobacteria.

Synthesis of MgO-doped ordered mesoporous carbons by Mg^(2+)-tannin coordination for efficient isomerization of glucose to fructose

In-situ MgO-doped ordered mesoporous carbon(OMC@MgO)was fabricated by formaldehyde-free self-assembly method,in which biomass-derived tannin was used as carbon precursor replacing fossil-based phenolics,Mg^(2+)as both cross-linker and precursor of catalytic sites.Up to~20 wt% MgO could be doped in the carbon skeleton with good dispersion retaining well-ordered mesoporous structures,while more MgO content(35 wt%)led to the failing in the formation of ordered mesoporous structure.The OMC@MgO possessed a high specific surface area(298.8 m^(2) g^(-1)),uniform pore size distribution(4.8 nm)and small crystallite size of MgO(1.73 nm)due to the confinement effect of ordered mesoporous structure.Using OMC@MgO as the heterogeneous catalyst,a maximum fructose yield of 32.4% with a selectivity up to 81.1%was achieved from glucose in water(90℃,60 min),which is much higher than that obtained using the MgO doped active carbon via conventional post-impregnation method(26.5%yield with 58.3% selectivity).Higher reaction temperature(>90℃)resulted in decrease of selectivity due to the formation of humins.The designed OMC@MgO displayed tolerant to high initial glucose concentrations(10 wt%)and could remain good recyclability without significant loss of activity for three cycles.

A novel synthesis of highly active and highly stable non-noble-nickel-modified persulfated Al_(2)O_(3)@ZrO_(2) core-shell catalysts for n-pentane isomerization

The non-noble metal modified sulfated zirconia was found easy to deactivate.Herein,highly active and highly stable non-noble core-shell Ni-S_(2)O_(8)^(2−)/Al_(2)O_(3)@ZrO_(2) catalysts(Ni-SA@Z-x,x=Al content in wt%)have been successfully prepared and investigated for n-pentane isomerization.The results showed that the core-shell Ni-SA@Z-30 provided a sustained high isopentane yield(63.1%)with little or no deactivation within 5000 min at a mild reaction pressure of 2.0 MPa,which can be attributed to the following factors:(i)carbon deposition was greatly suppressed by the large pore size and huge pore volume;(ii)the loss of sulfur entities was suppressed because the small and highly dispersed tetragonal ZrO_(2) particles can bond with the S species strongly;(iii)strong Brønsted acidity can be maintained well after the isomerization.The pore structures and acid nature of the core-shell Ni-SA@Z-x are entirely different from those of the normal structure Ni-S_(2)O_(8)^(2−)/ZrO_(2)-Al_(2)O_(3),even though the Al content and the compositions of the individual components are the same.The Al_(2)O_(3)cores endow the catalysts with high internal surface area and high mechanical strength.Meanwhile,the ZrO_(2) shell,which consists of more and smaller tetragonal ZrO_(2) particles because of the large surface area of the Al_(2)O_(3)core,promotes the formation of more stable sulfur species and stronger binding sites.

Quantum Dynamics Calculations on Isotope Effects of Hydrogen Transfer Isomerization in Formic Acid Dimer

We present a quantum dynamics study on the isotope effects of hydro-gen transfer isomerization in the formic acid dimer,and this is achieved by multidimensional dy-namics calculations with an efficient quantum mechanical theoretical scheme developed by our group,on a full-dimensional neural network ab initio potential energy surface.The ground-state and fundamental tun-neling splittings for four deuterium isotopologues of formic acid dimer are considered,and the calculated results are in very good general agreement with the avail-able experimental measurements.Strong isotope effects are revealed,the mode-specific funda-mental excitation effects on the tunneling rate are evidently influenced by the deuterium sub-stitution of H atom with the substitution on the OH bond being more effective than on the CH bond.Our studies are helpful for acquiring a better understanding of isotope effects in the double-hydrogen transfer processes.

Seed-solution-induced Synthesis of FER Zeolite and Its Catalytic Application in the Skeletal Isomerization of n-Butene

A series of Ferrierite(FER)zeolites were prepared via hydrothermal synthesis in the absence of organic templates with the aid of sodium-type FER zeolite(NaFER)or NaFER suspensions(NaFERsus)acquired by NaOH solution treatment as seeds.The differences in the structures and acid sites of the obtained FER zeolite catalysts arising from the choice of seed were investigated,and the catalytic performances of the obtained FER zeolites were evaluated in the skeletal isomerization of n-butene.The results indicate that the samples synthesized using NaFERsus feature more Br?nsted acid sites(BAS)in the 10-membered-ring(10-MR)at the expense of strong acid and Lewis acid sites(LAS),compared with samples derived from NaFER.Therefore,the FER samples synthesized using NaFERsus outperformed the NaFER counterparts as the BAS in 10-MR and LAS were the main active sites,while BAS in 8-MR and LAS were responsible for side reactions,such as polymerization,cracking,and carbon deposition in n-butene isomerization.The optimized FER catalyst was continuously used for 720 h at 350℃ at 0.1 MPa under an n-butene space velocity of 2.0 h^(-1),during which the n-butene conversion remained at>40%,and the isobutylene yield was>37.5%.

Isomerization of n-pentane catalyzed by amide-AlCl3-based ionic liquid analogs with various additives

The isomerization of n-pentane to generate high-quality blending components for clean gasoline was catalyzed by several amide-AlCl3-based ionic liquid(IL) analogs with various amides as donor molecules. The catalytic performance of these IL analogs was evaluated in a magnetic agitated autoclave operated in batch mode.IL analog based n-methylacetamide(NMA)-AlCl3 with the amide/AlCl3 molar ratio of 0.65 showed excellent performance toward n-pentane isomerization because 0.65 NMA-1.0 AlCl3 had a low viscosity and bidentate coordination structure. The influences of reaction time, reaction temperature, and stirring speed on the catalytic performance were also investigated. Optimal reaction conditions comprised the reaction time of 1 h, the reaction temperature of 40 °C, and the stirring speed of 1500 r·min-1. Under optimal condition, the n-C5 conversion,research octane number(RON) increment, total liquids yield, and isoparaffin yield in isomerized oil were56.80%, 13.51, 89.90 wt%, and 44.32 wt%, respectively. A new mathematical model was constructed to predict the relationships among RON increment, RON increment/n-C5 conversion ratio, and n-C5 conversion. The new model indicated that an appropriate conversion per pass of n-C5 did not exceed 50%–55%. Various cycloparaffin additives were used to improve the catalytic performance of 0.65 NMA-1.0 AlCl3. The n-C5 conversion increased from 56.80% to 67.32%. The RON increment, total liquids yield, and isoparaffin yield reached 17.83, 97.36 wt%,and 63.74 wt%, respectively.

Isomerization of linear C5–C7 over Pt loaded on protonated fibrous silica@Y zeolite（Pt/HSi@Y）

A novel fibrous silica Y zeolite (HSi@Y) loaded with Pt has been studied based on its ability to produce protonic acid sites originating from molecular hydrogen. The Pt/HSi@Y was prepared using seed assisted crystallization followed by protonation and Pt-loading. The product formed had a spherical morphology with bicontinuous lamellar with a diameter in the range of 500-700 nm. The catalytic activity of the Pt/HSi@Y has been assessed based on light linear alkane (C5-C7) isomerization in a micro-catalytic pulse reactor at 423-623 K. A pyridine IR study confirmed that the introduction of fibrous silica on Y zeolite increased the Lewis acid sites corresponding with the formation of extra-framework Al which led to the generation of more protonic acid sites. A hydrogen adsorbed IR study showed that the protonic acid sites which act as active sites in the isomerization were formed via dissociative-adsorption of molecular hydrogen releasing electrons to the nearby Lewis acid sites. Thus, it is suggested that the presence of Pt and HSi@Y with a high number of Lewis acid as well as weak Bronsted acid sites improved the activity and stability in C5, C6 and C7 isomerization via hydrogen spill-over mechanism.

Study on the pinene isomerization catalyzed by TiM

The isomerization reaction of pinene is one of the most important chemical reactions in the deep processing of pinene. The purpose of this study is to improve the performance of the metatitanic acid by composite. The composite metatitanic acid catalyst TiM was prepared by adding Mn elements in the preparation process. The catalytic performance of TiM was evaluated. Comparison of TiM and metatitanic acid catalyst(Ti-FGP), the reaction rate of TiM catalyst was faster, and after the reaction, the yield of camphene and tricyclene increased about 1%. The catalysts were characterized by an SEM, FT-IR and laser particle size analyzer. The results show that the pinene isomerization reaction requires the synergistic action of the Br?nsted acid and Lewis acid.Br?nsted acid has great influence on the activity of catalyst, and Lewis acid has a great influence on the selectivity of the catalyst. The structure and morphology of the catalyst have a certain effect on the selectivity of pinene isomerization reaction.

A Promising MoO_x-based Catalyst for n-Heptane Isomerization

The SiO2 and g-Al2O3 supported MoOx catalyst and a MoOx-SiO2 catalyst have been studied in a conventional fixed-bed flow reactor for n-alkanes isomerization. It is shown that the MoOx-SiO2 catalyst with SiO2 framework, in which the bulk MoOx phase is large enough to form typical mesoporous structure, is promising in terms of its advantages of both improved mechanical strength and high catalytic properties over the supported MoOx and bulk MoOx catalyst.

The Effect of n-Hexane on the Gonad Toxicity of Female Mice

Objective To investigate the toxic effects of n-hexane on the Ganod of female mice.Methods n-Hexane was administered to four groups of mice by inhalation at doses of 0,3.0,15.1,and 75.8 mL/m3 respectivelyfor five weeks.Each group consisted of 10 mice,of which half were injected in first with 10 IU of pregnant mare serum gonadotrophin（PMSG） on the 33rd days,and then with 10 IU of human chorionic gonadotrophin（HCG） 48 hrs later.After the treatment,mouse sera were sampled and ovulating hormone（LH）,follicle-stimulating hormone（FSH）,estradiol（E2）,and progesterone（P4） levels were measured by electrochemiluminescence immunoassays（ECLIA）.In each group,the right ovaries of the non-super-ovulated mice were stained with hematoxylin and eosin while ovaries on the left side were prepared with the TUNEL method in order to detect apoptotic cells.Results The duration of the diestrus stage decreased significantly（P0.05） in the 75.8 mL/m3 group.All super-ovulated mice in each treatment group produced fewer eggs than those in the control group（P0.05）.The number of follicles in ovaries in the 75.8 mL/m3 group was smaller compared with the control group（P0.05）.The serum P4 levels in each treatment group were lower than those in the control group（F=6.196,P0.01）.The cell apoptotic rate in the 75.8 mL/m3 group was higher（P0.05）.Conclusion n-Hexane may have directly mediated via alterations hormone secretion and promoted granulosal cell apoptotic,which may be one of the important mechanisms for n-hexane induced mouse ovary impairment.

Theoretical Study of Halogen Effect in Isomerization of 2-Halo-[9]-annulen Anion at the DFT Level

Cis-trans isomerization of [9]-annulenanion（1） and its 2-fluoro-,2-chloro-and 2-bromo-derivatives（2,3 and 4,respectively） were investigated at the HF/6-31G＊ and B3LYP/6-311＋＋G＊＊ levels of theory.Cis,cis,cis,cis structures appear more stable than their corresponding cis,cis,cis,trans-isomers.The relative height of energy barriers for cis-trans isomerization is：2cis 〉1cis 〉3cis〉 4cis.This trend for the reverse trans-cis isomerization follows the electronegativity of the substituent at C-2（2trans 3trans 4trans 1trans）.

Chloroaluminate ionic liquid catalyzed isomerization of n-pentane in the presence of product distribution improver

The ionic liquid Et3NHC1-2AIC13 can catalyze the isomerization of n-pentane. This paper investigates the ionic liquid catalyzed isomerization performance of n-pentane with several product distribution improvers in an autoclave. The product distribution of n-pentane isomerization could be improved by such improvers as benzene, cyelohexane, and methyl cyclohexane at the expense of conversion of n-pentane. The optimal product distribution improver was determined to be cyclohexane. The yield of isomerate and the selectivity of liquid isoalkanes increased, whereas the conversion of n-pentane decreased, with increasing cyclohexane amount. At the same conversion of n-pentane, the research octane number （RON） of liquid product, with cyclohexane amount of 0.5 wt%, was about 1.3 higher than that without cyclohexane. At the same reaction conditions, the presence of cyclohexane enhanced the yield of isomerate, the selectivity of liquid isoalkanes, and the RON of the liquid product, but reduced the conversion of n-pentane.

Triphenylphosphine-catalyzed isomerization of alkynyl ketones in aqueous solution

An efficient isomerization of alkynyl ketones to (E,E)-diene ketones was developed. The reaction catalyzed by 20 mol% triphenylphosphine in aqueous media gave the desired products in good yields.

Effect of Ni Loading on the Catalytic Properties of Molybdenum Oxides for the Isomerization of Heptane

The catalytic properties of MoOx and incorporation Ni onto the MoOx for the isomerization of heptane have been investigated under atmospheric pressure at different conditions such as different flow rate of H2, different reaction temperature etc.. Compared with MoOx, the Ni addition to the MoOx markedly improved the isomerization activity of heptane by improving the reducibility of MoO3 and activation of H2 in reaction.

Isomerization of n-octane on NiW/HSAPO-11 Catalyst

The catalyst NiW/HSAPO-11 was prepared by impregnating Ni and W onto HSAPO-11 zeolite with two different methods. The isomerization and aromatization properties were investigated with an microreactor using n-octane as a feedstock. NiW/HSAPO-11 shows a high hydroconversion activity of n-octane, and the optimum operating parameters for the catalyst to produce high octane number products were: 400℃, 2.0MPa, VH2:Vn-octane= 400:1, liquid hourly space velocity LHSV=1.0h-1. Under the optimum reaction condition, the conversion efficiency, C5 liquid + product selectivity, isomerization and aromatization product selectivity were 69.80%, 56.95%, 79.73% and 1.29% respectively. The catalyst (S1) impregnated with Ni and W after the HSAPO-11 zeolite was combined with Al2O3 matrix, performed better than the catalyst (S2) impregnated with Ni and W before combining with the Al2O3 matrix.

Explanation of Theoretical Mechanism of Isomerization of L-Alanine Conformation for Experimental Results

B3LYP/6-31＋＋G＊＊ method was applied to investigate the mechanism of alanine isomerization.12 minima and 22 transition states were obtained after optimization and several paths of isomerization were found.It is found that intramolecular single-bond rotation and proton transfer might lead to isomerization.The energy barrier of C–N bond rotation was lower than 2.52 kcal·mol 1,while the energy barrier ranges of the rotation of C–C and C–O were separately 0.43~ 7.01 and 4.69~12.19 kcal·mol 1,and the minimum energy barrier of proton transfer was 30.76 kcal·mol 1.The most probable isomerization path and mechanism for the two most stable conformations was discussed to find that the highest energy barrier to be crossed in this path was 11.87 kcal·mol 1.In order to understand the microscopic nature why only 4 conformations were detected in the experiment,thermodynamic properties of all conformations at the experimental temperature of 391 K was calculated.It is found that conformations XII,XI,X and IX can only unidirectionally convert into conformations rapidly with low energy and vanish immediately.The other conformations were distributed according to Maxwell-Boltzman＇s law,and the distribution probabilities of conformations I,II,III,IV,V,VI,VII and VIII were respectively 27.2%,26.5%,25.8%,6.4%,5.2%,4.8%,2.5% and 1.6%.Conformations I,II and III with bigger probability and stronger absorption peak were easy to detect in the experiment.Conformation IV had a relatively smaller probability（6.4%） and weak absorption peak which,however,could also be identified.The other conformations had too small probability to identify in the spectrum.