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.

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%.

Hydrocracking diversity in n-dodecane isomerization on Pt/ZSM-22 and Pt/ZSM-23 catalysts and their catalytic performance for hydrodewaxing of lube base oil

Nobel metallic Pt/ZSM-22 and Pt/ZSM-23 catalysts were prepared for hydroisomerization of normal dodecane and hydrodewaxing of heavy waxy lube base oil.The hydroisomerization performance of n-dodecane indicated that the Pt/ZSM-23 catalyst preferred to crack the C-C bond near the middle of n-dodecane chain,while the Pt/ZSM-22 catalyst was favorable for breaking the carbon chain near the end of n-dodecane.As a result,more than 2%of light products(gas plus naphtha)and3%more of heavy lube base oil with low-pour point and high viscosity index were produced on Pt/ZSM-22 than those on Pt/ZSM-23 while using the heavy waxy vacuum distillate oil as feedstock.

Novel endo-to exo-isomerization of dicyclopentadiene

Endo-dicyclopentadiene was isomerized to exo-isomer by thermal treatment at evaluated temperature and pressure. The reaction temperature and pressure are key factors for this novel isomerization. This result may have great potential for practical application.

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.

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.

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.

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.

AlCl3 Supported Catalysts for the Isomerization of <i>Endo</i>-Tetrahydrodicyclopentadiene

Two of zeolites such as Hβ and HY, and mesoporous HMCM-41 were used as supports to immobilize AlCl3 for the investigation of the isomerization of endo-tetrahydrodicyclopentadiene (endo-TCD). The dependences of porous structure and surface acidity of the AlCl3 immobilized catalysts on the activity and selectivity were studied. Based on characterization studies, both the large pore diameter and strong acid sites of the supported catalysts contributed to the high activities in the endo-TCD conversion. And specifically the stronger Lewis acid sites seems to be responsible for the higher selectivity onto exo-TCD, and the stronger Br?nsted acid sites were crucial to the formation of adamantane through the further isomerization of exo-TCD.

Stereo-Selective Synthesis of 5-Norbornene-2-<i>exo</i>-carboxylic Acid—Rapid Isomerization and Kinetically Selective Hydrolysis

Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.

γ-Al₂O₃Supported SO₄^2&#45/ZrO₂Solid Superacid Catalysts for n-Pentane Isomerization

A solid superacid catalyst Pt-SO42-/ZrO2-A12O3 for n-pentane isomerization, was prepared by incipient-wetness impregnation. Preparetion conditions, namely, calcination temperature, concentration of sulfuric acid solution used in impregnation and Al2O3 concentration, were varied to investigate the effects on catalytic performance of Pt-SO42-/ZrO2-A12O3. The results showed that the PtSZA catalyst exhibited excellent catalytic performance for n-pentane isomerization. Under optimized preparation conditions of calcination temperature of 650°C, reaction time for 3 h, concentration of sulfuric acid solution for 0.5 mol/L, 30% of Al2O3 concentration and 0.3% of Pt concentration, the n-pentane conversion and isopentane selectivity of Pt-SO42-/ZrO2-A12O3 could reach up to 62.17% and 91.60%, respectively.

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.

STUDIES ON ISOMERIZATION OF δ－NITRILES TO PYRIDONES CATALYZED BY INORGANIC ACID SALTS

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Effects of Pressure, Solvent, and Substituent on the Thermal Isomerization of 2-Oxo- spiro[diazirine-3,3'-indoline]

The kinetic effects of pressure, solvent, and substituent on the thermal isomerization from 2 oxospiro[diazirine 3,3 indoline] to 3 diazo 2 oxo indoline have been examined. The rate constants of the thermal isomerization increased with increasing external pressure and were related to the σ + P substituent constant of Hammett correlation. The results suggest that the thermal isomerization proceeds via a dipolar transition state involving heterolytic bond fission. However, the kinetic solvent effects on the thermal isomerization were not observed. The special solvent effects were discussed on the basis of the linear free energy relationship.

Application of kinetics and computational fluid dynamics in pinene isomerization

A reliable kinetic model to describe the effects of various factors on the reaction rate and selectivity of pinene isomerization is developed. Furthermore, computational fluid dynamics(CFD) is applied to simulate the solid–liquid dispersion in reactor. The catalyst Ti M is obtained by improving the composition and structure of hydrated titanium dioxide. The kinetic equation of pinene isomerization is deduced based on reaction mechanism and catalyst deactivation model. The kinetic equation of pinene isomerization reaction is fitted, and the results show that the fitted equation is correlated with the experimental data. The rate and selectivity of pinene isomerization reaction are affected by the amount of catalyst, deactivation of catalyst, structure of catalyst, reaction temperature and water content of catalyst. The solid–liquid distribution of the reactor is calculated by computational fluid dynamics numerical simulation, and the solid–liquid dispersion in commercial scale reactor is more uniform than that in lab-scale reactor.

A reaction density functional theory study of solvent effects on keto-enol tautomerism and isomerization in pyruvic acid

It is important to study the solvent effect on keto-enol tautomerism that has applications in many areas of chemical engineering.In this work,we use a multiscale reaction density functional theory(Rx DFT)to study the keto-enol tautomerism and isomerization of pyruvic acid.The results show that both effects of solvation and water assistance could reduce the reaction barriers.The water molecule participates the reaction as a catalyst to accept/give the protons with forming a hexagonal ring in the transition state.As a result of this temporary and intermediate hexagonal ring,the solute configuration undergoes a small variation during the reaction,giving a diminished contribution to the intrinsic reaction free energy.The solvent distribution shows a local ordering behavior near the solute that also reduces the contribution of solvation effect to the reaction barrier.Water assistance plays a major role in both pre-reaction and postreaction process.In terms of the driving force for the reaction,the effects of both solvation and water assistance are important.

A Novel MIL-101(Cr)Acidified by Silicotungstic Acid and Its Catalytic Performance for Isomerization of n-Heptane

The 0.4%Pt/xSTA-MIL-101(Cr)metal-acid bifunctional catalysts were prepared by impregnation using STA-MIL-101(Cr)as the support.The synthesized samples were verified to exhibit a typical octahedral structure of MIL-101(Cr)and the pore structure was arranged orderly.The specific surface area of the samples was extremely high and the samples were made of micro-mesoporous composite materials.Silicotungstic acid could retain its Keggin structure in the 0.4%Pt/xSTA-MIL-101(Cr)samples and the catalyst possessed moderately strong Brønsted acid sites.Besides,the dispersion of Pt particles in MIL-101(Cr)was relatively high.n-Heptane isomerization was first used as a probe to test the novel 0.4%Pt/xSTA-MIL-10(Cr)catalyst.Compared with the conventional silicate catalysts,the catalytic performance of 0.4%Pt/30%STA-MIL-101(Cr)was significantly improved with a n-heptane conversion of 58.93%and an iso-heptane selectivity of 95.68%,respectively,under conditions covering a reaction time of 2 h and a reaction temperature of 260°C.The catalyst could still maintain a relatively high catalytic performance after a reaction time of 5 h.Compared with the non-noble metal catalyst,the catalytic efficiency of 0.4%Pt/30%STA-MIL-101(Cr)is relatively high.The mechanism model of n-heptane isomerization over 0.4%Pt/xSTA-MIL-101(Cr)catalyst was established.