Reaction pathways and selectivity in the chemo-catalytic conversion of cellulose and its derivatives to ethylene glycol:A review

Biomass-to-ethylene glycol is an effective means to achieve high-value utilisation of cellulose but is hindered by low conversion efficiency and poor catalyst activity and stability.Glucose and cellobiose are derivatives of cellulose conversion to ethylene glycol,and it is found that studying the reaction process of both can help to understand the reaction mechanism of cellulose.It is desirable to develop a reusable,highly active catalyst to convert cellulose into ethylene glycol.This ideal catalyst might have one or more active sites described the conversion steps above.Here,we discuss the catalyst development of celluloseto-ethylene glycol,including tungsten,tin,lanthanide,and other transition metal catalysts,and special attention is given to the reaction mechanism and kinetics for preparing ethylene glycol from cellulose,and the economic advantages of biomass-to-ethylene glycol are briefly introduced.The insights given in this review will facilitate further development of efficient catalysts,for addressing the global energy crisis and climate change related to the use of fossil fuels.

Preparation and Thermo-Responsive Properties of Poly(Oligo(Ethylene Glycol)Methacrylate)Copolymers with Hydroxy-Terminated Side Chain

Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.

Analysis of Ethylene Glycol Degumming Process and Characterization of Hemp Fibers

To overcome the shortcomings of traditional degumming process,an efficient and environmentally friendly ethylene glycol(EG) degumming process was adopted to degum hemp fibers.The surface morphology,chemical composition,chemical structures,and mechanical properties of the fiber samples were analyzed to explore the mechanism of the degumming process.It was found that the EG degumming process could be divided into the main degumming stage(heating) and the supplementary degumming stage(insulation).The removal rates of hemicellulose and lignin in the main degumming stage were 70.56% and 60.17%,respectively.In the supplementary degumming stage,9.95% hemicellulose and 25.39% lignin were removed.It is confirmed that EG can separate hemp fibers effectively with less damage,which holds great potential for the biomass fiber separation technology.

Study of Thermal,Phase Morphological and Mechanical Properties of Poly(L-lactide)-b-Poly(ethylene glycol)-b-Poly(L-lactide)/Poly(ethylene glycol)Blend Bioplastics

A poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)(PLLA-PEG-PLLA)block copolymer has great potential for use as a flexible bioplastic.Highly flexible bioplastics are required for flexible packaging applications.In this work,a PEG was incorporated into block copolymer as a plasticizer by solvent casting.PLLA-PEG-PLLA/PEG blends with different blend ratios were prepared,and the plasticizing effect and miscibility of PEG in block copolymer were intensively investigated compared to PLLA/PEG blends.The results indicated that the PEG was an effective plasticizer for the block copolymer.The blending of PEG decreased glass-transition temperature and accelerated the crystallization of both the PLLA and PLLA-PEG-PLLA matrices.The PEG was completely miscible when blended with block copolymer and it improved thermal stability of the block copolymer matrix but not of the PLLA matrix.Film extensibility of PLLA-PEG-PLLA/PEG blends steadily increased as the PEG ratio increased.These non-toxic and highly flexible PLLA-PEG-PLLA/PEG bioplastics are promising candidates for several applications such as biomedical devices,tissue scaffolds and packaging materials.

Significance of Nanoparticles Aggregation with Cattaneo-Christov Heat Flux on the Water and Ethylene Glycol Mixture Based MWCNTs-Nanofluid Flow over a Stretching Cylinder

This work aims to analyze the flow of electrically conducting MWCNTs-nanofluid over a stretching cylinder with the aggregation and non-aggregation effects of nanoparticles. The working fluid comprised a combination of water and ethylene glycol, with volumetric proportions of (50:50) considered. Convective boundary constraints and modified Fourier law are implemented in heat transmission assessment. The mathematical flow model is formulated in the form of PDEs and is transformed into ODEs via similarity transformation. Numerical outcomes will be obtained with the use of the bvp4c technique and will be displayed with the help of graphs and tables. The results show that the surface drag coefficient is enhanced in the case of aggregation of nanoparticles whereas heat transfer rate is enhanced in the non-aggregation effect of nanoparticles. Furthermore, the temperature distribution enhances the increasing values of particle volume fraction in the case of aggregation effects of nanoparticles whereas temperature distribution lowers in the case of non-aggregation effect of nanoparticles. .

Synthesis of Nano-sized Yttria via a Sol-Gel Process Based on Hydrated Yttrium Nitrate and Ethylene Glycol and Its Catalytic Performance for Thermal Decomposition of NH_4ClO_4

Nano-sized yttria particles were synthesized via a non-aqueous sol-gel process based on hydrated yttrium nitrate and ethylene glycol. The effects of the molar ratio of ethylene glycol to yttrium ion and calcination temperature on crystallite size of the products were studied. The catalytic performance of the as-prepared yttria for the ammonium perchlorate （AP） decomposition was investigated by differential scanning calorimetry （DSC）. The results indicate that the nano-sized cubic yttria particles with less than 20 nm in average crystallite size can be obtained after 2 h reflux at 70℃, dried at 90 ℃, forming xerogel, and followed by annealing of xerogel for 2 h, and that the addition of the nano-sized yttria to AP incorporates two small exothermic peaks of AP in the temperature ranges of 310 - 350 ℃ and 400 - 470 ℃ into a strong exothermic peak of AP and increases the apparent decomposition heat from 515 to over 1110 J·g^- 1. It is also clear that the temperature of AP decomposition exothermic peak decreases and the apparent decomposition heat of AP increases with the increase of the amount of nano-sized yttria. The fact that the addition of the 5 % nano-sized yttria to AP decreases the temperature of AP exothermic peak to 337.7℃ by reduction of 114.6℃ and increases the apparent decomposition heat from 515 to 1240 J·g^-1, reveals that nano-sized yttria shows strong catalytic property for AP thermal decomposition.

Effect of copper loading on texture,structure and catalytic performance of Cu/SiO_2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol

Cu/SiO2 catalysts prepared by a convenient and efficient method using the urea hydrolysis deposition-precipitation （UHDP） technique have been proposed focusing on the effect of copper loading.The texture,structure and composition are systematically characterized by ICP,FTIR,N 2-physisorption,N2O chemisorption,TPR,XRD and XPS.The formation of copper phyllosilicate is observed in Cu/SiO2 catalyst by adopting UHDP method,and the amount of copper phyllosilicate is related to copper loading.It is found the structure properties and catalytic performance is profoundly affected by the amount of copper phyllosilicate.The excellent catalytic activity is attributed to the synergetic effect between Cu0 and Cu ＋.DMO conversion and EG selectivity are determined by the amount of Cu0 and Cu＋,respectively.The proper copper loading （30 wt%） provides with the highest ratio of Cu ＋ /Cu0,giving rise to the highest EG yield of 95% under the reaction conditions of p=2.0 MPa,T=473 K,H2/DMO=80 and LHSV=1.0h-1.

Interface tuning of Cu+/CuO by zirconia for dimethyl oxalate hydrogenation to ethylene glycol over Cu/SiO2 catalyst

An efficient ZrO2-doped Cu/SiO2 catalyst was fabricated through hydrolysis precipitation method(HP)and used to produce ethylene glycol(EG)through dimethyl oxalate(DMO)hydrogenation.The states for zirconia on copper catalyst and roles in DMO hydrogenation were investigated through various characterization tools,including N2 physical adsorption,XRD,H2-TPR,Methyl glycolate-TPD-MS,XPS,XAES as well.Compared with common ammonia evaporation and co-precipitation methods used in catalyst preparation,this HP method is found to effectively suppress the agglomeration and further size growth of copper nanoparticles by enhancing the interactions between copper and zirconia species.More importantly,uniform distribution of ZrO2 dopant is achieved due to the pseudo-homogeneous reactions in the mixing step of catalyst preparation.A proper amount of zirconium dopant helps achieve the desirable proportion of Cu+/(Cu++CuO)for surface copper species,especially promotes the production of Cu+species originated from Cu-ZrO2 species at the interface of copper and zirconia particles.In comparison with Cu+species formed from copper phyllosilicates reduction,the Cu+sites derived from Cu-ZrO2 species show higher adsorption ability of MG,an important intermediate species in ethylene glycol production.These adsorbed MG molecules further react with atomic hydrogen shifted from adjacent metallic copper surface,leading to a higher catalytic behavior.For the EG production via DMO hydrogenation,the turnover frequency(TOF)normalized by CuO species on CuZr/SiO2 catalyst is 1.8 times than that of traditional Cu/SiO2 counterpart.Due to the enhanced synergy effect between Cu+and Cuo active sites,a lower activation energy of ester hydrogenation on this ZrO2-doped Cu/SiO2 catalyst is believed to be responsible for the significant improvement.

SURFACE MODIFICATION OF BLEND FILMS COMPOSED OF SILK FIBROIN AND POLY(ETHYLENE GLYCOL) MACROMER AND THEIR IN VITRO ANTITHROMBOGENICITY

In order to improve the blood compatibility of silk fibroin (SF), poly(ethylene glycol) macromer (PEGM) in different amounts was added to the SF film to incorporate C=C group into the surface of blend films which were then modified by SO2 gas plasma treatment. ATR-FITR and XPS were used to analyze the chemical change which had occurred on the film's surface. When the content of sulfur on the surface of blend films surpasses 1.59%, the antithrombogenicity of plasma treated films increases remarkably due to surface sulfonation. This result implies that SF with blend of PEGM after SO2 plasma treatment have potential use for making blood-contacting biomaterials.

Catalytic Performance and Texture of TEOS Based Cu/SiO_2 Catalysts for Hydrogenation of Dimethyl Oxalate to Ethylene Glycol

Highly active and selective Cu/SiO2 catalysts for hydrogenation of dimethyl oxalate（DMO） to ethylene glycol（EG） were successfully prepared by means of a convenient one-pot synthetic method with tetraethoxysi lane（TEOS） as the source of silica. XRD, H2-TPR, SEM, TEM, XRF and N2 physisorption measurements were performed to characterize the texture and structure of Cu/SiO2 catalysts with different copper loadings. The active components were highly dispersed on SiO2 supports. Furthermore, the coexistence of Cu0 and Cu＋ contributed a lot to the excellent performance of Cu-TEOS catalysts. The DMO conversion reached 100% and the EG selectivity reached 95% at 498 K and 2 MPa with a high liquid hourly space velocity over the 27-Cu-TEOS catalyst with an actual cop per loading of 19.0%（mass fraction）.

The adsorption properties of NaY zeolite for separation of ethylene glycol and 1,2-butanediol: Experiment and molecular modelling

The separation of ethylene glycol(EG)and 1,2-butanediol(1,2-BDO)azeotrope in the synthesis process of EG via coal and biomass is becoming of increasing commercial and environmental importance.Selective adsorption is deemed as the most promising methods because of energy saving and environment favorable.In this paper,NaY zeolite was used to separate 1,2-BDO from EG,and its adsorption properties was then investigated.The isotherms of EG and 1,2-BDO in vapor and liquid phases from 298 to 328 K indicated that they fitted Langmuir model quite well,and the NaY zeolite absorbent favored EG more than 1,2-BDO.The Grand Canonical Monte Carlo(GCMC)and molecular dynamics(MD)simulation techniques were conducted to investigate the competition adsorption and diffusion characteristics in different adsorption regions.It was observed that EG and 1,2-BDO molecules all have the most probable locations of the center of the 12-membered ring near the Na cations.The diffusivities of EG are lower than those of 1,2-BDO at the same adsorption concentration.At last,the breakthrough curves of the binary mixture regressed from the empirical Dose–Response model in fixed-bed column showed that the adsorption selectivity of EG could reach to as high as 2.43,verified that the NaY zeolite could effectively separate EG from 1,2-BDO.This work is also helpful for further separation of other dihydric alcohol mixtures from coal and biomass fermentation.

PREPARATION OF HIGH DENSITY POLYETHYLENE/POLYETHYLENE-BLOCK-POLY(ETHYLENE GLYCOL)COPOLYMER BLEND POROUS MEMBRANES VIA THERMALLY INDUCED PHASE SEPARATION PROCESS AND THEIR PROPERTIES

High density polyethylene （HDPE）/polyethylene-block-poly（ethylene glycol） （PE-b-PEG） blend porous membranes were prepared via thermally induced phase separation （TIPS） process using diphenyl ether （DPE） as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry （DSC）. By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy （SEM） and wide angle X-ray diffraction （WAXD）. The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection （FTIR-ATR） and X-ray photoelectron spectroscopy （XPS）. Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.

Poly(L-lactide)-Poly(ethylene glycol) Multiblock Copolymers: Synthesis and Properties

Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.

THE STRUCTURE AND PROPERTIES OF CHITOSAN/POLYETHYLENE GLYCOL/SILICA TERNARY HYBRID ORGANIC-INORGANIC FILMS

The ternary hybrid films consisting of chitosan(CS),polyethylene glycol(PEG)and nano-sized silica which was surface-modified by amino groups(RNSA)were prepared.The structures of the blend membranes were characterized by attenuation total reflection-infrared spectroscopy(ATR-IR),X-ray diffraction(XRD),optical microscopy(OM)and differential scanning calorimetry(DSC).The results showed that the addition of silica affected not only the distribution and crystallinity of PEG on the sample surface,but also the pha...

Influence of Ethylene Glycol on the Formation of Calcium Phosphate Nanocrystals

A synthesis route of using calcium hydroxide Ca(OH)2 with ethylene glycol solvent and orthophosphoric acid (H3PO4) as reagents is described. Three ratios of ethylene glycol to distilled water 1:0, 1:1 and 0:1 are used as diluting media for Ca(OH)2. Crystals of different morphology and composition are formed under weak alkaline circumstance at pH 7.0-8.0. Acicular calcium phosphate nanocrystals are prepared in pure ethylene glycol while rod-like calcium phosphate nanocrystals form in pure distilled water. The nanograde size of the former is smaller than that of the latter. Calcium-deficient apatite (CDAP) is obtained with a Ca/P molar ratio of 1.66. Therefore, it was deduced that the usage of ethylene glycol solvent could influence the formation of calcium phosphate crystal lattice.

Flexible transparent wood enabled by epoxy resin and ethylene glycol diglycidyl ether

Transparent wood has potential application in intelligent building,solar cell,electronics,and other advanced materials,while its single functionability hinders its further development.Flexible transparent wood(FTW)was prepared by alkaline pretreatment and bleaching treat-ment of paulownia wood followed by impregnation of epoxy resin and ethylene glycol diglycidyl ether(EDGE).The eff ect of delignifi cation degree on the optical and mechani-cal properties of FTW was studied,and the infl uence of the epoxy/EDGE ratio on the fl exibility and mechanical proper-ties of FTW was also investigated.The results showed that higher delignifi cation degree resulted in higher transmit-tance of FTW.More EDGE addition led to better fl exibility of FTW,while overmuch addition of EDGE will reduce the mechanical properties.The optimal FTW sample resulted in a high transmittance of 89%and an ultrahigh haze value of 97%with outstanding fl exibility and excellent mechanical properties.The investigation of FTW broadens the research fi eld of transparent wood,and provides great possibility for its application in fl exible wearable devices and fl exible materials.

Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP

Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （ATRP）. A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly（ethylene glycol） monomethyl ether （PEG）. The copolymers were obtained via the ATRP ofN-isopropylacrylamide （NIPAM） at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O （v/v = 3：1） mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography （GPC） and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions （PDI 〈 1.15）. Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry （DSC）. As a result, the phase transition temperature of PEG45-b-（PNIPAM55）2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.

In situ IR study of dimethyl oxalate hydrogenation to ethylene glycol over Cu/SiO_2 catalyst

The mechanism of dimethyl oxalate hydrogenation to ethylene glycol over Cu/SiO2 catalyst was investigated by in situ Fourier transform infrared （FTIR） spectroscopy. It was found that dimethyl oxalate and methyl glycolate proceeded via dissociative adsorption on Cu/SiO2 catalyst, and four main intermediates, CH3OC（O）（O）C-M （1655 cm-1）, M-C（O）（O）C-M （1618 cm-1）, HOCH2（O）C--M （1682 cm-1） and CH3O-M （2924-2926 cm-1）, were identified during the reaction. It was concluded that dimethyl oxalate hydrogenation to ethylene glycol mainly proceeded along the route： dimethyl oxalate ／rightarrow CH3OC（O）（O）C-M → methyl glycolate →HOCH2（O）C-M → ethylene glycol. Finally a schematic reaction network was proposed.

Novel Salt-Assisted Combustion Synthesis of High Surface Area Ceria Nanopowders by An Ethylene Glycol-Nitrate Combustion Process

A novel salt-assisted combustion process with ethylene glycol as a fuel and nitrate as an oxidant to synthesize high surface area celia nanopowders was reported. The effects of various tunable conditions, such as fuel-to-oxidant ratio, type of salts, and amount of added salts, on the characteristics of the as-prepared powders were investigated by X-ray diffraction, transmission electron microscopy and BET surface area measurement. A mechanism scheme was proposed to illustrate the possible formation processes of well-dispersed ceria nanoparticles in the salt-assisted combustion synthesis. It was verified that the simple introduction of leachable inert inorganic salts as an excellent agglomeration inhibitor into the redox mixture precursor leads to the formation of well-dispersed ceria particles with particle size in the range of 4 ～6 nm and a drastic increase in the surface area. The presence of KCl results in an over ten-fold increment in specific surface area from 14.10 m^2·g^-1 for the produced ceria powders via the conventional combustion synthesis process to 156.74 m^2·g^-1 for the product by the salt-assisted combustion synthesis process at the same molar ratio of ethylene glycol-nitrate.

Ethylene glycol purification by melt crystallization:Removal of 2-methoxyethanol impurity

The coal(syngas)-to-ethylene glycol(CTEG),is contaminated with the naughty impurity 2-Methoxyethanol(ME)generated during the hydrogenation stage,which affect the quality of EG for fiber-grade polyester production.Distillation,is the employed separation process in industrial,which makes production complicated because of the heat sensitivity of the impurities system.Melt crystallization has been regarded as an effective technology to obtain high-purity organic compounds based on the melting points difference,which could avoid the problems by heating.In this work,we have explored the feasibility of the static melt crystallization on the separation of EG/ME in a jacketed crystallization tube.The experimental parameters were investigated,which covers crystallization and sweating stage in each step.The results showed that the purity of EG could reach≥99.8%from the binary system studied via the quaternary separation process.