The high-efficient development of shale oil is one of the urgent problems in the petroleum industry. The technology of CO_(2) enhanced oil recovery(EOR) has shown significant effects in developing shale oil. The effec...The high-efficient development of shale oil is one of the urgent problems in the petroleum industry. The technology of CO_(2) enhanced oil recovery(EOR) has shown significant effects in developing shale oil. The effects of several glycol ether additives with low molecular weight on the interactions between CO_(2) and oil were investigated here. The solubility of glycol ether additive in CO_(2) was firstly characterized. Then,the effects of glycol ether additives on the interfacial tension(IFT) between CO_(2) and hexadecane and the volume expansion and extraction performance between CO_(2) and hexadecane under different pressures was investigated. The experimental results show that diethylene glycol dimethyl ether(DEG), triethylene glycol dimethyl ether(TEG), and tetraethylene glycol dimethyl ether(TTEG) all have low cloud point pressure and high affinity with CO_(2). Under the same mass fraction, DGE has the best effect to reduce the IFT between hexadecane and CO_(2) by more than 30.0%, while an overall reduction of 20.0%-30.0% for TEG and 10.0%-20.0% for TTEG. A new method to measure the extraction and expansion rates has been established and can calculate the swelling factor accurately. After adding 1.0% DEG, the expansion and extraction amounts of CO_(2) for hexadecane are respectively increased to 1.75 times and 2.25 times. The results show that glycol ether additives assisted CO_(2) have potential application for EOR. This study can provide theoretical guidance for the optimization of CO_(2) composite systems for oil displacement.展开更多
Methyl glycolate is a good solvent and can be used as feedstock for the synthesis of some important organic chemicals. Catalytic hydrogenation of dimethyl oxalate （DMO） over copper-silver catalyst supported on silic...Methyl glycolate is a good solvent and can be used as feedstock for the synthesis of some important organic chemicals. Catalytic hydrogenation of dimethyl oxalate （DMO） over copper-silver catalyst supported on silica was studied. The Cu-Ag/SiO2 catalyst supported on silica sol was prepared by homogeneous deposition-precipitation of the mixture of aqueous euprammonia complex and silica sol. The proper active temperature of Cu-Ag/SiO2 catalyst for hydrogenation of DMO was 523-623 K. The most preferable reaction conditions for methyl glycolate （MG） were optimized： temperature at 468-478 K, 40-60 mesh catalyst diameter, H2/DMO ratio 40, and 1.0 h^-1 of LHSV.展开更多
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 a...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.展开更多
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 ca...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.展开更多
The directly selective hydrogenolysis of xylitol to ethylene glycol(EG) and 1,2-propylene glycol(1,2-PDO)was performed on Cu–Ni–ZrO_2 catalysts prepared by a co-precipitation method. Upon optimizing the reaction con...The directly selective hydrogenolysis of xylitol to ethylene glycol(EG) and 1,2-propylene glycol(1,2-PDO)was performed on Cu–Ni–ZrO_2 catalysts prepared by a co-precipitation method. Upon optimizing the reaction conditions(518 K, 4.0 MPaH_2 and 3 h), 97.0% conversion of xylitol and 63.1% yield of glycols were obtained in water without extra inorganic base. The catalyst still remained stable activity after six cycles and above 80% total selectivity of glycols was obtained when using 20.0% xylitol concentration. XRD, TEM and ICP results indicated that Cu–Ni–ZrO_2 catalysts possess favorable stability. Cu and Ni are beneficial to the cleavage of C–O and C–H bond, respectively. To reduce the hydrogen consumption, isopropanol was added as in-situ hydrogen source and 96.4% conversion of xylitol with 43.6% yield of glycols were realized.展开更多
MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the...MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the roles of nickel, ZnO and MnOx were investigated. The results show that nickel provided a new pathway of glucose to sorbitol and played an important role in the hydrogenation of C3 intermediates to 1,2-propanediol(1,2-PDO). The high yield of 1, 2-PDO was attributed to effective C–C bond cleavage performance of ZnO support promoted by MnOx. ZnO and MnOx contribute to the conversion of glycerol to lactic acid(LA) and LA to 1, 2-PDO, respectively. A concise pathway for hydrogenation of glucose over Ni-based catalyst was proposed.展开更多
Hydrogen production by steam reforming of ethylene glycol(EG) at 300℃ was investigated over SiO2 and CeO2 supported Pt–Ni bimetallic catalysts prepared by incipient wetness impregnation methods. It was observed that...Hydrogen production by steam reforming of ethylene glycol(EG) at 300℃ was investigated over SiO2 and CeO2 supported Pt–Ni bimetallic catalysts prepared by incipient wetness impregnation methods. It was observed that impregnation sequence of Pt and Ni can affect the performance of catalysts apparently. Catalyst with Pt first and then Ni addition showed higher EG conversion and H2 yield owing to the Ni enrichment on the surface and the proper interaction between Pt and Ni. It was observed that although SiO2 supported catalysts exhibited better activity and H2 selectivity, CeO2 supported ones had better stability. This is attributed to the less coke formation on CeO2. Increasing Pt/Ni ratio enhanced the reaction activity, and Pt3–Ni7 catalysts with 3 wt% Pt and 7 wt% Ni showed the highest activity and stability. Ni surficial enrichment facilitated the C-C bond rupture and water gas shift reactions;and Pt addition inhibited methanation reaction. Electron transfer and hydrogen spillover from Pt to Ni suppressed carbon deposition. These combined effects lead to the excellent performance of Pt3–Ni7 supported catalysts.展开更多
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 d...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.展开更多
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 glyc...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.展开更多
Mud shale hydration and swelling are major challenges in the development of water-based drilling fuids(WBDFs).In this work,the inhibition performance and inhibition mechanism of polyethylene glycol(PEG)and potassium c...Mud shale hydration and swelling are major challenges in the development of water-based drilling fuids(WBDFs).In this work,the inhibition performance and inhibition mechanism of polyethylene glycol(PEG)and potassium chloride(KCl)were investigated by hot rolling recovery tests,linear swell tests,Fourier transform infrared spectroscopy,X-ray difraction,atomic absorption spectrophotometry and X-ray photoelectron spectroscopy.The experimental results show that the combination of PEG and KCl achieved higher recovery and lower linear swelling rate than those obtained by individual PEG or KCl.Compared to the d-spacing of Na-montmorillonite(Na-Mt)with PEG or KCl,the d-spacing of Na-Mt with PEG+KCl was lower,which indicates that KCl and PEG have synergistic inhibition efect.This synergistic efect can replace sodium ions and water molecules from the interlayer space of Na-Mt and decrease the d-spacing of Na-Mt.Based on the above experimental results and analysis,a method for optimizing PEG and KCl concentrations was proposed and further verifed by rheological and hot rolling recovery tests of WBDFs.Hence,the results of this work can provide valuable theoretical guidance for developing other synergistic inhibitors.展开更多
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...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.展开更多
The selective aerobic oxidation of alkynes to corresponding α,β-acetylenic ketones was achieved in polyethylene glycol/dense CO2/O2 biphasic system without any catalyst or additive. The effects of reaction parameter...The selective aerobic oxidation of alkynes to corresponding α,β-acetylenic ketones was achieved in polyethylene glycol/dense CO2/O2 biphasic system without any catalyst or additive. The effects of reaction parameters, e.g. temperature, CO2 pressure, PEG molecular weight and loading on the reaction were carefully examined. Moreover, various substrates worked well in the presence of PEG 1000 under 5 MPa of CO2 and 2 MPa of O2 at 100 ℃ for 12 to 24 h and acceptable yield and selectivity could be obtained in most cases. Preliminary mechanistic investigations were also discussed.展开更多
Physical solvents such as ethylene glycol （EG）, diethylene glycol （DEG）, and triethylene glycol （TEG） are commonly used in wet gas dehydration processes with TEG being the most popular due to ease of regeneratio...Physical solvents such as ethylene glycol （EG）, diethylene glycol （DEG）, and triethylene glycol （TEG） are commonly used in wet gas dehydration processes with TEG being the most popular due to ease of regeneration and low solvent losses. Unfortunately, TEG absorbs significantly more hydrocarbons and acid gases than EG or DEG. Quantifying this amount of absorption is therefore critical in order to minimize hydrocarbon losses or to optimize hydrocarbon recovery depending on the objective of the process. In this article, a new correlation that fully covers the operating ranges of TEG dehydration units is developed in order to determine the solubility of light alkanes and acid gases in TEG solvent. The influence of several parameters on hydrocarbon and acid gas solubility including temperature, pressure, and solvent content is also examined.展开更多
Electrodes prepared by anodic oxidation of Ti foils are robust and not toxic materials for the electrocatalytic reduction of oxalic acid to glycolic acid, allowing the development of a renewable energy-driven process ...Electrodes prepared by anodic oxidation of Ti foils are robust and not toxic materials for the electrocatalytic reduction of oxalic acid to glycolic acid, allowing the development of a renewable energy-driven process for producing an alcoholic compound from an organic acid at low potential and room temperature. Coupled with the electrochemical synthesis of the oxalic acid from CO_(2),this process represents a new green and low-carbon path to produce added value chemicals from CO_(2). Various electrodes prepared by anodic oxidation of Ti foils were investigated. They were characterized by the presence of a TiO_(2) nanotube array together with the presence of small patches, debris, or TiO_(2) nanoparticles. The concentration of oxygen vacancies, the amount of Ti^(3+) measured by X-ray photoelectron spectroscopy(XPS) and the intensity of the anodic peak measured by cyclic voltammetry, were positively correlated with the achieved oxalic acid conversion and glycolic acid yield. The analysis of the results indicates the presence of small amorphous TiO_(2) nanoparticles(or surface patches or debris) interacting with TiO_(2) nanotubes, the sites responsible for the conversion of oxalic acid and glycolic acid yield. By varying this structural characteristic of the electrodes, it is possible to tune the glycolic acid to glyoxylic acid relative ratio. A best cumulative Faradaic efficiency(FE) of about 84% with FE to glycolic acid around 60% and oxalic conversion about 30% was observed.展开更多
The mechanism of the hydrophobized poly(ethylene glycol)(PEG)/K^(+) system inhibiting shale hydration was studied by laboratory experiment. The inhibition performance was evaluated through cuttings hot-rolling dispers...The mechanism of the hydrophobized poly(ethylene glycol)(PEG)/K^(+) system inhibiting shale hydration was studied by laboratory experiment. The inhibition performance was evaluated through cuttings hot-rolling dispersion, bentonite inhibition and contact angle tests. The inhibition became stronger as contact angle and PEG concentration increased. A modified cuttings hot-rolling dispersion experiment suggested that these molecular systems did not act through the thermally activated mud emulsion(TAME) mechanism. The interaction of the PEG/K^(+) with clay samples was investigated through adsorption studies and by Fourier transform infrared spectroscopy(FT-IR), X-ray diffraction(XRD) and thermogravimetric analysis(TGA). The adsorption isotherms showed that the presence of K^(+) increased the PEG affinity for the clay surface. This inhibition effect was accompanied by a reduction of the bentonite hydration with PEG adsorption, evidenced by FT-IR, TGA and differential thermogravimetric(DTG) curves. XRD patterns were conclusive in showing that the presence of K^(+) ions limited the expansion of the clay interlamellar region to only one PEG layer, and the terminal hydrophobic segments of the PEG chains turned out to be determinant in enhancement of the inhibitory efficiency. The cuttings hot-rolling dispersion was carried out on water-base drilling fluid with PEG/K^(+), which proved the inhibition performance of PEG/K^(+) in oil field drilling.展开更多
Chitosan is a natural biopolymer, derived from chitin, which is used for wood modification. Polyethylene glycol（PEG） was reacted with wood to provide possible fixation of the chitosan to wood. Wood blocks were treat...Chitosan is a natural biopolymer, derived from chitin, which is used for wood modification. Polyethylene glycol（PEG） was reacted with wood to provide possible fixation of the chitosan to wood. Wood blocks were treated with chitosan and PEG, as well as pre-treatment with the PEG at different temperatures and further reaction with the chitosan. The samples were soaked in water to study leaching of the chemicals, water absorption, swelling, as well as anti-swelling efficiency. Any prior reaction of the wood with PEG provided better reaction to the chitosan.Bulking was increased after the treatment of the wood with PEG. Swelling was reduced in the PEG-treated wood blocks as well as the pre-treated samples. Chitosan was not able to protect wood against water penetration： the treated samples showed more water absorption and swelling.However, pre-treatment of the samples decreased swelling in the wood, and the density was not noticeably affected by the treatments. Heating during the treatment caused more reduction in swelling for PEG–chitosan treated samples.展开更多
Doppler broadening and coincidence Doppler broadening of annihilation radiation experiments have been performed in three kinds of polyethylene glycol（PEG） membrane formed with different average molecular weight usin...Doppler broadening and coincidence Doppler broadening of annihilation radiation experiments have been performed in three kinds of polyethylene glycol（PEG） membrane formed with different average molecular weight using the tunable monoenergy slow positron probe as a function of implantion energy. The obtained positron annihilation parameters are interpreted from two aspects： surface effect and differences in micro-structure or chemical environment of positron annihilation. The experimental results show that the regulation of densification of PEG molecular packing and distribution uniformity from the near surface layer to the bulk region in the film forming process can be well realized by changing its molecular weight. Combining a variable monoenergetic slow positron beam and these two positron annihilation spectroscopy methods is a powerful tool to study positron annihilation characteristics and for polymeric thin-film fine structure analysis.展开更多
Mass attenuation coefficient(μ_m) for polyethylene glycol(PEG) of different molecular weights was determined by using NaI(Tl) scintillator and Win Xcom mixture rule at gamma energies of 59.5, 302.9, 356.0, 661.7, 117...Mass attenuation coefficient(μ_m) for polyethylene glycol(PEG) of different molecular weights was determined by using NaI(Tl) scintillator and Win Xcom mixture rule at gamma energies of 59.5, 302.9, 356.0, 661.7, 1173.2 and 1332.5 keV. The total atomic, molecular and electronic cross sections, half-value layer, effective atomic and electron numbers, mass energy-absorption coefficients and kerma relative to air are calculated. The energy and compositional dependence of μ_m values, and the related radiation absorption parameters, are evaluated and discussed. The experimental results agree well with the theoretical ones, within an uncertainty of 1% in the effective atomic number for all PEG samples at the designated energies.展开更多
Positron lifetimes in polyethylene glycol (PEG) polymer have been measured as a function of polymerization degree N (N = 25 - 500). It is observed that all the positron parameters are strongly dependent on N when N≤2...Positron lifetimes in polyethylene glycol (PEG) polymer have been measured as a function of polymerization degree N (N = 25 - 500). It is observed that all the positron parameters are strongly dependent on N when N≤250, and then tend to constant levels when N≥250. The variations of the longest-lived component (I3,τ3) show that the size of free- volume holes has a minimum at N - 100 and the hole concentration decreases with N. These trends may be due to the variations in crystallinity, the chain ends, entanglements and the Van der Waals interaction between segments. The variations of the second component (I2,τ2) with N reflect the changes of defect properties in crystalline regions of PEG.展开更多
Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal proper...Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal properties and structures of Pebax1074/PEG blend membranes were characterized by DSC and SEM, and the gas permeation properties of CO_2 and N_2 were also investigated at different temperatures. For Pebax1074/PEG blend membranes with low molecular weight PEG(MW≤ 600), higher gas permeabilities than Pebax1074 were achieved. The permeability increased with the increase of PEG molecular weight. The addition of low molecular weight PEG resulted in decrease in activation energy of permeation. For Pebax1074/PEG blend membranes with high molecular weight PEG(MW≥ 1500), due to the melt of PEO phase crystals, the gas permeation properties of blend membranes were temperaturedependent, which could be divided into crystalline region, transition region and amorphous region according to two different transition temperatures. PEG molecular weight and operation temperature determined different gas permeation properties of Pebax1074/PEG blend membranes in three regions. The activation energies of permeation in crystalline region were larger than those in amorphous region.展开更多
基金financial supports from the National Natural Science Foundation of China (Grant Nos. 42090024, 52174049)the Natural Science Foundation of Shandong Province of China (No. ZR2019MEE058)。
文摘The high-efficient development of shale oil is one of the urgent problems in the petroleum industry. The technology of CO_(2) enhanced oil recovery(EOR) has shown significant effects in developing shale oil. The effects of several glycol ether additives with low molecular weight on the interactions between CO_(2) and oil were investigated here. The solubility of glycol ether additive in CO_(2) was firstly characterized. Then,the effects of glycol ether additives on the interfacial tension(IFT) between CO_(2) and hexadecane and the volume expansion and extraction performance between CO_(2) and hexadecane under different pressures was investigated. The experimental results show that diethylene glycol dimethyl ether(DEG), triethylene glycol dimethyl ether(TEG), and tetraethylene glycol dimethyl ether(TTEG) all have low cloud point pressure and high affinity with CO_(2). Under the same mass fraction, DGE has the best effect to reduce the IFT between hexadecane and CO_(2) by more than 30.0%, while an overall reduction of 20.0%-30.0% for TEG and 10.0%-20.0% for TTEG. A new method to measure the extraction and expansion rates has been established and can calculate the swelling factor accurately. After adding 1.0% DEG, the expansion and extraction amounts of CO_(2) for hexadecane are respectively increased to 1.75 times and 2.25 times. The results show that glycol ether additives assisted CO_(2) have potential application for EOR. This study can provide theoretical guidance for the optimization of CO_(2) composite systems for oil displacement.
文摘Methyl glycolate is a good solvent and can be used as feedstock for the synthesis of some important organic chemicals. Catalytic hydrogenation of dimethyl oxalate （DMO） over copper-silver catalyst supported on silica was studied. The Cu-Ag/SiO2 catalyst supported on silica sol was prepared by homogeneous deposition-precipitation of the mixture of aqueous euprammonia complex and silica sol. The proper active temperature of Cu-Ag/SiO2 catalyst for hydrogenation of DMO was 523-623 K. The most preferable reaction conditions for methyl glycolate （MG） were optimized： temperature at 468-478 K, 40-60 mesh catalyst diameter, H2/DMO ratio 40, and 1.0 h^-1 of LHSV.
文摘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.
基金financial support from the National Natural Science Foundation of China(21878227,U1510203)。
文摘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.
基金financial supports provided by the National Natural Science Foundation of China (21406255)the Shanghai Science and Technology Committee (16dz1207200)the Youth Innovation Promotion Association CAS (2015231)
文摘The directly selective hydrogenolysis of xylitol to ethylene glycol(EG) and 1,2-propylene glycol(1,2-PDO)was performed on Cu–Ni–ZrO_2 catalysts prepared by a co-precipitation method. Upon optimizing the reaction conditions(518 K, 4.0 MPaH_2 and 3 h), 97.0% conversion of xylitol and 63.1% yield of glycols were obtained in water without extra inorganic base. The catalyst still remained stable activity after six cycles and above 80% total selectivity of glycols was obtained when using 20.0% xylitol concentration. XRD, TEM and ICP results indicated that Cu–Ni–ZrO_2 catalysts possess favorable stability. Cu and Ni are beneficial to the cleavage of C–O and C–H bond, respectively. To reduce the hydrogen consumption, isopropanol was added as in-situ hydrogen source and 96.4% conversion of xylitol with 43.6% yield of glycols were realized.
基金financially supported by the National Science Foundation of China (21671132)Shanghai Science and Technology Committee(16dz1207200)the Youth Innovation Promotion Association CAS(2015231)
文摘MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the roles of nickel, ZnO and MnOx were investigated. The results show that nickel provided a new pathway of glucose to sorbitol and played an important role in the hydrogenation of C3 intermediates to 1,2-propanediol(1,2-PDO). The high yield of 1, 2-PDO was attributed to effective C–C bond cleavage performance of ZnO support promoted by MnOx. ZnO and MnOx contribute to the conversion of glycerol to lactic acid(LA) and LA to 1, 2-PDO, respectively. A concise pathway for hydrogenation of glucose over Ni-based catalyst was proposed.
基金supported by Natural Science Foundation of China (Grant 21273193, 21473231 and 20973148)
文摘Hydrogen production by steam reforming of ethylene glycol(EG) at 300℃ was investigated over SiO2 and CeO2 supported Pt–Ni bimetallic catalysts prepared by incipient wetness impregnation methods. It was observed that impregnation sequence of Pt and Ni can affect the performance of catalysts apparently. Catalyst with Pt first and then Ni addition showed higher EG conversion and H2 yield owing to the Ni enrichment on the surface and the proper interaction between Pt and Ni. It was observed that although SiO2 supported catalysts exhibited better activity and H2 selectivity, CeO2 supported ones had better stability. This is attributed to the less coke formation on CeO2. Increasing Pt/Ni ratio enhanced the reaction activity, and Pt3–Ni7 catalysts with 3 wt% Pt and 7 wt% Ni showed the highest activity and stability. Ni surficial enrichment facilitated the C-C bond rupture and water gas shift reactions;and Pt addition inhibited methanation reaction. Electron transfer and hydrogen spillover from Pt to Ni suppressed carbon deposition. These combined effects lead to the excellent performance of Pt3–Ni7 supported catalysts.
基金the National Natural Science Foundation of China(21576272)“Transformational Technologies for Clean Energy and Demonstration”Strategic Priority Research Program of Chinese Academy of Sciences,Grant No.XDA 21030600,Science and Technology Service Network Initiative,Chinese Academy of Sciences(KFJ-STS-QYZD-138).
文摘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.
文摘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.
基金This work was financially supported by the Natural Science Foundation of China(51974270)Innovation Union of China National Petroleum Corporation and Southwest Petroleum University(2020CX040102,2020CX040201)Open Fund(PLN201814)of the State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation(Southwest Petroleum University).
文摘Mud shale hydration and swelling are major challenges in the development of water-based drilling fuids(WBDFs).In this work,the inhibition performance and inhibition mechanism of polyethylene glycol(PEG)and potassium chloride(KCl)were investigated by hot rolling recovery tests,linear swell tests,Fourier transform infrared spectroscopy,X-ray difraction,atomic absorption spectrophotometry and X-ray photoelectron spectroscopy.The experimental results show that the combination of PEG and KCl achieved higher recovery and lower linear swelling rate than those obtained by individual PEG or KCl.Compared to the d-spacing of Na-montmorillonite(Na-Mt)with PEG or KCl,the d-spacing of Na-Mt with PEG+KCl was lower,which indicates that KCl and PEG have synergistic inhibition efect.This synergistic efect can replace sodium ions and water molecules from the interlayer space of Na-Mt and decrease the d-spacing of Na-Mt.Based on the above experimental results and analysis,a method for optimizing PEG and KCl concentrations was proposed and further verifed by rheological and hot rolling recovery tests of WBDFs.Hence,the results of this work can provide valuable theoretical guidance for developing other synergistic inhibitors.
基金funded by the National Natural Science Foundation of China(31760183)the Natural Science Foundation of Guangxi(2016GXNSFCA380025)+1 种基金the Project Funded by China Postdoctoral Science Foundation(2017M620361)the Scientifi c Research Foundation of Guangxi University(XGZ150513).
文摘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.
基金supported by the National Natural Science Foundation of China(No.21172125)the Ministry of Science and Technology (2012BAD32B10)+1 种基金the "111" Project of Ministry of Education of China(Project No.B06005)the Committee of Science and Technology of Tianjin
文摘The selective aerobic oxidation of alkynes to corresponding α,β-acetylenic ketones was achieved in polyethylene glycol/dense CO2/O2 biphasic system without any catalyst or additive. The effects of reaction parameters, e.g. temperature, CO2 pressure, PEG molecular weight and loading on the reaction were carefully examined. Moreover, various substrates worked well in the presence of PEG 1000 under 5 MPa of CO2 and 2 MPa of O2 at 100 ℃ for 12 to 24 h and acceptable yield and selectivity could be obtained in most cases. Preliminary mechanistic investigations were also discussed.
文摘Physical solvents such as ethylene glycol （EG）, diethylene glycol （DEG）, and triethylene glycol （TEG） are commonly used in wet gas dehydration processes with TEG being the most popular due to ease of regeneration and low solvent losses. Unfortunately, TEG absorbs significantly more hydrocarbons and acid gases than EG or DEG. Quantifying this amount of absorption is therefore critical in order to minimize hydrocarbon losses or to optimize hydrocarbon recovery depending on the objective of the process. In this article, a new correlation that fully covers the operating ranges of TEG dehydration units is developed in order to determine the solubility of light alkanes and acid gases in TEG solvent. The influence of several parameters on hydrocarbon and acid gas solubility including temperature, pressure, and solvent content is also examined.
基金funding from the European Union’s Horizon 2020 research and innovation program under grant agreement ID 767798 (OCEAN)MIUR PRIN 2017 project CO_(2) ONLY project nr. 2017WR2LRS。
文摘Electrodes prepared by anodic oxidation of Ti foils are robust and not toxic materials for the electrocatalytic reduction of oxalic acid to glycolic acid, allowing the development of a renewable energy-driven process for producing an alcoholic compound from an organic acid at low potential and room temperature. Coupled with the electrochemical synthesis of the oxalic acid from CO_(2),this process represents a new green and low-carbon path to produce added value chemicals from CO_(2). Various electrodes prepared by anodic oxidation of Ti foils were investigated. They were characterized by the presence of a TiO_(2) nanotube array together with the presence of small patches, debris, or TiO_(2) nanoparticles. The concentration of oxygen vacancies, the amount of Ti^(3+) measured by X-ray photoelectron spectroscopy(XPS) and the intensity of the anodic peak measured by cyclic voltammetry, were positively correlated with the achieved oxalic acid conversion and glycolic acid yield. The analysis of the results indicates the presence of small amorphous TiO_(2) nanoparticles(or surface patches or debris) interacting with TiO_(2) nanotubes, the sites responsible for the conversion of oxalic acid and glycolic acid yield. By varying this structural characteristic of the electrodes, it is possible to tune the glycolic acid to glyoxylic acid relative ratio. A best cumulative Faradaic efficiency(FE) of about 84% with FE to glycolic acid around 60% and oxalic conversion about 30% was observed.
基金The authors gratefully acknowledge to ANP(Brazilian Petroleum National Agency)COLFUTURO(Foundation for the future of Colombia)for the financial support.
文摘The mechanism of the hydrophobized poly(ethylene glycol)(PEG)/K^(+) system inhibiting shale hydration was studied by laboratory experiment. The inhibition performance was evaluated through cuttings hot-rolling dispersion, bentonite inhibition and contact angle tests. The inhibition became stronger as contact angle and PEG concentration increased. A modified cuttings hot-rolling dispersion experiment suggested that these molecular systems did not act through the thermally activated mud emulsion(TAME) mechanism. The interaction of the PEG/K^(+) with clay samples was investigated through adsorption studies and by Fourier transform infrared spectroscopy(FT-IR), X-ray diffraction(XRD) and thermogravimetric analysis(TGA). The adsorption isotherms showed that the presence of K^(+) increased the PEG affinity for the clay surface. This inhibition effect was accompanied by a reduction of the bentonite hydration with PEG adsorption, evidenced by FT-IR, TGA and differential thermogravimetric(DTG) curves. XRD patterns were conclusive in showing that the presence of K^(+) ions limited the expansion of the clay interlamellar region to only one PEG layer, and the terminal hydrophobic segments of the PEG chains turned out to be determinant in enhancement of the inhibitory efficiency. The cuttings hot-rolling dispersion was carried out on water-base drilling fluid with PEG/K^(+), which proved the inhibition performance of PEG/K^(+) in oil field drilling.
文摘Chitosan is a natural biopolymer, derived from chitin, which is used for wood modification. Polyethylene glycol（PEG） was reacted with wood to provide possible fixation of the chitosan to wood. Wood blocks were treated with chitosan and PEG, as well as pre-treatment with the PEG at different temperatures and further reaction with the chitosan. The samples were soaked in water to study leaching of the chemicals, water absorption, swelling, as well as anti-swelling efficiency. Any prior reaction of the wood with PEG provided better reaction to the chitosan.Bulking was increased after the treatment of the wood with PEG. Swelling was reduced in the PEG-treated wood blocks as well as the pre-treated samples. Chitosan was not able to protect wood against water penetration： the treated samples showed more water absorption and swelling.However, pre-treatment of the samples decreased swelling in the wood, and the density was not noticeably affected by the treatments. Heating during the treatment caused more reduction in swelling for PEG–chitosan treated samples.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11575205,11475197,11675188,and 11475193)
文摘Doppler broadening and coincidence Doppler broadening of annihilation radiation experiments have been performed in three kinds of polyethylene glycol（PEG） membrane formed with different average molecular weight using the tunable monoenergy slow positron probe as a function of implantion energy. The obtained positron annihilation parameters are interpreted from two aspects： surface effect and differences in micro-structure or chemical environment of positron annihilation. The experimental results show that the regulation of densification of PEG molecular packing and distribution uniformity from the near surface layer to the bulk region in the film forming process can be well realized by changing its molecular weight. Combining a variable monoenergetic slow positron beam and these two positron annihilation spectroscopy methods is a powerful tool to study positron annihilation characteristics and for polymeric thin-film fine structure analysis.
基金Deanship of Scientific Research at Al Imam Mohammad Ibn Saud Islamic University for the grant and financial assistance to accomplish this work
文摘Mass attenuation coefficient(μ_m) for polyethylene glycol(PEG) of different molecular weights was determined by using NaI(Tl) scintillator and Win Xcom mixture rule at gamma energies of 59.5, 302.9, 356.0, 661.7, 1173.2 and 1332.5 keV. The total atomic, molecular and electronic cross sections, half-value layer, effective atomic and electron numbers, mass energy-absorption coefficients and kerma relative to air are calculated. The energy and compositional dependence of μ_m values, and the related radiation absorption parameters, are evaluated and discussed. The experimental results agree well with the theoretical ones, within an uncertainty of 1% in the effective atomic number for all PEG samples at the designated energies.
基金The Project Supported by National Natural Science Foundation of China
文摘Positron lifetimes in polyethylene glycol (PEG) polymer have been measured as a function of polymerization degree N (N = 25 - 500). It is observed that all the positron parameters are strongly dependent on N when N≤250, and then tend to constant levels when N≥250. The variations of the longest-lived component (I3,τ3) show that the size of free- volume holes has a minimum at N - 100 and the hole concentration decreases with N. These trends may be due to the variations in crystallinity, the chain ends, entanglements and the Van der Waals interaction between segments. The variations of the second component (I2,τ2) with N reflect the changes of defect properties in crystalline regions of PEG.
基金Financial support from the National Science and Technology Planning Project (No. 2011BAC08B00)the National High Technology Research and Development Program of China (863 Program) (No.2012AA03A611)
文摘Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal properties and structures of Pebax1074/PEG blend membranes were characterized by DSC and SEM, and the gas permeation properties of CO_2 and N_2 were also investigated at different temperatures. For Pebax1074/PEG blend membranes with low molecular weight PEG(MW≤ 600), higher gas permeabilities than Pebax1074 were achieved. The permeability increased with the increase of PEG molecular weight. The addition of low molecular weight PEG resulted in decrease in activation energy of permeation. For Pebax1074/PEG blend membranes with high molecular weight PEG(MW≥ 1500), due to the melt of PEO phase crystals, the gas permeation properties of blend membranes were temperaturedependent, which could be divided into crystalline region, transition region and amorphous region according to two different transition temperatures. PEG molecular weight and operation temperature determined different gas permeation properties of Pebax1074/PEG blend membranes in three regions. The activation energies of permeation in crystalline region were larger than those in amorphous region.
