A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of app...A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of appropriate amounts of Ce into the catalyst was beneficial to the formation of sole tetragonal ZrO2 and effectively prevented from the formation of monoclinic ZrO〉 and restrained the loss of sulfated species. XRD revealed the presence of tetragonal Ce0.16Zr0.84O2phase in the case of S2O8^2-/ZrO2-CeO2 calcined above 500 ℃. Catalytic activities of S2O8^2-/ZrO2-CeO2 for the esterification of lactic acid with n-butanol was studied. The results showed that the optimum conditions were as follows： calcination temperature of the catalyst 600 ℃, n（lactic acid）：n（n-butyl alcohol）=1.0：3.0, w（S2O8^2-/ZrO2- CeO2）=12.0%, reaction temperature 145 ℃, and reaction time 2 h. The esterification efficiency of lactic acid was about 96.6%.展开更多
The Knoevenagel condensation of carbonyl substrates with active methylene compounds proceeds smoothly with ammonium acetate as catalyst in n-butyl pyridinium nitrate to afford the desired products of good purity in mo...The Knoevenagel condensation of carbonyl substrates with active methylene compounds proceeds smoothly with ammonium acetate as catalyst in n-butyl pyridinium nitrate to afford the desired products of good purity in moderate yields.展开更多
La-SO42-/SBA-15 was synthesized with various amounts of lanthanum via incipient-wetness impregnation. Characterization was done by X-ray diffraction（XRD）, transmission electron micrographs（TEM）, nitrogen adsorptio...La-SO42-/SBA-15 was synthesized with various amounts of lanthanum via incipient-wetness impregnation. Characterization was done by X-ray diffraction（XRD）, transmission electron micrographs（TEM）, nitrogen adsorption, FTIR spectroscopic analysis, thermogravimetric analysis, and the total amount of acidity of catalyst was estimated by TPD of NH3. The results indicate that lanthanum has been incorporated into SBA-15 molecular sieve. The prepared materials（La-SO42-/SBA-15） keep the highly ordered mesoporous two-dimensional hexagonal structure and do not change the mesoporous channel structure of the support SBA-15. The catalyst showed best catalytic activity in the synthesis of n-butyl acetate. The optimum conditions of the esterification by orthogonal experiments were studied： the molar ratio of n-butanol to acetic acid 1：1.2, the amount of catalyst 7.5%, reaction time 80 min. The yield of n-butyl acetate could reach 93.2% under the optimum conditions. The catalyst was recyclable, cost effective and environmental friendly.展开更多
Levulinic acid has been identified as a promising green, biomass-derived platform chemical. n-Butyl levulinate is used as an important intermediate having diverse applications. The present work focuses on the synthesi...Levulinic acid has been identified as a promising green, biomass-derived platform chemical. n-Butyl levulinate is used as an important intermediate having diverse applications. The present work focuses on the synthesis of n-butyl levulinate by esterification of levulinic acid with n-butanol using heteropolyacid （HPA） supported on acid-treated clay montmorillonite （K10）. 20% （w/w） dodecatungestophosphoric acid （DTPA） supported on K10 was found to be the most efficient catalyst with 97% levulinic acid conversion and 100% selectivity towards n-butyl levulinate. Effects of various process parameters were studied to examine the efficacy of 20% （w/w） DTPA/K10 for optimization of the activity.展开更多
AIM： To study the prevalence, predictors and control of bleeding following N-butyl 2 cyanoacrylate （NBC） sclerotherapy of gastric varix （GV）. METHODS： We analyzed case records of 1436 patients with portal hypert...AIM： To study the prevalence, predictors and control of bleeding following N-butyl 2 cyanoacrylate （NBC） sclerotherapy of gastric varix （GV）. METHODS： We analyzed case records of 1436 patients with portal hypertension, who underwent endoscopy during the past five years for variceal screening or upper gastrointestinal （GI） bleeding. Fifty patients with bleeding GV underwent sclerotherapy with a mean of 2 mL NBC for control of bleeding. Outcome parameters were primary hemostasis （bleeding control within the first 48 h）, recurrent bleeding （after 48 h of esophagogastro-duodenoscopy） and in-hospital mortality were analyzed. RESULTS： The prevalence of GV in patients with portal hypertension was 15% （220/1436） and the incidence of bleeding was 22.7% （50/220）. Out of the 50 bleeding GV patients, isolated gastric varices （IGV-Ⅰ） were seen in 22 （44%）, gastro-oesophageal varices （GOV） on lesser curvature （GOV-Ⅰ） in 16 （32%）, and GOV on greater curvature （GOV-Ⅱ） in 15 （30%）. IGV-Ⅰ was seen in 44% （22/50） patients who had bleeding as compared to 23% （39/170） who did not have bleeding （P 〈 0.003）. Primary hernostasis was achieved with NBC in all patients. Re-bleeding occurred in 7 （14%） patients after 48 h of initial sclerotherapy. Secondary hemostasis was achieved with repeat NBC sclerotherapy in 4/7 （57%）. Three patients died after repeat sclerotherapy, one during transjugular intrahepatic portosystemic stem shunt （TIPSS）, one during surgery and one due to uncontrolled bleeding. Treatment failure-related mortality rate was 6% （3/50）. CONCLUSION： GV can be seen in 15% of patients with portal hypertension and the incidence of bleeding is 22.7%. NBC is highly effective in controlling GV bleeding. In hospital mortality of patients with bleeding GV is 6%.展开更多
Butyl levulinate（BL） is a promising new candidate as diesel fuel and fuel additive. In this study, an efficient process for a one-pot synthesis of BL from biomass-derived carbohydrates in butanol medium with the cat...Butyl levulinate（BL） is a promising new candidate as diesel fuel and fuel additive. In this study, an efficient process for a one-pot synthesis of BL from biomass-derived carbohydrates in butanol medium with the catalysis of metal sulfates was developed. The catalytic activity of a series of metal sulfates for the synthesis of BL from fructose was investigated. Among various metal sulfates, ferric sulfate Fe（SO）was found to be the most efficient catalyst, which gave a remarkably high BL yield of 62.8 mol% under the conditions of 463 K, 3 h, a catalyst dosage of 5.0 g/L, and fructose concentration of 25 g/L. Different carbohydrates including glucose, cellulose, inulin and sucrose were also used for one-pot synthesis of BL with the catalysis of Fe（SO）, showing the yields of 39.6, 30.5, 56.6 and 50.1 mol%, respectively. In addition,the recycling and reuse of Fe（SO）was studied by characterizing them using powder X-ray diffraction（XRD）, scanning electron microscope（SEM）, X-ray photoelectron spectroscopy（XPS）. A plausible reaction pathway for the one-pot synthesis of BL from fructose was proposed. This study provides a facile and feasible way for the synthesis of BL from biomass.展开更多
Heterogeneous Fenton-like process using fly ash as a catalyst was studied to degrade n-butyl xanthate form aqueous solution. The different reaction parameters on the degradation efficiency of the process were investig...Heterogeneous Fenton-like process using fly ash as a catalyst was studied to degrade n-butyl xanthate form aqueous solution. The different reaction parameters on the degradation efficiency of the process were investigated. The fly ash/H2O2 catalyst possesses a high oxidation activity for n-butyl xanthate degradation in aqueous solution. It is found that both the dosage of catalyst and initial solution pH significantly affect the n-butyl xanthate conversion efficient. The results indicate that by using 1.176 mmol/L H2O2 and 1.0 g/L fly ash catalyst with mass fraction of 4.14% Fe(III) oxide at pH 3.0, almost 96.90% n-butyl xanthate conversion and over 96.66% COD removal can be achieved within 120 min with heterogeneous catalysis by fly ash. CS2 as an intermediate of n-butyl xanthate oxidation. Finally, it is demonstrated that the fly ash/H2O2 catalytic oxidation process can be an efficient method for the treatment of n-butyl xanthate containing wastewater.展开更多
A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential therma...A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential thermal analyses(TG/DTA),Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),pyridine infrared spectroscopy(Py-IR) and scanning electron microscopy(SEM).Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol.The effects of various parameters such as molar ratio of n-butanol to acetic acid,reaction temperature,reaction time,and catalyst amount have been studied by single factor experiment.The results show that Ce2P2W18O62·16H2O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate.The optimum synthetic conditions were determined as follows︰molar ratio of n-butanol to acetic acid at 2.0︰1.0,mass of the catalyst being 1.44% of the total reaction mixture,reaction temperature of 120 ℃ and reaction time of 150 min.Under above conditions,the conversion of acetic acid was above 97.8%.The selectivity of n-butyl acetate based on acetic acid was,in all cases,nearly 100%.The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction.It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products.Compared with using sulfuric acid as catalyst,the present procedure with Ce2P2W18O62·16H2O is a green productive technology due to simple process,higher yield,catalyst recycling and no corrosion for the production facilities.展开更多
A novel Ce-Y/SBA-15 catalyst was prepared by modifying HY/SBA-15 microporous-mesoporous composite molecular sieve with cerium using the impregnation method. The characterization results from scanning electron microsco...A novel Ce-Y/SBA-15 catalyst was prepared by modifying HY/SBA-15 microporous-mesoporous composite molecular sieve with cerium using the impregnation method. The characterization results from scanning electron microscopy/energy dispersive X-ray dispersive spectroscopy（SEM/EDS）, transmission electron microscopy（TEM）, and X-ray fluorescence（XRF） studies indicated that the Ce-modified catalyst maintained the microporous-mesoporous structure of Y/SBA-15. The Ce ions were found to be uniformly dispersed in the pores of the molecular sieve without aggregation. The results from pyrolysis coupled-Fourier transform infrared spectroscopy（Pyridine-FTIR） and temperature programmed desorption of ammonia（NH3-TPD） showed that the loading of cerium caused the hydroxyl group in the catalyst to display stronger Bronsted acidity. The efficiency of the modified Ce-Y/SBA-15 catalyst was evaluated by using it to catalyze the synthesis of n-butyl acetate. The optimal synthesis conditions were determined by orthogonal experiments. The highest esterification yield of 94.4% was obtained when the reaction time was 2.0 h, with acid/alcohol molar ratio of 1：1.2, and catalyst loading of 10 wt.%. The results in this study demonstrated that the loading of cerium and the structure of Y/SBA-15 microporous-mesoporous composite molecular sieve helped in improving the catalytic activity of this acidic catalyst.展开更多
Objective To investigate the relationship between atopic allergy and depression and the role of DBP in the development of depression. Methods BALB/c mice were randomly divided into eight groups：saline;ovalbumin （OVA...Objective To investigate the relationship between atopic allergy and depression and the role of DBP in the development of depression. Methods BALB/c mice were randomly divided into eight groups：saline;ovalbumin （OVA）-immunized;saline＋DBP （0.45 mg/kg·183;d）; saline＋DBP （45 mg/kg·d）; DBP （0.45 mg/kg·d） OVA-immunized; DBP （45 mg/kg·d） OVA-immunized; saline＋hydrocortisone （30 mg/kg·d）; and hydrocortisone （30 mg/kg·d）-exposed OVA-immunized. Behavior （e.g. open-field, tail suspension, and forced swimming tests）, viscera coefficients （brain and spleen）, oxidative damage [e.g. reactive oxygen species （ROS）, malondialdehyde （MDA）, and glutathione （GSH）], as well as levels of IgE and IL-4, were then analyzed. Results In the saline and OVA groups, the degree of depression symptoms in mice increased with increasing DBP concentration. Additionally, the OVA-immunity groups were associated with more serious depressive behavior compared with the same exposure concentration in the saline group. Oxidative damage was associated with a dose-dependent increase in DBP in the different groups. IL-4 and IgE levels were associated with low-dose DBP stimulation, which changed to high-dose inhibition with increasing DBP exposure, possibly due to spleen injury seen at high DBP concentrations.Conclusion Development of an atopic allergy has the potential to increase the risk of depression in mice, and it seems that DBP helps OVA to exert its effect in our present model. Moreover, the results of our study implicate a certain connection between brain oxidative stress and depression, which deserves a further exploration.展开更多
In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model f...In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.展开更多
In this study,sulfonic acid-functionalized lignin-montmorillonite complex(LMT-SO_(3)H)was pre-pared and employed as an efficient heterogeneous catalyst for the esterification of levulinic acid(LA)into n-butyl levulina...In this study,sulfonic acid-functionalized lignin-montmorillonite complex(LMT-SO_(3)H)was pre-pared and employed as an efficient heterogeneous catalyst for the esterification of levulinic acid(LA)into n-butyl levulinate(BL).An intermediate pseudo-butyl levulinate(p-BL)was determined by distilled water treatment and nuclear magnetic resonance(NMR)analysis,and a possible mech-anism for the esterification of LA is proposed.The effects of various process parameters were studied and the results showed that the LMT-SO_(3)H catalyst had the excellent catalytic perfor-mance for esterification of the LA.Under optimum reaction conditions,the yield of BL was 99.3%and the conversion of LA was 99.8%.The LMT-SO_(3)H catalyst exhibited strong acidic sites and high stability even after seven cycles of usage.Furthermore,esterification of the LA with various alcohols over the LMT-SO_(3)H was further investigated.展开更多
Reactive dividing-wall column(RDWC) technology plays a critical role in the energy saving and high efficiency of chemical process.In this article, the process of co-producing ethyl acetate(EA) and n-butyl acetate(BA) ...Reactive dividing-wall column(RDWC) technology plays a critical role in the energy saving and high efficiency of chemical process.In this article, the process of co-producing ethyl acetate(EA) and n-butyl acetate(BA) with RDWC was studied.BA was not only the product, but also acted as entrainer to remove the water generated by the two esterification reactions.Experiments and simulations of the co-production process were carried out.It was found that the experimental results were in good agreement with the simulation results.Two kinds of RDWC structures(RDWC-FC and RDWC-RS) were proposed, and the co-production process operating parameters of the two types of RDWC were optimized by Aspen Plus respectively.The optimal operating parameters of the RDWC-FC were determined as follows: 0.6 of the reflux ratio of aqueous phase(RR), 0.66 of the vapor split(R_V) and 0.51 of the liquid split(R_L).And the optimal operating parameters of the RDWC-RS were shown as follows: RR was 0.295 and R_V was 0.61.Furthermore, the energy saving analysis of the co-production process was based on the annual output of 10000 tons of EA, compared with the traditional reaction distillation(RD) to prepare EA and BA, the reboiler duty of the RDWC-FC column could save 20.4%, TAC saving 23.6%; RDWC-RS reboiler energy consumption could save 17.0%, TAC 22.2%.展开更多
Semiconductor metal oxides have attracted wide attention in the area of gas sensor due to that they have unique advantages in the rapid and accurate detection of harmful gases.A simple strategy is to synthesize porous...Semiconductor metal oxides have attracted wide attention in the area of gas sensor due to that they have unique advantages in the rapid and accurate detection of harmful gases.A simple strategy is to synthesize porous NiO hollow microspheres via a simple hydrothermal method with trisodium citrate as structure guide agent is presented in this paper,and the shell of the microsphere is composed of porous and lamellar assembly units.The cavity proportion can be adjusted by changing the amount of trisodium citrate.A reasonable mechanism was proposed to explain the formation of porous NiO hollow microspheres.As a gas-sensing material,porous NiO hollow microspheres show excellent gas selectivity and rapid response recovery time for n-butyl alcohol gas.When the content of trisodium citrate was 0.10 g,the synthesized hollow sphere NiO had the highest response value(25.6)to 100×10^(-6) of n-butyl alcohol at 300℃ and the response and recovery times were only 68 and 10 s.展开更多
The vapor-liquid equilibrium (VLE) data for the dimethyl carbonate-n-butyl acetate binary system were measured by an Ellis equilibrated distillator. The experimental data were checked for their thermodynamic consisten...The vapor-liquid equilibrium (VLE) data for the dimethyl carbonate-n-butyl acetate binary system were measured by an Ellis equilibrated distillator. The experimental data were checked for their thermodynamic consistency through statistical methods. The VLE data was correlated with Wilson and NRTL activity coefficient models and also with the calculation of the vapor phase fugacity coefficient by the modified Peng-Robinson equation of state.展开更多
Silver nanoparticles were synthesized in different alcoholic medium such as ethylene glycol and n-butyl alcohol by solvothermal method. The nanoparticles have been successfully synthesized by reducing silver nitrate w...Silver nanoparticles were synthesized in different alcoholic medium such as ethylene glycol and n-butyl alcohol by solvothermal method. The nanoparticles have been successfully synthesized by reducing silver nitrate with the above solvents in the presence of trioctyl phosphine oxide (TOPO) as the capping agent at room temperature for 1 h. Electron microscopy, X-ray diffraction, and absorption spectra have been used to investigate the products, and the mechanism is proposed to interpret the controlled synthesis of the products. The results indicate that this approach provides a versatile route to prepare silver nanowires and nanoparticles with controllable diameters. The formation of nano products by this method is rapid, simple and stable.展开更多
A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of n-butyl methacrylate catalyzed by H3PW12O40/...A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of n-butyl methacrylate catalyzed by H3PW12O40/MCM-48 was studied with methacrylic acid and n-butyl alcohol as reactants. H3PW12O40/MCM-48 is an excellent catalyst for synthesizing n-butyl methacrylate and Keggin structure of H3PW12O40 kept unchanged after being impregnated on surface of the molecular sieve support. Effects of n（methacrylic acid）：n（n-butyl alcohol）, catalyst dosage, cyclohexane（water-stripped reagent） and reaction time on yields of the product were investigated. The optimum conditions have been found, that is, molar ratio of acid to alcohol is 1：1.6, mass ratio of catalyst used to the reactants is 0.5% and reaction time is 2.0 h. Under these conditions, the yield of n-butyl methacrylate can reach 93.7%.展开更多
The oil-in-water microemulsion containing N-butyl maleimide(NBMI. M_1) and styrene(St, M_2) was prepared. The complexation properties of NBMI and St in microemulsion were investigated by means of 1H-NMR. With the part...The oil-in-water microemulsion containing N-butyl maleimide(NBMI. M_1) and styrene(St, M_2) was prepared. The complexation properties of NBMI and St in microemulsion were investigated by means of 1H-NMR. With the participation of charge-transfer complex(CTC). four reactivity ratios and the relative reactivity of free monomers and CTC were obtained. The result was compared with that measured by Mayo-Lewis method.展开更多
The vapor pressures of n-butyl carbamate were measured in the temperature range from 372.37 K to 479.27 K and fitted with Antoine equation. The compressibility factor of the vapor was calculated with the Virial equati...The vapor pressures of n-butyl carbamate were measured in the temperature range from 372.37 K to 479.27 K and fitted with Antoine equation. The compressibility factor of the vapor was calculated with the Virial equation and the second virial coefficient was determined by the Vetere model. Then the standard enthalpy of vaporization for n-butyl carbamate was estimated. The heat capacity was measured for the solid state(299.39–324.2 K) and liquid state(336.65–453.21 K) by means of adiabatic calorimeter. The standard enthalpy of formation ΔfH[crystal(cr),298.15 K] and standard entropy S(crystal,298.15 K) of the substance were calculated on the basis of the gas-phase standard enthalpy of formation ΔfH(g,298.15 K)and gas-phase standard entropy S(g,298.15 K), which were estimated by the Benson method. The results are acceptable, validated by a thermochemical cycle.展开更多
基金supported by the Science and Technique Foundation of Shaaxi Province of China (2008K07-32)the Foundation of Shaanxi Educa- tional Committee of China (08JK228)the Graduate Innovation Fund of Shaanxi University of Science and Technology
文摘A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of appropriate amounts of Ce into the catalyst was beneficial to the formation of sole tetragonal ZrO2 and effectively prevented from the formation of monoclinic ZrO〉 and restrained the loss of sulfated species. XRD revealed the presence of tetragonal Ce0.16Zr0.84O2phase in the case of S2O8^2-/ZrO2-CeO2 calcined above 500 ℃. Catalytic activities of S2O8^2-/ZrO2-CeO2 for the esterification of lactic acid with n-butanol was studied. The results showed that the optimum conditions were as follows： calcination temperature of the catalyst 600 ℃, n（lactic acid）：n（n-butyl alcohol）=1.0：3.0, w（S2O8^2-/ZrO2- CeO2）=12.0%, reaction temperature 145 ℃, and reaction time 2 h. The esterification efficiency of lactic acid was about 96.6%.
基金The project sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministrypartly supported by the Natural Science Foundation of Guangdong Province(Grant No 97104).
文摘The Knoevenagel condensation of carbonyl substrates with active methylene compounds proceeds smoothly with ammonium acetate as catalyst in n-butyl pyridinium nitrate to afford the desired products of good purity in moderate yields.
基金the Graduate Student Innovation Scientific Research Projects of Heilongjiang Province, China (No.YJSCX2007-0282-HLJ)
文摘La-SO42-/SBA-15 was synthesized with various amounts of lanthanum via incipient-wetness impregnation. Characterization was done by X-ray diffraction（XRD）, transmission electron micrographs（TEM）, nitrogen adsorption, FTIR spectroscopic analysis, thermogravimetric analysis, and the total amount of acidity of catalyst was estimated by TPD of NH3. The results indicate that lanthanum has been incorporated into SBA-15 molecular sieve. The prepared materials（La-SO42-/SBA-15） keep the highly ordered mesoporous two-dimensional hexagonal structure and do not change the mesoporous channel structure of the support SBA-15. The catalyst showed best catalytic activity in the synthesis of n-butyl acetate. The optimum conditions of the esterification by orthogonal experiments were studied： the molar ratio of n-butanol to acetic acid 1：1.2, the amount of catalyst 7.5%, reaction time 80 min. The yield of n-butyl acetate could reach 93.2% under the optimum conditions. The catalyst was recyclable, cost effective and environmental friendly.
基金S. Dharne thanks Director, NCL, Pune for permission to workas an M. E. (Chemical Engineering) project trainee
文摘Levulinic acid has been identified as a promising green, biomass-derived platform chemical. n-Butyl levulinate is used as an important intermediate having diverse applications. The present work focuses on the synthesis of n-butyl levulinate by esterification of levulinic acid with n-butanol using heteropolyacid （HPA） supported on acid-treated clay montmorillonite （K10）. 20% （w/w） dodecatungestophosphoric acid （DTPA） supported on K10 was found to be the most efficient catalyst with 97% levulinic acid conversion and 100% selectivity towards n-butyl levulinate. Effects of various process parameters were studied to examine the efficacy of 20% （w/w） DTPA/K10 for optimization of the activity.
文摘AIM： To study the prevalence, predictors and control of bleeding following N-butyl 2 cyanoacrylate （NBC） sclerotherapy of gastric varix （GV）. METHODS： We analyzed case records of 1436 patients with portal hypertension, who underwent endoscopy during the past five years for variceal screening or upper gastrointestinal （GI） bleeding. Fifty patients with bleeding GV underwent sclerotherapy with a mean of 2 mL NBC for control of bleeding. Outcome parameters were primary hemostasis （bleeding control within the first 48 h）, recurrent bleeding （after 48 h of esophagogastro-duodenoscopy） and in-hospital mortality were analyzed. RESULTS： The prevalence of GV in patients with portal hypertension was 15% （220/1436） and the incidence of bleeding was 22.7% （50/220）. Out of the 50 bleeding GV patients, isolated gastric varices （IGV-Ⅰ） were seen in 22 （44%）, gastro-oesophageal varices （GOV） on lesser curvature （GOV-Ⅰ） in 16 （32%）, and GOV on greater curvature （GOV-Ⅱ） in 15 （30%）. IGV-Ⅰ was seen in 44% （22/50） patients who had bleeding as compared to 23% （39/170） who did not have bleeding （P 〈 0.003）. Primary hernostasis was achieved with NBC in all patients. Re-bleeding occurred in 7 （14%） patients after 48 h of initial sclerotherapy. Secondary hemostasis was achieved with repeat NBC sclerotherapy in 4/7 （57%）. Three patients died after repeat sclerotherapy, one during transjugular intrahepatic portosystemic stem shunt （TIPSS）, one during surgery and one due to uncontrolled bleeding. Treatment failure-related mortality rate was 6% （3/50）. CONCLUSION： GV can be seen in 15% of patients with portal hypertension and the incidence of bleeding is 22.7%. NBC is highly effective in controlling GV bleeding. In hospital mortality of patients with bleeding GV is 6%.
基金financially supported by the National Natural Science Foundation of China (nos.21176227 and U1404519)
文摘Butyl levulinate（BL） is a promising new candidate as diesel fuel and fuel additive. In this study, an efficient process for a one-pot synthesis of BL from biomass-derived carbohydrates in butanol medium with the catalysis of metal sulfates was developed. The catalytic activity of a series of metal sulfates for the synthesis of BL from fructose was investigated. Among various metal sulfates, ferric sulfate Fe（SO）was found to be the most efficient catalyst, which gave a remarkably high BL yield of 62.8 mol% under the conditions of 463 K, 3 h, a catalyst dosage of 5.0 g/L, and fructose concentration of 25 g/L. Different carbohydrates including glucose, cellulose, inulin and sucrose were also used for one-pot synthesis of BL with the catalysis of Fe（SO）, showing the yields of 39.6, 30.5, 56.6 and 50.1 mol%, respectively. In addition,the recycling and reuse of Fe（SO）was studied by characterizing them using powder X-ray diffraction（XRD）, scanning electron microscope（SEM）, X-ray photoelectron spectroscopy（XPS）. A plausible reaction pathway for the one-pot synthesis of BL from fructose was proposed. This study provides a facile and feasible way for the synthesis of BL from biomass.
基金Project(CZQ13002)supported by the Special Fund for Basic Scientific Research of Central Universities,China
文摘Heterogeneous Fenton-like process using fly ash as a catalyst was studied to degrade n-butyl xanthate form aqueous solution. The different reaction parameters on the degradation efficiency of the process were investigated. The fly ash/H2O2 catalyst possesses a high oxidation activity for n-butyl xanthate degradation in aqueous solution. It is found that both the dosage of catalyst and initial solution pH significantly affect the n-butyl xanthate conversion efficient. The results indicate that by using 1.176 mmol/L H2O2 and 1.0 g/L fly ash catalyst with mass fraction of 4.14% Fe(III) oxide at pH 3.0, almost 96.90% n-butyl xanthate conversion and over 96.66% COD removal can be achieved within 120 min with heterogeneous catalysis by fly ash. CS2 as an intermediate of n-butyl xanthate oxidation. Finally, it is demonstrated that the fly ash/H2O2 catalytic oxidation process can be an efficient method for the treatment of n-butyl xanthate containing wastewater.
基金Supported by the National Natural Science Foundation of China（21161009）the Natural Science Foundation of Jiangxi Province（20122BAB213001,20114BAB213002）the Science and Technology Foundation of Jiangxi Province（GJJ11613）
文摘A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential thermal analyses(TG/DTA),Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),pyridine infrared spectroscopy(Py-IR) and scanning electron microscopy(SEM).Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol.The effects of various parameters such as molar ratio of n-butanol to acetic acid,reaction temperature,reaction time,and catalyst amount have been studied by single factor experiment.The results show that Ce2P2W18O62·16H2O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate.The optimum synthetic conditions were determined as follows︰molar ratio of n-butanol to acetic acid at 2.0︰1.0,mass of the catalyst being 1.44% of the total reaction mixture,reaction temperature of 120 ℃ and reaction time of 150 min.Under above conditions,the conversion of acetic acid was above 97.8%.The selectivity of n-butyl acetate based on acetic acid was,in all cases,nearly 100%.The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction.It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products.Compared with using sulfuric acid as catalyst,the present procedure with Ce2P2W18O62·16H2O is a green productive technology due to simple process,higher yield,catalyst recycling and no corrosion for the production facilities.
基金Project supported by the Research Fund for the Doctoral Program of Higher Education(20100042110008)the Talent Scientific Research Fund of Liaoning Shihua University
文摘A novel Ce-Y/SBA-15 catalyst was prepared by modifying HY/SBA-15 microporous-mesoporous composite molecular sieve with cerium using the impregnation method. The characterization results from scanning electron microscopy/energy dispersive X-ray dispersive spectroscopy（SEM/EDS）, transmission electron microscopy（TEM）, and X-ray fluorescence（XRF） studies indicated that the Ce-modified catalyst maintained the microporous-mesoporous structure of Y/SBA-15. The Ce ions were found to be uniformly dispersed in the pores of the molecular sieve without aggregation. The results from pyrolysis coupled-Fourier transform infrared spectroscopy（Pyridine-FTIR） and temperature programmed desorption of ammonia（NH3-TPD） showed that the loading of cerium caused the hydroxyl group in the catalyst to display stronger Bronsted acidity. The efficiency of the modified Ce-Y/SBA-15 catalyst was evaluated by using it to catalyze the synthesis of n-butyl acetate. The optimal synthesis conditions were determined by orthogonal experiments. The highest esterification yield of 94.4% was obtained when the reaction time was 2.0 h, with acid/alcohol molar ratio of 1：1.2, and catalyst loading of 10 wt.%. The results in this study demonstrated that the loading of cerium and the structure of Y/SBA-15 microporous-mesoporous composite molecular sieve helped in improving the catalytic activity of this acidic catalyst.
基金financially supported by the Key Project of International Cooperation from the Chinese Ministry of Science and Technology(2010DFA31790)the China National Natural Science Foundation of China(51136002)China Key Technologies R&D Program(2012BAJ02B03)
文摘Objective To investigate the relationship between atopic allergy and depression and the role of DBP in the development of depression. Methods BALB/c mice were randomly divided into eight groups：saline;ovalbumin （OVA）-immunized;saline＋DBP （0.45 mg/kg·183;d）; saline＋DBP （45 mg/kg·d）; DBP （0.45 mg/kg·d） OVA-immunized; DBP （45 mg/kg·d） OVA-immunized; saline＋hydrocortisone （30 mg/kg·d）; and hydrocortisone （30 mg/kg·d）-exposed OVA-immunized. Behavior （e.g. open-field, tail suspension, and forced swimming tests）, viscera coefficients （brain and spleen）, oxidative damage [e.g. reactive oxygen species （ROS）, malondialdehyde （MDA）, and glutathione （GSH）], as well as levels of IgE and IL-4, were then analyzed. Results In the saline and OVA groups, the degree of depression symptoms in mice increased with increasing DBP concentration. Additionally, the OVA-immunity groups were associated with more serious depressive behavior compared with the same exposure concentration in the saline group. Oxidative damage was associated with a dose-dependent increase in DBP in the different groups. IL-4 and IgE levels were associated with low-dose DBP stimulation, which changed to high-dose inhibition with increasing DBP exposure, possibly due to spleen injury seen at high DBP concentrations.Conclusion Development of an atopic allergy has the potential to increase the risk of depression in mice, and it seems that DBP helps OVA to exert its effect in our present model. Moreover, the results of our study implicate a certain connection between brain oxidative stress and depression, which deserves a further exploration.
文摘In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.
基金the financial support of the National Natural Science Foundation of China(Nos.21606082,21776068 and 21975070)Hunan Provincial Natural Science Foundation of China(No.2018JJ3334),and China Postdoctoral Science Foundation(No.2019M662787).
文摘In this study,sulfonic acid-functionalized lignin-montmorillonite complex(LMT-SO_(3)H)was pre-pared and employed as an efficient heterogeneous catalyst for the esterification of levulinic acid(LA)into n-butyl levulinate(BL).An intermediate pseudo-butyl levulinate(p-BL)was determined by distilled water treatment and nuclear magnetic resonance(NMR)analysis,and a possible mech-anism for the esterification of LA is proposed.The effects of various process parameters were studied and the results showed that the LMT-SO_(3)H catalyst had the excellent catalytic perfor-mance for esterification of the LA.Under optimum reaction conditions,the yield of BL was 99.3%and the conversion of LA was 99.8%.The LMT-SO_(3)H catalyst exhibited strong acidic sites and high stability even after seven cycles of usage.Furthermore,esterification of the LA with various alcohols over the LMT-SO_(3)H was further investigated.
基金Supported by the National Key R&D Program of China(2017YFB0602500)the Key Basic Research Items in Application Basic Research Program of Hebei Province,China(16964502D)
文摘Reactive dividing-wall column(RDWC) technology plays a critical role in the energy saving and high efficiency of chemical process.In this article, the process of co-producing ethyl acetate(EA) and n-butyl acetate(BA) with RDWC was studied.BA was not only the product, but also acted as entrainer to remove the water generated by the two esterification reactions.Experiments and simulations of the co-production process were carried out.It was found that the experimental results were in good agreement with the simulation results.Two kinds of RDWC structures(RDWC-FC and RDWC-RS) were proposed, and the co-production process operating parameters of the two types of RDWC were optimized by Aspen Plus respectively.The optimal operating parameters of the RDWC-FC were determined as follows: 0.6 of the reflux ratio of aqueous phase(RR), 0.66 of the vapor split(R_V) and 0.51 of the liquid split(R_L).And the optimal operating parameters of the RDWC-RS were shown as follows: RR was 0.295 and R_V was 0.61.Furthermore, the energy saving analysis of the co-production process was based on the annual output of 10000 tons of EA, compared with the traditional reaction distillation(RD) to prepare EA and BA, the reboiler duty of the RDWC-FC column could save 20.4%, TAC saving 23.6%; RDWC-RS reboiler energy consumption could save 17.0%, TAC 22.2%.
基金financially supported by the Natural Science Basic Research Plan in Shaanxi Province of China(No.2018JM2015)the Fundamental Research Funds for the Central Universities(No.3102017jc01001)the National Key Research and Development Program of China(No.2017YFC0211500)。
文摘Semiconductor metal oxides have attracted wide attention in the area of gas sensor due to that they have unique advantages in the rapid and accurate detection of harmful gases.A simple strategy is to synthesize porous NiO hollow microspheres via a simple hydrothermal method with trisodium citrate as structure guide agent is presented in this paper,and the shell of the microsphere is composed of porous and lamellar assembly units.The cavity proportion can be adjusted by changing the amount of trisodium citrate.A reasonable mechanism was proposed to explain the formation of porous NiO hollow microspheres.As a gas-sensing material,porous NiO hollow microspheres show excellent gas selectivity and rapid response recovery time for n-butyl alcohol gas.When the content of trisodium citrate was 0.10 g,the synthesized hollow sphere NiO had the highest response value(25.6)to 100×10^(-6) of n-butyl alcohol at 300℃ and the response and recovery times were only 68 and 10 s.
基金Supported by the China Petrochemical Corporation.
文摘The vapor-liquid equilibrium (VLE) data for the dimethyl carbonate-n-butyl acetate binary system were measured by an Ellis equilibrated distillator. The experimental data were checked for their thermodynamic consistency through statistical methods. The VLE data was correlated with Wilson and NRTL activity coefficient models and also with the calculation of the vapor phase fugacity coefficient by the modified Peng-Robinson equation of state.
文摘Silver nanoparticles were synthesized in different alcoholic medium such as ethylene glycol and n-butyl alcohol by solvothermal method. The nanoparticles have been successfully synthesized by reducing silver nitrate with the above solvents in the presence of trioctyl phosphine oxide (TOPO) as the capping agent at room temperature for 1 h. Electron microscopy, X-ray diffraction, and absorption spectra have been used to investigate the products, and the mechanism is proposed to interpret the controlled synthesis of the products. The results indicate that this approach provides a versatile route to prepare silver nanowires and nanoparticles with controllable diameters. The formation of nano products by this method is rapid, simple and stable.
基金Funded by the Natural Science Foundation of Hubei Province,China(No.2005ABA053)the National Natural ScienceFoundation of China(No.20471044)
文摘A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of n-butyl methacrylate catalyzed by H3PW12O40/MCM-48 was studied with methacrylic acid and n-butyl alcohol as reactants. H3PW12O40/MCM-48 is an excellent catalyst for synthesizing n-butyl methacrylate and Keggin structure of H3PW12O40 kept unchanged after being impregnated on surface of the molecular sieve support. Effects of n（methacrylic acid）：n（n-butyl alcohol）, catalyst dosage, cyclohexane（water-stripped reagent） and reaction time on yields of the product were investigated. The optimum conditions have been found, that is, molar ratio of acid to alcohol is 1：1.6, mass ratio of catalyst used to the reactants is 0.5% and reaction time is 2.0 h. Under these conditions, the yield of n-butyl methacrylate can reach 93.7%.
文摘The oil-in-water microemulsion containing N-butyl maleimide(NBMI. M_1) and styrene(St, M_2) was prepared. The complexation properties of NBMI and St in microemulsion were investigated by means of 1H-NMR. With the participation of charge-transfer complex(CTC). four reactivity ratios and the relative reactivity of free monomers and CTC were obtained. The result was compared with that measured by Mayo-Lewis method.
文摘The vapor pressures of n-butyl carbamate were measured in the temperature range from 372.37 K to 479.27 K and fitted with Antoine equation. The compressibility factor of the vapor was calculated with the Virial equation and the second virial coefficient was determined by the Vetere model. Then the standard enthalpy of vaporization for n-butyl carbamate was estimated. The heat capacity was measured for the solid state(299.39–324.2 K) and liquid state(336.65–453.21 K) by means of adiabatic calorimeter. The standard enthalpy of formation ΔfH[crystal(cr),298.15 K] and standard entropy S(crystal,298.15 K) of the substance were calculated on the basis of the gas-phase standard enthalpy of formation ΔfH(g,298.15 K)and gas-phase standard entropy S(g,298.15 K), which were estimated by the Benson method. The results are acceptable, validated by a thermochemical cycle.
