高温液态水中葡萄糖无催化降解反应动力学

The decomposition kinetics of glucose was studied in high-temperature liquid water （HTLW） from 180 to 220℃ under a pressure of 10 MPa. It was found the main products from glucose decomposition were 5-hydroxymethylfurfural （5-HMF） and levulinic acid （LA）. The decomposition kinetics of 5-HMF and stability of LA in HTLW were further investigated. A kinetic model for glucose decomposition was proposed accordingly. In the model, a series of first-order reactions with the consideration of parallel by-reactions were used to illustrate the decomposition of glucose. The decomposition activation energies of glucose, 5-HMF, and LA were evaluated as 118.85, 95.40, and 31.29 kJ·mol^-1, respectively.     

二苯并呋喃在活性炭床层中的吸附动力学

The adsorption of dibenzofuran （DBF） on three commercial granular activated carbons （GAC） was investigated to correlate the adsorption equilibrium and kinetics with the morphological characteristics of activated carbons. Breakthrough experiment was conducted to determine the isotherm and kinetics of dibenzofuran on the activated carbons. All-the experiment runs were performed in a fixed bed with a process temperature of 368 K. The effects of adsorbent morphological properties on the kinetics of the adsorption process were studied. The equilibrium data are found satisfactory fitted to the Langmuir isotherm. An intraparticle diffusion model based on the obtained Langmuir isotherm was＇developed for predicting the fixed bed adsorption of dibenzofuran. The result indicated that this model fit all the breakthrough curves well. The surface diffusion coefficients of dibenzofuran on the activated carbon are calculated, and a relationship with the microporosity is found. As it was expected, the dibenzofuran molecule finds more kinetic restrictions for the diffusion in those carbons with narrower pore diameter.     

Kinetics of Asymmetric Reduction of Phenylglyoxylic Acid to R-(－)-Mandelic Acid by Saccharomyces Cerevisiae FD11b

The kinetics of asymmetric production of R-(-)-mandelic acid (R-MA) from phenylglyoxylic acid (PGA)catalyzed by Saccharomyces cerevisiae sp. strain FD11b was studied by fed-batch cultures. The concentrations of glucose and PGA were controlled respectively with a dual feeding system. When the electron donor glucose was supplied at the rate of 0.0833mmol·gdw-1·h-1, the specific production rate (qp) and the enantiomeric excess of R-MAreached the maximum 0.353mmol·gdw-1·h-1 and 97.1％, respectively. The apparent reduction activity of yeast FD11b was obviously affected by both substrate PGA and product MA. The qp value reached the maximum 0.36-0.38mmol·gdw-1·h-1 when the PGA concentration was controlled between 25 and 35mmol·L-1. The obvious substrate inhibition of bioconversion was observed at the PGA concentrations higher than 40mmol· L-1. The accumulation of product MA also caused a severe feed-back inhibition for its production when the product concentration was above 60mmol· L-1. The kinetic model with the inhibition effect of both substrate and product was simulated by a computer-based least-square arithmatic. The established kinetic model was in good agreement with the experimental data.     

L-抗坏血酸在葡萄糖和蔗糖溶液中的黏度及其热力学性质的研究

Visosities and densities at ,several temperatures from 293.15 K to 313.15K are reported for L-ascorbic acid in aqueous glucose and sucrose solutions at different concentrations.The parameters of density,Viscosity coefficient B and partial molar volume are calculated by regression.The experimental results show that densities and viscositis decrease as temperature increases at the same solute and solvent (glucose and sucrose aueous solution)concentrations,and increase with concentration of glucose and sucrose at the same solute concentration and temperature,B increases with concentration of glucose and sucrose and temaperature,L-ascorbic acid is sturcture-breaker or structure-making for the glucose and sucrose aqueous solutions ,Furthermore,the solute-solvent interactions in ternary systems of water-glucose-electrolyte and water-sucrose-electrolyte are discussed.     

大团囊虫草菌胞内多糖发酵优化和抗氧化活性研究(英文)

Cordyceps ophioglossoides is a valuable traditional medicinal material.We have found that intracellular polysaccharide(IPS) is the major biologically active ingredient in Cordyceps ophioglossoides.This study is the first time to optimize the yield of IPS from Cordyceps ophioglossoides.The optimal medium for IPS production consists of glucose 54.50 g·L·1,yeast powder 25.50 g·L·1,NaH2PO4 0.4 g·L·1 and K2HPO4 0.4 g·L·1.The suggested culture conditions are 24 ℃,initial pH 4.5 with a rotary speed of 120 r·min·1 for 168 h.The yield of IPS is 737.93 mg·L·1,which is 50% higher than the yield under the conditions prior to optimization.The anti-oxidative activities of IPS in Cordyceps ophioglossoides L2 are also characterized using various in vitro assay.The anti-oxidative activity may explain the reason why IPS from Cordyceps ophioglossoides can be used to fight against neurodegenerative dis-eases and menopausal symptoms.     

Process development for producing a food-grade glucose solution from rice straws

In this paper, processes for producing a food-grade glucose solution through enzymatic hydrolysis of celluloserich solids obtained from rice straws are presented. The rice straws were pretreated by acid-catalyzed steam explosion, and the reaction efficiency, toxicity control, and process economic feasibility were studied. Mass transfer resistance to the hydrolysis reaction was reduced by grinding with glass beads. A higher glucose concentration could be obtained by feeding more cellulose in the hydrolysis reaction; however, this also resulted in the production of undesired byproducts. Thus, a soaking process for the cellulose solids in water was developed to effectively reduce the generation of byproducts in the hydrolysis reaction. The resulting food-grade glucose solution can provide 414 kilocalories per liter, and could be used during a food-shortage crisis in the future.The current production cost is estimated to be 0.82 USD·L~(-1).     

Solventless ketalization of glycerol to solketal with acetone over the ionic liquid[P(C4H9)3C14H29][TsO]

The ketalization of glycerol with acetone was conducted over an ionic liquid [P(C_4H_9)_3C_(14)H_(29)][Ts O](TTPT) in a batch reactor. A scheme to obtain the purified product using TTPT as a homogeneous catalyst is proposed and a maximum solketal yield of 86% is achieved at acetone/glycerol molar ratio of 6/1, reaction time of 0.5 h, reaction temperature of 303 K, catalyst amount of 5 wt% of glycerol. TTPT was recycled and reused for ten times without obvious losses in terms of quantity and activity. Furthermore, effects of various experimental parameters(stirring speed, catalyst loadings, temperature and reactant composition) on the reaction kinetics are investigated. In terms of kinetics modeling, Kγis fitted by reactant composition at the temperature range 298 K–323 K, which was a concise strategy that showed good precision in the kinetics fitting. The activation energy for this ketalization reaction was evaluated to be 28.2 k J·mol~(-1). In addition, the kinetics of the reaction at a temperature exceeding the boiling point of acetone were also studied. We believe that all the results are important for further development of a technology for the continuous synthesis of solketal.     

聚醚与含氢硅油的硅氢加成反应的动力学研究

The hydrosilylation of polyhydrosiloxane and unsaturated allylic polyether terminated with ester group is processed with chloroplatinic acid as catalyst and ethyl acetate as solvent to exclude the mass transfer resistance in the system. The kinetic study is performed by means of Gel Permeation Chromatography. Within the experimental range （mass ratio of the whole reactants to solvent is 1：4, the tool ratio of Si-H bond to carbon-carbon double bond is 1： 1.3, the catalyst concentration from 1.0×10^-4mol·L^-1 （Pt） to 3.1×10^-4mol·L^-1 （Pt）, temperature between 338.15K and 350.35K）, a kinetic model of zero-th order reaction is built up and the evaluated model parameters are found to change linearly with the catalyst concentration.     

高压乙醇中的无限稀释扩散系数:实验测定与模型评价

The infinite diffusion coefficients of benzene, toluene, naphthalene, pyridine and p-nitroaniline in ethanol were measured by Taylor dispersion technique under 318-473 K and 0-16 MPa. The measurement accuracy of the established apparatus was first checked. The measured diffusion coefficient of the five organic solutes in ethanol did not change with pressure at low temperature, but it was significantly reduced with pressure increase when the temperature is higher than 373 K. Of the correlations available for polar solvents, the modified Wilke-Chang equation, the Yang-Zhang equation as well as the He-Yu equation were used to calculate the infinite diffusion coefficient. At low temperature,the three equations all agreed well with experimental results for both polar and non-polar solutes.However, the prediction accuracy was decreased sharply when the temperature was higher than 373 K,where the association factor of the solvent was varied with temperature as well as pressure.     

重组大肠杆菌分批-补料高密度发酵生产类人胶原蛋白的动力学

The kinetics of batch and fed-batch cultures of recombinant Escherichia coli producing human-like collagen was investigated. In the batch culture, a kinetic model of a simple growth-association system was concluded without consideration of cell endogeneous metabolism. The cell lag time, the maximum specific growth rate and Yx/s were determined as 1.75h, 0.65h^-1 and 0.51g·g^-1, respectively. In the fed-batch culture, different specific growth rates were set at （0.15, 0.2, 0.25h^-1） by the method of pseudo-exponential feeding, and the expressions for the specific rate of substrate consumption, the growth kinetics and the product formation kinetics of each phase were obtained. The result shows that the concentrations of cell and product can reach 77.5g·L^-1 and 10.2g·L^-1 respectively. The modal predictions are in good agreement with the experimental data.     

A Hydrogen-Permselective Silicon Oxycarbide Membrane Derived from Polydimethylsilane

A novel microporous membrane has been prepared by modifying an asymmetric SiC support using polydimethylsilane (PMS). One membrane, pyrolyzed at 573 K, possesses H₂/N₂ selectivity of ∼100 and H₂ permeance of 8.9 × 10⁻⁸ mol·m⁻²·s⁻¹·Pa⁻¹ at 473 K. The other membrane, pyrolyzed at 873 K, has a lower H₂/N₂ selectivity of ∼40 and lower H₂ permeance of 4.9 × 10⁻⁹ mol·m⁻²·s⁻¹·Pa⁻¹ at 473 K. Permeation in both membranes exhibits the characteristics of activated diffusion at elevated temperatures. A higher pyrolysis temperature results in a less-permeable membrane. The support preparation and the thermal events of PMS are analyzed. The effects of pyrolysis temperature on membrane property are discussed.     

EQUILIBRIUM CONSTANTS FOR ETHYL tert-BUTYL ETHER LIQUID-PHASE SYNTHESIS

Thermodynamic equilibrium constants for the liquid-phase synthesis of ethyl terl-butyl ether (ETBE) were determined experimentally in the temperature range 40-80°C (313-353 K) at 1.6 MPa for an initial molar ratio of ethanol to isobutene ranging from 1 to 1.5. To reach etherification equilibrium a macroporous sulphonic acid resin (K-2631, Bayer) was used as a catalyst. The thermodynamic equilibrium constant and the enthalpy, free energy, and entropy changes are given as a temperature function. At 298 K, ΔH° = -34.8 kj mol^-1, ΔG° = -11.7kJmol^-1, and ΔS° = -77.3J mol^-1 K^-1. A comparison with the values obtained for MTBE is also included.     

Methanol decomposition to synthesis gas at low temperature over palladium supported on ceria–zirconia solid solutions

The Ce_xZr_1−xO₂ solid solution was used as a support of a palladium catalyst for methanol decomposition to synthesis gas at low temperature. All Pd-containing catalysts tested in this study showed high selectivity to synthesis gas (over 96%). The Pd supported on the composite oxide with a Ce/Zr molar ratio of 4/1 exhibited the highest activity. Pd/Ce_0.8Zr_0.2O₂ (17 wt.%) (cop) (prepared by coprecipitation method) showed a conversion of 51.2% for the methanol decomposition at 473 K, which was higher than those over 17 wt.% Pd/CeO₂ (cop) (40.7%) and 17 wt.% Pd/ZrO₂ (cop) (24.3%) at 473 K. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed a higher BET surface area and smaller Pd particles than those of 17 wt.% Pd/CeO₂ (cop). Moreover, a more active Pd^σ+ state could be maintained by Zr⁴⁺ ion modification due to promotion of the oxygen mobility and enhancement of the reductibility and increase in the acid sites of the CeO₂ support. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed a much higher conversion (51.2%) than that over 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (imp) (prepared by impregnation method) (17.2%) at 473 K. This is due to the 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) possessing many small Pd particles. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed an initial conversion of 51.2% at 473 K but the conversion decreased to 43.1% after 24 h on stream. This deactivation was attributed to carbonaceous deposit on the catalyst surface. The amounts of coke on the 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst were 0.9 wt.% after 24 h on stream at 473 K and 2.1 wt.% after 1 h on stream at 523 K.     

Pd-Fe/α-Al2O3/cordierite monolithic catalysts for the synthesis of dimethyl oxalate: effects of calcination and structure

Cordierite monoliths coated with Pd-Fe/α-Al₂O₃ catalysts were prepared at various calcination temperatures and characterized by thermogravimetry, temperature-programmed reduction, transmission electron microscopy, diffuse reflectance infrared Fourier transformation spectroscopy and X-ray diffraction. The performance of the catalytic monoliths for the synthesis of dimethyl oxalate (DMO) through a CO coupling reaction was evaluated. Monolithic catalysts with calcination temperatures ranging from 473 K to 673 K exhibited excellent dispersion of Pd, good CO adsorption properties, and excellent performance for the coupling reaction. The optimized monolithic catalyst exhibited a much higher Pd efficiency (denoted as DMO (g)·Pd (g)^-1·h^-1) (733 h^-1) than that of the granular catalyst (60.2 h^-1), which can be attributed to its honeycomb structure and the large pore sizes in the α-Al₂O₃ washcoat which was accompanied with an even distribution of the active component in the coating layer along the monoliths channels.     

Kinetics of halogen-exchange fluorination of 2,6-dichlorobenzaldehyde

Under the conditions of phase transfer catalysis and nitrobenzene as the solvent, the halogen-exchange fluorination of 2,6-dichlorobenzaldehyde using KF as fluorinating agent was studied. The kinetics was investigated and the reaction rate constants were obtained under the optimum conditions of n(KF):n(2,6-dichlorobenzaldehyde):n(Ph₄PBr):n(acetone-furan crown ether) = 4:1:0.1:0.05 and temperatures of 433 K, 443 K, 453 K and 463 K. The results illustrated the activation energy of the first and the second step is 4.57 × 10⁴ J·mol^-l and 3.53 × 10⁴ J·mol^-1, respectively. The pre-exponential factor is 4.50 × 10⁵ h^-1 and 1.08 × 10⁴ h^-1, respectively. Thus a reliable kinetics data could be obtained for further research.     

Heterogeneity of Adsorption Sites and Adsorption Kinetics of n-Hexane on Metal-Organic Framework MIL-101(Cr)

abstract The heterogeneity of adsorption sites and adsorption kinetics of n-hexane on a chromium terephthalate-based metal-organic framework MIL-101(Cr) were studied by gravimetric method and temperatu...     

改性超细煤粉对甲基橙的吸附行为研究

The adsorption of methyl orange onto ultrafine coal powder (UCP) and modified ultrafine coal powder (MUCP) from aqueous solutions were studied, in which the influence of contact time, dosage, temperature, pH, and methyl orange concentration in the solution were investigated. The adsorption kinetics of methyl orange by UCP and MUCP can be described by the Lagergren first-order and pseudo second-order kinetic models, respectively. The adsorption isotherms of methyl orange onto MUCP at 303, 313 and 323 K follow the Freundlich and Langmuir isotherm equation. Values of G0 for methyl orange adsorption onto MUCP are -22.55, -23.10 and -23.79 kJ•mol－1 at 303, 313, and 323 K, respectively. The values of ΔH0 and ΔS0 are -3.74 kJ•mol－1 and 61.99 J•mol－1, respectively. The adsorption process is spontaneous and exothermic.     

D-tracer study of butadiene hydrogenation and tetrahydrothiophen hydrodesulphurisation catalysed by Co9S8

H₂/D₂ exchange (473–583 K), 1,3-butadiene hydrogenation (418–513 K) and tetrahydrothiophen hydrodesulphurisation (428–557 K) have been studied over powdered Co₉S₈ (surface area, 7 m² g⁻¹) using D₂ as an isotopic tracer. Hydrogen exchange proceeded as a first order process at a modest rate (k₅₄₀ = 1.0 h⁻¹ m⁻²) with an apparent activation energy of 67 kJ mol⁻¹. Butadiene hydrogenation was diagnostic as to the surface state of Co₉S₈; samples showed either predominant 1:2-addition or 1:4-addition of hydrogen, interpreted as indicating the presence in the surface of single sites or pair/ensemble sites, respectively. Reactions at 473 K in the presence of D₂ gave butenes containing 0–6 D-atoms: exchange patterns obtained from these D-distributions showed that a proportion of butadiene molecules underwent extensive dehydrogenation during the normal progress of hydrogenation. At 633 K this dehydrogenation activity was evident as self-hydrogenation which occurred in the absence of D₂. Tetrahydrothiophen was desulphurised in the presence of D₂ to thiophen (void of D), butadiene (containing 0–5 D-atoms) and 1-butene (containing mostly 0 and 4 D-atoms). Increase in temperature or in deuterium pressure favoured butene formation so that it became the dominant product (88%). Tetrahydrothiophen also underwent self-hydrodesulphurisation in the absence of D₂. A mechanism is proposed, consistent with this D-tracer information, that accommodates dehydrogenation, desulphurisation and hydrogenation steps in the overall process. The activity of powdered Co₉S₈ exceeded that of powdered MoS₂.     

负载型Co基双功能催化剂上戊酸酯生物燃料的制备

采用浸渍法制备了HZSM-5、HY、Hβ以及MCM-22四种载体上负载Co的催化剂,在高压反应釜中,开展了以乙酰丙酸乙酯为原料一步法加氢脱氧合成戊酸乙酯以及戊酸生物燃料的研究。采用XRD、XPS、TEM、FT-IR、NH₃-TPD、H₂-TPR、py-FTIR、ICP-AES等对催化剂进行表征。结果表明,10Co/HZSM-5催化剂由于Co在HZSM-5上分布均匀,并且B酸酸性、总酸量以及还原性能最优,在保持较高的反应性能的同时,提高了产物的选择性,具有较高的催化性能。进一步对反应温度、反应压力等进行优化,在反应温度为240℃、压力为3 MPa、反应3 h时,以正辛烷作溶剂,催化剂表现出较高的催化性能,乙酰丙酸乙酯的转化率达到100%,戊酸酯和戊酸的总收率可达90%。     

Activity, selectivity and durability of VO–ZSM-5 catalysts for the selective catalytic reduction of NO by ammonia

ZSM-5 zeolite was loaded with vanadyl ions (VO²⁺) by treatment of Na–ZSM-5 with aqueous VOSO₄ solution at pH 1.5–2. The catalytic material was tested for the selective catalytic reduction of NO with ammonia at temperatures between 473 and 823 K and normal pressure using a feed of 1000 ppm NO, 1000 (or 1100) ppm NH₃ and 2% O₂ in He. The catalyst proved to be highly active, providing, e.g. initial NO conversions of >90% at 620 l g⁻¹ h⁻¹ (≈400 000 h⁻¹) and 723 K, and selective, providing nitrogen yields equal to NO conversion at equimolar feed in a wide temperature range and only minor N₂O formation at NH₃ excess. Admixture of SO₂ (200 ppm) resulted in an upward shift of the useful temperature range, but did not affect the catalytic behaviour at temperatures ≥623 K. No SO₂ conversion was noted at T ≤ 723 K and 450 l g⁻¹ h⁻¹. The poisoning effect of water (up to 4.5 vol%) was weak at temperatures between 623 and 773 K. VO-ZSM-5 catalysts are gradually deactivated already under dry conditions, probably by oxidation of the vanadyl ions into pentavalent V species. This deactivation is considerably accelerated in the presence of water.