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SCI和EI收录∣中国化工学会会刊
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English
本期目录
2003年 第11卷 第3期 刊出日期:2003-06-28
上一期
下一期
RESEARCH PAPERS
金属硫化物作为阳极材料对H
2
S固体氧化物燃料电池性能研究
钟理, 刘曼, 韦国林, CHUANG Karl
. 2003, 11(3): 245-248. doi:
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Two anode catalysts with Pt, MoS2 and composite metal sulfides (MoS2+NiS), are investigated
forelectrochemical oxidation of hydrogen sulfide in solid oxide fuel cell (SOFC) at
temperatures 750-850℃. Thecatalysts comprising MoS2 and MoS2+NiS exhibited good electrical
conductivity and catalytic activity. MoS2 andcomposite catalysts were found to be more
active than Pt, a widely used catalyst for high temperature H2S/O2fuel cell at 750-850℃.
However, MoS2 itself sublimes above 450℃. In contrast, composite catalysts containingboth
Mo and transition metal (Ni) are shown to be stable and effective in promoting the
oxidation of H2S in SOFCup to 850℃. However, electric contact is poor between the platinum
current collecting layer and the compositemetal sulfide layer, so that the cell performance
becomes worse. This problem is overcome by adding conductiveAg powder into the anode layer
(forming MoS2+NiS+Ag anode material) to increase anode electrical conductanceinstead of
applying a thin layer of platinum on the top of anode.
助滤剂特性的理论分析与研究
谭蔚, 鲁淑群, 伍云涛, 朱企新
. 2003, 11(3): 249-252. doi:
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Pressure filtration and filter aids should be adopted in filtration of high-viscosity
molten chemical fibercontaining foreign materials and gel particles. Theoretical analysis
and argumentations on manners of assistedfiltration and specific requirements of filter
aids are performed. Measurement and comparison on properties ofseveral filter aids are also
carried out, conclusions and suggestions are put forward.
超临界条件下苯酚在活性炭和聚合物吸附剂上吸附等温线的测定
奚红霞, 谢兰英, 李祥斌, 李忠
. 2003, 11(3): 253-256. doi:
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A method named as "volume-expanding and pressure-reducing adsorption" is proposed. It can
be usedto measure the isotherms under supercritical condition. The adsorption isotherms of
phenol on activated carbonsand polymeric adsorbents are estimated and compared respectively
for the systems of "phenol-activated carbon-supercritical fluid CO2" and "phenol-polymeric
adsorbent-supercritical fluid CO2". The results show that theamount of phenol adsorbed on
the activated carbons and the polymeric adsorbents under the supercritical conditionis much
less than that under the general condition, which can be utilized to develop a technology
regenerating theactivated carbon with supercritical fluid. Moreover, the effects of ethyl
alcohol, used as the third component, on theisotherms of phenol on the activated carbons
and polymeric adsorbents under the supercritical condition are alsoinvestigated.
含再生再利用的用水系统的最小新鲜水和相应的再生水用量的确定
徐冬梅, 胡仰栋, 华贲, 王修林
. 2003, 11(3): 257-263. doi:
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A sequential three-step programming method is proposed for determining the minimum flowrate
of freshwater and corresponding regenerated water in water-using system of single
contaminant with regeneration reuse.In step 1, a programming with the objective of min fws
is used to determine the minimum flowrate of fresh water,in which the mathematical
representation is a mixed integer nonlinear programming (MINLP1). Then under thesame
constraints with step 1, a programming with the objective of min freg in step 2 and a
programming withthe objective of min Cr in step 3 are subsequently used to determine the
minimum flowrate of regenerated waterand the minimum inlet concentration to regeneration
process corresponding to the minimum flowrate of fresh waterbased on step 1. The method is
easy to apply because we only need to change the objective function but keep theconstraints
constant to go along the following steps after step 1. In addition, the relationship
between the freshwater flowrate required, fws, and inlet concentration to regeneration
process, Cr, is investigated. It is found thatthere exist three relationships between fws
and Cr, which indicate three possibilities for Cb: below the pinch, abovethe pinch or at
the pinch. Therefore, a new conclusion is drawn, which differs from that "regeneration of
water atpinch minimizes fresh water flowrate" derived in literature and indicates that in
some cases, regeneration at otherpoint also minimizes fresh water flowrate.
N-异丙基丙烯酰胺凝胶在乙醇水溶液中的溶胀平衡
许小平, HUTHER Andreas, MAURER Gerd
. 2003, 11(3): 264-268. doi:
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N-isopropylacrylamide (NIPAAm) was used to synthesize NIPAAm homopolymer (nonionized)
andNIPAAm-sodium methacrylate copolymer (ionized). The swelling equilibria for both gels
were obtained in aqueoussolution of ethanol with concentration ranging from 0 to 100%(by
mass) at 25℃. The swollen gel in water shrankfirst with the addition of a small amount of
ethanol and then reswelled with further addition of ethanol showing notonly a discontinuous
volume phase transition but also a typical reentrant phenomenon. A thermodynamic modelbased
on the UNIQUAC with the "free-volume" contribution was applied to correlate and predict the
swellingbehavior of the poly(NIPAAM)-gels in ethanol-water mixture.
接枝量对等离子体接枝聚异丙基丙烯酰胺开关的多孔膜的温度感应透过性的影响
褚良银, 朱家骅, 陈文梅,NIITSUMA Takuya, YAMAGUCHI Takeo, NAKAO Shin-ichi
. 2003, 11(3): 269-275. doi:
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The effect of graft yield on both the thermo-responsive hydraulic permeability and the
thermo-responsivediffusional permeability through porous membranes with plasma-grafted
poly(N-isopropylacrylamide) (PNIPAM)gates was investigated. Both thermo-responsive flat
membranes and core-shell microcapsule membranes with a widerange of graft yield of PNIPAM
were prepared using a plasma-graft pore-filling polymerization method. The graftedPNIPAM
was formed homogeneously throughout the entire thickness of both the flat polyethylene
membranes andthe microcapsule polyamide membranes. Both the hydraulic permeability and the
diffusional permeability wereheavily dependent on the PNIPAM graft yield. With increasing
the graft yield, the hydraulic permeability (waterflux) decreases rapidly at 25℃ because
of the decrease of the pore size; however, the water flux at 40℃ increasesfirstly to a
peak because of the increase of hydrophobicity of the pore surface, and then decreases and
finally tends tozero because of the pore size becoming smaller and smaller. For the
diffusional permeability, the temperature showsdifferent effects on the diffusional
permeability coefficients of solutes across the membranes. When the graft yieldwas low, the
diffusional coefficient of solute across the membrane was higher at temperature above the
lower criticalsolution temperature (LCST) than that below the LCST; however, when the graft
yield was high, the diffusionalcoefficient was lower at temperature above the LCST than
that below the LCST. It is very important to choose ordesign a proper graft yield of PNIPAM
for obtaining a desired thermo-responsive "on/of" hydraulic or diffusionalpermeability.
天然气水合物生成焓的实验研究
高军, Kenneth N. Marsh
. 2003, 11(3): 276-279. doi:
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This paper reports the measurements of enthalpies of natural gas hydrates in typical
natural gas mixturecontaining methane, ethane, propane and iso-butane at pressure in the
vicinity of 2000 kPa (300 psi) and 6900 kPa(1000psi). The measurements were made in a
multi-cell differential scanning calorimeter using modified highpressure cells. The
enthalpy of water and the enthalpy of dissociation of the gas hydrate were determined
fromthe calorimeter response during slow temperature scanning at constant pressure. The
amount of gas released fromthe dissociation of hydrate was determined from the pumped
volume of the high pressure pump. The occupationratio (mole ratio) of the water to gas and
the enthalpy of hydrate formation are subject to uncertainty of 1.5%.The results show that
the enthalpy of hydrate formation and the occupation ratio are essentially independent of
pressure.
基于矩法和时间域分析法研究稠密CO
2
中甲苯和对氯苯在硅胶固定床系统中的吸附和传递性质
杨晓宁
. 2003, 11(3): 280-288. doi:
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Based on chromatographic theory, the moment method and the time-domain fitting analysis
wereapplied to measure and evaluate the adsorption equilibrium constant and mass transfer
properties (axial dispersioncoefficient and effective intra- particle diffusivity) for
toluene and p-dichlorobenzene on silica gel adsorbent in thesubcritical and supercritical
CO2. An apparatus based on supercritical fluid chromatography was established and
theexperiments were performed at temperatures of 298.15-318.15 K and pressures of 7.5-17.8
MPa. The two methodshave been compared. The results show that for the systems studied here
the moment method can give reasonablevalues for both adsorption equilibrium constant and
mass transfer properties, but the time-domain analysis only canobtain the adsorption
equilibrium constant. The dependence of adsorption equilibrium constant and mass
transferproperties on temperature and pressure was investigated.
用于甲烷偶联的SrCe0.95Yb0.05O3-α中空纤维膜反应器建模
谭小耀, 杨乃涛, K.Li
. 2003, 11(3): 289-296. doi:
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Proton-hole mixed conductor, SrCe0.95Yb0.05O3-α(SCYb), has the potential to be used as a
mem-brane for dehydrogenation reactions such as methane coupling due to its high C2-
selectivity and its simplicity forfabricating reactor systems. In addition, the mixed
conducting membrane in the hollow fibre geometry is capable ofproviding high surface area
per unit volume. In this study, mechanism of methane coupling reaction on the SCYbmembrane
was proposed and the kinetic parameters were obtained by regression of experimental data. A
math-ematical model describing the methane coupling in the SCYb hollow fibre membrane
reactor was also developed.With this mathematical model, various operating conditions such
as the operation mode, operation pressure andfeed concentrations affecting performance of
the reactor were investigated. The simulation results show that thecocurrent flow in the
reactor exhibits higher conversion of methane and higher yield of ethylene compared to
thecountercurrent flow. In order to achieve the highest C2 yield, especially of ethylene,
pure methane should be usedas feed and the operating pressure be 300kPa. Air can be used as
the source of oxygen for the reaction and itsoptimum feed velocity is twice of the methane
feed velocity. The air pressure in the lumen side should be kept thesame as or slightly
lower than the pressure of shell side.
萃取精馏分离C4的过程设计
雷志刚, 陈标华, 李建伟
. 2003, 11(3): 297-301. doi:
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C4 components are useful in industry and should be separated as individuals. A new process
wasproposed to separate them by extractive distillation, with the advantages of low
equipment investment, energyconsumption and liquid load in the columns. One principle to
improve the extractive distillation process was putforward. Moreover, the analysis of
operation state of the new process was done. There were eight operation statesfound for the
whole process, but only one operation state was desirable. This work provides a way to
effectivelyseparate C4 mixtures and helps the reasonable utilization of C4 resource.
纳米碳酸钙在非等温条件下热分解动力学及机理研究
刘润静, 陈建峰, 郭奋, 吉米, 沈志刚
. 2003, 11(3): 302-306. doi:
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Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a
thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to
20 K@min-1). The Coats andRedfern’s equation was used to determine the apparent activation
energy and the pre-exponential factors. Themechanism of thermal decomposition was evaluated
using the master plots, Coats and Redfern’s equation and thekinetic compensation law. It
was found that the thermal decomposition property of nano-sized calcium carbonatewas
different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640
℃, which was 180℃lower than the reported value for calcite. The experimental results of
kinetics were compatible with the mechanismof one-dimensional phase boundary movement. The
apparent activation energy of nano-sized calcium carbonate wasestimated to be 151kJ@mol-1
while the literature value for normal calcite was approximately 200kJ@mol-1. Theorder of
magnitude of pre-exponential factors was estimated to be 109 s-1.
利用人工神经网络和遗传算法对热偶精馏过程进行模拟优化
王延敏, 姚平经
. 2003, 11(3): 307-311. doi:
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In this paper, a new approach using artificial neural network and genetic algorithm for the
optimizationof the thermally coupled distillation is presented. Mathematical model can be
constructed with artificial neuralnetwork based on the simulation results with ASPEN PLUS.
Modified genetic algorithm was used to optimize themodel. With the proposed model and
optimization arithmetic, mathematical model can be calculated, decisionvariables and target
value can be reached automatically and quickly. A practical example is used to
demonstratethe algorithm.
质量交换网络集成的状态空间法
马蔚钧, 胡山鹰, 李有润, 沈静珠
. 2003, 11(3): 312-317. doi:
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State space approach is an effective method to mass-exchange network (MEN) synthesis. By
decom-posing the network into two interactive parts, a distribution network and a process
operator, the synthesis problemcan be formulated into a mixed integer nonlinear programming
(MINLP) model. In this article, a generalized statespace model based on typical MEN is
established and verified in two cases. A new asymmetrical operator and costindex are also
adopted to speed up the solution process. The results demonstrate the efficiency of the
proposedapproach.
聚苯乙烯负载钼(Ⅵ)配合物的合成、表征及其催化环己烯环氧化活性研究
章亚东, 高晓蕾, 陈霞, 王朝进, 蒋登高
. 2003, 11(3): 318-325. doi:
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Molybdenum (Ⅵ) complex, namely molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] used
asepoxidation catalyst species, was synthesized and characterized by elemental analysis and
infrared spectrum.Polystyrene-supported molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2]
for synthesis of epoxycyclohexanewas prepared by phase transfer catalysis method. Effects
of various factors in synthesis of epoxycyclohexane by re-action of cyclohexene and t-BuOOH
in the atmosphere of nitrogen catalyzed by polystyrene-supported MoO2 (acac)2were also
investigated. Under the following conditions, n(cyclohexene):n(t-BuOOH)=3.5:1 (based on
0.1 mol of t-BuOOH), volume of solvent ~10 ml, reaction temperature ~80℃, reaction time
~60 min, and mass of molybdenumin the catalyst ~ 2.30 × 10-3 g, the yield of
epoxycyclohexane on the basis of t-BuOOH is over 99.5%, and thepurity of epoxycyclohexane
is about 99.9% by gas chromatogram(GC) analysis.
REVIEWS
聚合物基有机-无机纳米复合材料的制备、性能及应用
任杰, 刘艳, 唐小真
. 2003, 11(3): 326-333. doi:
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Six preparation methods for polymeric organic-inorganic nanocomposites and their respective
mecha-nisms and features are reviewed. The extraordinary properties of polymeric organic-
inorganic nanocomposites arediscussed,and their potential applications are evaluated.
CHEMICAL ENGINEERING DATA
对苯二甲酸在几种溶剂中的固液平衡研究
马沛生, 陈明鸣
. 2003, 11(3): 334-337. doi:
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Terephthalic acid(PTA) is practically one of the main materials of polyester. Its
corresponding solid-liquid equilibrium data will provide essential support for industry
design and further theoretical studies. In this work,solid-liquid equilibriums of
terephthalic acid in four solvents, N,N-dimethylformamide, N,N-
dimethylacetamide,dimethylsulphoxide and N-methyl-2-ketopyrrolidene, were determined in the
temperature range from 293.15 K to364.6 K by dynamic method. All these data were regressed
by λh model, Wilson model and NRTL model, averageabsolute relative deviations of which are
1.25%, 15.02% and 7.22% respectively. It indicates that λh model is mostsuitable for
description of the solid-liquid equilibrium containing PTA.
RESEARCH NOTES
用管式反应技术制备乙二醇乙醚乙酸酯
蔡振云, 卢祖国, 李小波
. 2003, 11(3): 338-340. doi:
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Ethylene glycol monoethyl ether acetate (EGEA), an excellent solvent, is prepared with
ethylene oxide(EO) and ethyl acetate (EA) in a tubular reactor under suitable reaction
condition. The single circulation yield canreach 81%. This technology is not only safe but
also makes it possible to continuously produce EGEA in industry,with low content of high
boiling point by-products.
烟草过氧化物酶(TOPI)的分离与纯化的研究
夏炳乐, 刘清亮, 李敏莉, 徐小龙, 施春华, 解永树
. 2003, 11(3): 341-343. doi:
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A new isoenzyme of tobacco peroxidase(TOP) I was purified from tobacco (K326) by using
acetonepowder, ammonium sulfate precipitation and column chromatography on DEAE-52
cellulose Sephadex G-75 andDEAE-Sephadex A-50. It is an iron-protein containing
haemachrome, whose molecular weight is 21888.5 and theisoelectric point is 3.5. The optimum
pH value and temperature of this enzyme is 6.0 and 45℃ respectively. Theenzyme is stable
in the pH range from 3.0 to 10.0 and has a favorable thermostability.
微滤膜聚并破乳的机理研究
邹财松, 骆广生, 孙永, 戴猷元
. 2003, 11(3): 344-347. doi:
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A study on the membrane coalescence demulsification was carried out with four working
systems ofwater/n-butyl alcohol, water/n-octanol, water/30%TBP(in kerosene) and
water/kerosene. The membranes madeof polytetrafluoroethylene (PTFE) with 1.0μm pore size
were used. The results indicated that the excellent demul-sification efficiency for
emulsions with various oil contents was obtained. A conductivity probe was used to studythe
demulsification mechanism. An electrode probe was designed and used to determine the oil
content near themembrane surface. The obtained data showed that the oil content in the
permeated stream was much higher thanthat in the feed emulsion. A physical mechanism to
explain the membrane demulsification was put forward.
电沉积Ni-W梯度镀层及其结构表征
王宏智, 姚素薇, 张卫国
. 2003, 11(3): 348-351. doi:
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The Ni-W gradient deposit with nano-structure was prepared by an electrochemical deposition
method.X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDXA) indicate that
the crystallite size of the depositdecreases from 10.3nm to 1.5nm and the crystal grating
aberrance increases with the increase of W content in thegrowing direction of the deposit.
The structure of deposit changes from crystalline to amorphous stepwise withassociated
increase of crystal grating aberrance, and presents gradient distribution. These show that
the deposit isgradient with nano-structure.
邻氯苯酚废水的催化湿式氧化处理
徐新华, 汪大翚
. 2003, 11(3): 352-354. doi:
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Catalytic wet air oxidation (CWAO) was investigated in laboratory-scale experiments for the
treatmentof o-chlorophenol in wastewater. Experimental results showed that wet air
oxidation (WAO) process in the absence ofcatalyst was also effective for o-chlorophenol in
wastewater treatment. Up to 80% of the initial CODCr was removedby wet air oxidation at 270
℃ with twice amount of the required stoichiometric oxygen supply. At temperatureof 150℃,
the removal rate of CODCr was only 30%. Fe2(SO4)3, CuSO4, Cu(NO3)2 and MnSO4 exhibited
highcatalytic activity. Higher removal rate of CODCr was obtained by CWAO. More than 96% of
the initial CODCrwas removed at 270℃ and 84.6%-93.6% of the initial CODCr was removed at
150℃. Mixed catalysts had bettercatalytic activity for the degradation of o-chlorophenol
in wastewater.
有机溶剂中树脂催化丙酮氰醇分解反应的动力学模型
章亭洲, 杨立荣, 朱自强, 吴坚平
. 2003, 11(3): 355-357. doi:
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Decomposition of acetone cyanohydrin is the first-step reaction for preparing (S)-α-cyano
-3-phenoxybenzyl alcohol (CPBA) by the one-pot method in organic media. Considering the
compatibility of bio-catalysts with chemical catalysts and the successive operation in the
bioreactor, anion exchange resin (D301) wasused as catalyst for this reaction. External
diffusion limitation was excluded by raising rotational speed to higherthan 190r@min-1 in
both solvents. Internal diffusion limitation was verified to be insignificant in this
reactionsystem. The effect of acetone cyanohydrin concentration on the reaction was also
investigated. An intrinsic kineticmodel was proposed when the mass transfer limitation was
excluded, and the average deviation of the model is10.5%.
伴有生物质热解的流化床中的混沌传递现象
唐松涛, 李定凯, 吕子安, 沈幼庭
. 2003, 11(3): 358-361. doi:
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Experiments of biomass pyrolysis were carried out in a fluidized bed, and dynamic signals
of pressure andtemperature were recorded. Correlation dimension was employed to
characterize the chaotic behavior of pressure andtemperature signals. Both pressure and
temperature signals exhibit chaotic behavior, and the chaotic behavior oftemperature
signals is always weaker than that of pressure signals. Chaos transfer theory was advanced
to explain theabove phenomena. The discussion on the algorithm of the correlation dimension
shows that the distance definitionbased on rhombic neighborhood is a better choice than the
traditional one based on spherical neighborhood. Theformer provides a satisfactory result
in a much shorter time.
搅拌萃取塔内单相流动不同雷诺平均湍流模型结果的比较
尤学一, H.J.Bart
. 2003, 11(3): 362-366. doi:
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The flow field of liquid phase (water) of agitated extraction columns is simulated with the
help ofcomputational fluid dynamics (CFD). Four kinds of Reynolds-averaged turbulence
models, i.e. the standard k-εmodel, the RNG (renormalization group) k-ε model, the
realizable k-ε model and the Reynolds stress model, arecompared in detail in order to
judge which is the best model in terms of the accuracy, less CPU time and memoryrequired.
The performance of the realizable k-ε model is obviously improved by reducing the model
constant fromc2 = 1.90 to c2 = 1.61. It is concluded that the improved realizable k-ε
model is the optimal model.
预分散萃取方法提取槲皮素研究
胡伟, 孙瑛, 叶汝强, 吴树森, 刘洪来,
. 2003, 11(3): 367-370. doi:
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Pre-dispersed solvent extraction (PDSE) was used to extract quercentin from its diluted
solution. Theinfluences of temperature, phase volume ratio (PVR), concentration of sodium
Dodecyl benzene sulphonate andpH value etc. on the extraction efficiency were examined. It
is found that, compared with traditional extractiontechniques under the same condition, a
higher extraction productivity can be obtained by PDSE. The stabilityof colloidal liquid
aphrons plays an important role in this process. In a certain scope, the extraction
efficiencyincreases with PVR. Excessive amount of solvent is not much helpful. A new
analytical method by using ultravioletspectrometer to determine the concentration of
quercentin is established.
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主编:费维扬
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主管:中国科学技术协会
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ISSN: 1004-9541
CN: 11-3270/TQ
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