Heat of vaporization of liquid is very important thermodynamic data for research and many applications in chemical engineering.After analyzing the drawbacks of the Watson’s equation for estimating ΔH_bi, a new equation was proposed from the viewpoint of molecular thermodynamics theory and the equation of heat of vaporization at T_b.The physical meaning of Eq.(5) was clear and definite.The average error of Eq.(5) was 0.69% for 310 experiment values.The applicable temperature range was large,from near melting point to near critical point.The accuracy of the equation was over 4.4 times higher than that of Watson’s equation for 39 structural types such as alcohol, aldehyde, ketone, ether, amine, pyrrole, pyridine, and so on, in chemical engineering, especially petrochemical engineering and fine chemicals.

The oscillating heat pipes (OHPs) are complex two-phase systems which have multiple parameters and multi-disciplinary physics，and investigations on OHPs are still at a primary stage.In this paper, a detailed theoretical model was developed by analyzing the forces and the heat and mass transfer in the systems. An n-shaped OHP with a single water plug and two vapor bubbles was investigated, and the governing equations were solved by using an explicit finite difference scheme to simulate the oscillating behavior of the liquid plug and heat and mass transfer characteristics.The results showed that the overall and local oscillations and the sudden increase and subsequent decrease in amplitude and frequency were the typical behavior of the liquid plug.The pressure difference between two bubbles was the main driving force of the oscillating plug.Capillary force could be neglected in comparison with other forces, and the plug gravity must be considered when OHP did not work horizontally.Instantaneous dry-up of the liquid film could enhance the amplitude and frequency of plug velocity and the overall heat transfer rate.

A superhydrophilic heat transfer surface was formed by a special nano-material coating process. The enhanced heat transfer characteristics and enhanced heat transfer mechanism of water jet boiling on the superhydrophilic surface was investigated and the jet boiling characteristics on the superhydrophilic surface was compared with those on the common metal heat transfer surface. The quantitative effects of flow condition, heating mode, heating condition and superhydrophilic coating process on critical heat flux (CHF) were studied and enhanced heat transfer characteristics in the nucleate boiling regime were confirmed. The heat transfer characteristics of jet boiling on the superhydrophilic surface were summarized with semi-theoretical, semi-empirical correlations.

The flow resistance of the inlet section of heat exchanger with longitudinal flow in shell side was studied with the distributed fluid flow method.Transverse velocity and longitudinal velocity were investigated，and the resistance coefficient of transverse flow was analyzed as well.Prediction was made for the flow resistance of inlet section based on a number of experiments and the corresponding equation was obtained.The deviation of the calculated results with the equation from the experiment data was less than 5%.

Three-dimensional gas flow field in the new vortex quick separation system with an inner component of FCC disengager was simulated based on the Reynolds stress model（RSM）provided by CFX. Predictions with the Reynolds stress model（RSM） were in reasonable agreement with experimental results measured by intelligent five-hole probe.The trajectory of the particles was computed by introducing the discrete random walk tracking model, through which the grading efficiency and general efficiency of the vortex quick separator could be simulated.Numerical calculation showed that the inner component could eliminate the short-circuit flow near the vortex head and help to improve the separation efficiency of the vortex quick separator.Comparison of the particle trajectory and separation efficiency between the generally used VQS system and this new system with an inner component showed the performance of the latter better than the former.

Planar laser induced fluorescence (PLIF) technique was established to study the liquid-liquid turbulent micromixing process. A typical process of liquid-liquid cross-flow mixing in flow channels at millimeter scale was visualized by using this non-invasive measurement technique.Transient measurements of concentration field highlighted by the excited fluorescence dye were recorded. A wave-like vortex structure at the scale of 1 to 2 millimeter was found after the two liquid cross flows met each other. The results showed that the development of the vortex was the main factor affecting the mixing performance.The mixing process was also analyzed quantitatively by using the intensity of segregation (IOS).The trend of IOS value vs y locations was also illustrated and the effect of velocity ratio of two liquid flows and Reynolds number of the mixing liquid flow on the mixing process was studied.

The Hilbert-Huang transform(HHT) was used to analyze the differential fluctuation signal of gas-liquid two-phase flow in a horizontal pipeline. By using the empirical mode decomposition(EMD) method, the signal was decomposed into a finite and small number of intrinsic mode function(IMF), and then the Hilbert transform was applied to each of these intrinsic mode functions to get the energy-frequency-time distribution, designated as the Hilbert spectrum. The energy characteristics of different intrinsic mode functions was extracted to characterize the differential pressure fluctuation signal. Based on the above analysis, a comparison of the results for different diameters of pipeline was presented and the relationship between the energy distribution of signals of different frequency bands and flow pattern conversion was analysed. Meanwhile, the differences between the wavelet method and HHT method were also discussed. The experimental results show that the HHT is an extremely powerful tool for the analysis of nonlinear and non-stationary signals，and the extracted energy characteristics can reflect the flow state of gas-liquid two-phase flow and flow pattern conversion.This method could be useful for the signal analysis in gas-liquid two-phase flow in a horizontal pipeline.

Shannon entropy(SE) analysis of pressure fluctuation time series was developed to characterize the flow characteristics in a spout-fluid bed coal gasifier cold model with cross section of 300 mm×30 mm and height of 2000 mm.A multi-channel pressure signal acquisition system was established to obtain the pressure fluctuation time series at various bed locations, and a high-resolution digital CCD camera used to record the flow patterns in various operating conditions.The effects of spouting gas velocity and fluidizing gas flow rate on SE were examined. The characteristics of dynamic behavior were discussed according to the operating parameters and SE. SE was found different for different flow patterns, and was used to identify the flow patterns. SE was also found significantly different at various bed locations. It indicated that a spout-fluid bed at a high spouting gas velocity or a high fluidizing gas flow rate showed no periodic nature but chaotic nature since the SE at all bed locations increased sharply and flow instabilities existed.Research results showed that SE analysis could help to understand the complex flow characteristics of spout-fluid beds, providing reference to the engineering of spout-fluid bed coal gasifiers.

A new nonlinear method-chaotic analysis was used to analyze the pressure fluctuation in the impinging region of SCISR. The signals of pressure fluctuation were filtered by using the wavelet theory. The chaotic attractors were reconstructed on the basis of the phase space theory.Three characteristic parameters to describe chaos, such as correlation dimension, Kolmogorov entropy and Lyapunov exponent, were calculated. The chaotic profiles were shown in the impinging region of SCISR by studying the value of these three parameters at different rotary speeds and on different positions of area-y.At the same time, the trend of these three parameters changed similarly at different rotary speeds and on different positions.

The macrokinetics of CO gas coupling reaction on Pd catalyst was studied in a fixed-bed reactor.The size of the catalyst was φ 1.5 mm×(2—3) mm.The experiments were carried out on Pd catalyst at the optimum CO coupling reaction conditions of temperature 110—130℃, space velocity 0.146—0.292 mol•g^-1•h^-1, EN mole concentration 5%—15% and CO mole concentration 20%—35%.The Runge-Kutta and simplx methods were used to determine the parameters of kinetics models.The statistic test and residual error distribution were made to prove the validity of the kinetics models.The calculated results by the model were in agreement with the experimental data.The macrokinetics could provide theoretical foundation and guidance for simulation and scale-up of the reactor.

The Cu-Zr-Ce-O mixed oxides with various ZrO₂ contents were prepared by the co-precipitation method for selective CO oxidation and characterized by H₂-TPR,CO-TPR techniques.The effects of ZrO2 loading and different pretreatments on the activity of Cu-Zr-Ce-O catalysts were studied.The results showed that higher CO conversion (>99%) and selectivity in a wider temperature range（160—200℃） were obtained when the catalyst composition was Cu₁Zr₁Ce₉O_δ.The addition of an appropriate quantity of ZrO₂ could improve thermal stability and oxygen storage capacity, enhance the absorbed oxygen transforming to surface lattice oxygen and facilitate the oxidation of CO simultaneously.The Cu₁Zr₁Ce₉O_δ catalyst pretreated in oxygen had the best catalytic performance. The amounts of surface lattice oxygen and Cu⁺/Cu²⁺ ionic pair both affected the activity of the catalysts，but in hydrogen-rich atmosphere, the influence of the content of surface lattice oxygen was greater.

The kinetics of methanol to olefins in the fixed-bed isothermal integral reactor was studied. The lumping idea was introduced into the kinetics study, in which the influence of water and coke deposition was taken into consideration.The equations of kinetics on fresh and deactivated catalyst were calculated with the help of the simplex optimization and Runge-Kutta methods.The obtained general kinetics equations could be used to calculate the reaction rates of corresponding lump. Subsequently, the respective reaction rate of ethylene, propylene, butene in any conditions were calculated based on the relation of ratios between olefins (ethylene/propylene and propylene/butene) and reaction temperature.The results showed that the error of statistical test and comparison of calculated values with the experimental values was in the allowable range.

Using sodium carbonate as catalyst, carbon dioxide gasification kinetics for four kinds of low activity anthracites（V_ad=2.69%—4.35%） was investigated with isothermal thermo-gravimetric analysis under ambient pressure.The reaction control conditions, eliminating both inner and outer diffusion effects, were examined.The relationships of coal conversion versus reaction time for these low activity anthracites were measured from 750 ℃ to 950 ℃.The shrinkingcore model (SCM), homogeneous model (HM) and modification volumetric model (MVM) were used to correlate the relationships between conversion and time and to obtain the reaction rate constants at different temperatures.Then the reaction activation energy and the pre-exponential factor of four anthracites were predicted respectively by using the Arrhenius equation.According to the order of reaction rate constant determined by the above three models(SCM, HM, MVM), the activity order of the four anthracites
was Shangjing coal>Yong’an Jiashai coal>Yong’an Fengshai coal>Yongding coal.The activation energy, ranging from 122.27—214.72 kJ•mol^-1 estimated by this study, agreed well with the literature reported for the case of potassium chloride catalytic gasification by carbon dioxide for higher activity coals.

The MgCl₂/SiO₂ complex support was prepared by spray drying using alcoholic suspension which contained MgCl₂ and SiO₂. The complex support reacted with TiCl₄ and di-n-butyl phthalate, give the catalyst for propylene polymerization. The catalyst was spherical and porous with high specific surface area. The multistage polymerization of propylene for high impact propylene was studied with the catalyst system. It was found that the final high impact polypropylene after two stages of reaction was still freeflowing, spherical granules. Homopolypropylene with pore diameter between 100 nm and 10000 nm was suitable for EPR to fill in during ethylene-propylene copolymerization. The high impact polypropylene showed good balance between stiffness and toughness.

On the basis of literature survey, trialkyl phosphine oxide(TRPO) was selected as the extractant. Nine kinds of mono-carboxylic acids, formic, acetic, propionic, butyric, caproic, monochloroacetic, dichloroacetic, trichloroacetic and lactic acids, were used as solutes to be extracted. Kerosene was investigated for their abilities to affect the relative basicity of extractant (pK_a,BS). The dependence of TRPO concentration, hydrophobicity and pK_a of the acid on pK_a,BS was studied in order to explore the feasibility of mathematical models based on the chemical reactive theory to describe the extractive equilibrium behavior with only two parameters, hydrophobicity and pKa,that affect pK_a,BS.The pK_a,BS value hardly changed with TRPO concentration, while the properties of carboxylic acid, hydrophobicity and pK_a affect pK_a,BS obviously.The mathematic models proposed in this paper could be used to predict the extractive equilibrium of monocarboxylic acid extracted by TRPO.A simple and feasible modification method for measuring pK_a,BS was also suggested.

A model aqueous solution containing seven important flavor compounds in beer was used to investigate the effect of feed temperature on pervaporation (PV) performance and coupling effects between ethanol and flavor compounds.The results showed that the presence of the flavor compounds weakened the preferred permeation of ethanol.The lower the feed temperature, the greater the impact. The presence of ethanol had different effects on the flavor compounds which was much related to the solubility properties of the compounds. Both total flux and partial flux of each component could be well described by the Arrhenius Law despite the existence of coupling effects.

Investigations have revealed the permeation performance of electrolytes in the separation process by nanofiltration membranes in single salt solutions. However, there is still not much information about the separation process of mixed electrolyte solutions, and by now most of the investigations have been on solutions containing three kinds of ions, in which anions are mostly NO^-₃, Cl^- and SO^2-₄, and cations are mostly Na⁺，Ca²⁺ and Mg²⁺. In this work, permeation experiments of three kinds of nanofiltration membranes(ESNA 1-LF, ESNA 1 and LES 90) for binary electrolyte solutions(NaNO₃, Ca(NO₃)₂; NaCl, NaNO₃; NaCl, Ca(NO₃)₂; etc.) were carried out, and the interactions between co-ions and counter-ions were investigated.The result showed that the ion with better permeation performance would permeate first,thus depressing the rejection of itself and enhancing the rejection of the co-ion with poor permeation performance. Interaction between co-ions with similar permeation performance was not obvious. Counter-ions influenced each other mainly through the electroneutrality principle.

Ant colony optimization(ACO) has high optimizing efficiency, but can only be applied to combinational optimization problems. For adapting ACO to continuous optimization problems, the concise evolution mechanism of evolution program(EP) was introduced to reconstruct ACO, in which the objective was to search optimal food source other than the best sequence. The ant colony was divided into global ants and local ants, which guided the individuals to perform global exploratory optimization and local excavating optimization respectively.Ants released pheromone on the individuals, and the pheromone was shared by all ants, which inherited the collective autocatalytic behaviour characterised by positive feedback mechanism of ACO.Under the support of eugenic strategy, the EP-ACO algorithm was constructed. The experimentations on optimization of complex functions showed that EP-ACO could be well fit for solving continuous optimization problems with high global optimization efficiency and showed good adaptability to high dimension problems. Finally, EP-ACO was successfully applied to the operation optimization of the equipment of xylene isomerization.The results were better than the referenced methods.

The state of the art process modeling and optimization software was reviewed. Motivated by increasing demand on modeling and optimization of systems with large-scale and high complexity characteristics, a new application mode with service-oriented open architecture was proposed.ASCEND (advanced system for computations in engineering design) was chosen as the base for equation-oriented modeling. Its inherent structure, data flow, working mode and communication interface were redefined and reconstructed. With support from COM/DCOM/AUTOMATION technology, AscendServer was built as the core service providing modeling and optimization functionalities. Some key issues such as componentization, event handling and coordination between processes were discussed in details. Within this superstructure, modeling and optimization for large-scale complex systems could be integrated with more extensive data exchange, more flexible application mode and more adaptative capabilities. A data reconciliation system of water consumption balancing for a petrochemical company was given to verify the efficiency and functionalities of the new open structure service for modeling and optimization.

The appearance，formation and development of corrosion products on archaeological iron in simulated soil media (0.06 mol•L^-1 NaCl+0.03 mol•L^-1 Na₂SO₄+0.01 mol•L^-1 NaHCO₃ aqueous solution) were investigated through metallographic technique，micro-Raman spectrometry and X-ray diffraction.The study showed that，selective corrosion of iron occurred on the cast iron in the solution in the first 34 h，with some white wreath-shaped Fe(OH)₂ depositing on the surface and dispersed Fe(OH)₂ depositing inside the wreath. After 120 h，the surface of the sample was covered with a layer of green rust(GR)，which mainly consisted of GR(Cl^-)(molecular formula:Fe^Ⅱ₃Fe^Ⅲ(OH)₈Cl•2H₂O)and GR(SO^2-₄)(molecular formula:Fe^Ⅱ₄Fe^Ⅲ₂(OH)₁₂SO₄•2H₂O)，and the outside of the green rust changed into γ-FeOOH when contacting with air. About 288 h later，the corrosion products became double layers: the inner layer was composed of crystalloid black FeO and Fe₃O₄，and the outer layer was brick red γ-FeOOH, which was devastating to the conservation of iron artifacts because of its loose structure.So such ions as Cl- and SO^2-₄ which contributed to the formation of γ-FeOOH must be removed from the corrosion products of archaeological iron in order to prolong the life of iron antiquities.

Thin films of cathodically deposited nickel hexacyanoferrate (NiHCF) on different substrates were investigated as electrochemically switched ion exchange (ESIX) materials for the selective separation of alkali cations in aqueous nitrate solutions. The films were deposited on platinum, aluminum and graphite substrates with different preparation conditions. In 1 mol•L^-1 KNO₃ solution cyclic voltammetry (CV) was used to reversibly intercalate and deintercalate K⁺ from the matrix and to investigate the electroactivity, ion-exchange capacity and the regeneration capability of NiHCF films. In 1 mol•L^-1(KNO₃+CsNO₃) mixture solution CV combining electrochemical impedance spectra (EIS) was used to investigate the ion selectivity of the films. The effect of synthesis condition on electrochemical performance of the films and the relationship between composition and electrochemical behavior of the NiHCF films were also studied by using CV and energy dispersive X-ray spectroscopy (EDS). Experimental results showed that different electrolytic solutions could prepare different NiHCF films which were dominated by either “soluble” or “insoluble” structure and the electroactive NiHCF films could be successfully deposited onto Pt, Al and graphite substrates. The NiHCF films formed on graphite and Al substrates also had good ESIX performance.

A new method was used to analyze, characterize and simulate the kinetic behavior of bio-macromolecular enzymatic hydrolysis reaction based on bio-informatics, HPSEC and graphic processing. Tryptic hydrolysis of whole casein was selected as a model system. The possible reaction mechanism was deduced from a series of chromatographic results and experimental analysis. According to programming calculation and molecular simulation, product information, such as cleavage sites of protein and structure model of active peptides, was also obtained. Furthermore, a 3-D continuous surface and corresponding contour were plotted to characterize the dynamic process of protein enzymatic hydrolysis, and mathematical analysis of the surface-fit function was also carried out. The optimized polynominal equation can be applied to adjustment and control of the complex reaction. It is also beneficial to directional and quantitative preparation of target active peptides.

On the basis of chromatography analysis and reaction mechanism of enzymatic hydrolysis, the four-lumping kinetic model for the process of casein tryptic hydrolysis was established. According to the molecular mass, the hydrolysates were combined into four lumps and the simplified reaction network was described with intrinsic kinetics equation, which contained product inhibition, substrate inhibition and enzyme inactivation. The lumps were prepared by membrane separation, and the lumping kinetic constants were estimated by the Marquardt method. The ability of prediction and extrapolation of the lumping kinetic model was fitted and tested by comparing the computed values with the experimental ones, which demonstrated that the lumping method could characterize the kinetic behavior of complicated bio-reaction and predict the concentration distribution of multi-products.

To study the extra-cellular electron transfer process by which electrons can be transferred from microbial cells to Fe(Ⅲ) oxides, two experiment systems were established: traditional anaerobic cultivation system and novel microbial fuel cell system. Comparing the data gathered from these two systems,it was proposed that direct contact was a very important way for ferric oxides reduction by Geobacter metallireducens.Electron shuttles played a less important role after most of the surface of mineral oxides were covered by microorganisms,and the reduction rate was to some extent related to the surface area of solid electron acceptors.

The effects of two different phosphorus sources, corn steep liquor（CSL）and KH₂PO₄, on the growth of Candida glycerinogenes and glycerol production in batch fermentations were investigated. The glucose consumption in glycerol production, cell growth, maintenance, and byproducts formation during different fermentation phases was also analyzed kinetically.The results showed that the influence of CSL on cell growth and glucose consumption was so prominent that even minor variation of its quality or quantity caused much difference in experimental results. It was also found that the relationship between glycerol synthesis and cell growth was very close with CSL as phosphorus source,while it was rather loose with KH₂PO₄ as phosphorus source. With the increase in phosphorus concentration,glucose consumption in cell growth and maintenance was kept basically stable during the whole fermentation process. However,glucose consumption in glycerol production gradually decreased,and the byproducts which were mainly formed during the rapid growth phase increased. Further studies indicated that the yield of glycerol on glucose reached the peak of 53.44 % and 52.76 % with 14 g•L^-1 CSL and 0.57 g•L^-1 KH₂PO₄, respectively.Accordingly the yield of byproducts also decreased to the minimum value of 5.84 % and 4.25 %, respectively.

The emission of NO_x when coal was burning in O₂/CO₂ was compared with the case of burning in air, and the effects of temperature and excess air ratio on NO_x formation were analyzed by using a one-dimensional drop-tube furnace. The formation and reduction mechanisms of NO_x in O₂/CO₂ were studied.There was a NO_x peak in both two atmospheres, and the peak of high volatile matter coal appeared much earlier than the peak of low volatile matter coal.The peak in O₂/CO₂ atmosphere appeared earlier than the peak in air and the peak value was lower than that in air.The amount of NO_x increased quickly with temperature in air, but the amount of NO_x changed slowly with temperature in O₂/CO₂ atmosphere.In both atmospheres the NO_x peak value increased with excess air ratio.The peak value of high volatile matter coal in O₂/CO₂ was lower than that in air but the low volatile matter coal was less affected.

A method of estimating the thermal properties from the transient experiment based on the solution of the nonlinear inverse problem of parameter estimation by using the Levenberg-Marquardt iterative procedure was presented. In the application of the inverse method a one-dimensional unsteady heat conduction problem was used and simulated “measured” transient temperature data were generated by adding uniform random errors to the computed exact temperature. Temperature independent and dependent thermal conductivity and volumetric heat capacity were respectively estimated by using the method.The results showed that the method was suitable for practical calculation of thermal properties based on general transient experimental techniques and for analysis of inverse heat conduction problems.It could also provide useful information to optimize the experiment.

The boundary element method (BEM) in injection molding cooling analysis generate full-matrix equations. If the element number is too large, its calculating work will be beyond the computer’s ability. There is no valid numerical method to solve these equations today. The key problem is the computation speed.This not only means a long time of computation, but also means that the calculation does not convergent easily.This paper presents a new method to deal with the problem. Because the temperature variation on mold surface is successional, when two points are close to each other, their temperature is nearly equal. So the new method neglected the temperature difference and incorporated the adjacent elements in one group. After incorporation, the size of cooling model was reduced. The average temperatures of elements in one group were solved firstly. Using these temperature results, the temperature of every element in one group would be computed in the next step. In this way, one large size equations was decomposed into several small size equations. The computational work was reduced and the calculating time was less than one quarter of the conventional method.On the other hand, element incorporation reduced the size of data and helped to weaken the effect of truncation error which caused distorted results. This could enhance the treatable number of element one time more than that of original method.

The blends low-density polyethylene(LDPE) and lignin were compatilized by the graft copolymer of maleic anhydride(MAH) onto low-density polyethylene.The effects of LDPE-g-MAH contents on thermal properties,FTIR spectral analyses mechanical properties, rheological behavior and morphology of LDPE/lignin blends were investigated.The results of TG-DSC indicated the addition of compatibilizer decreased melting temperature, improved thermal stability.FTIR elucidated the existence of an intermolecular hydrogen-bonding interaction between lignin and LDPE-g-MAH.Rheological behavior analysis for the blends demonstrated that the blends were processable.Scanning electron microscopy (SEM) micrograph showed that the compatibilizer LDPE-g-MAH could improve the dispersity of lignin in LDPE and reduce the dispersed phase size.The introduction of LDPE-g-MAH effectively improved the mechanical properties of LDPE/lignin blow film.When mass ratios of lignin, LDPE and LDPE-g-MAH were 25/75/10, the blow film had excellent mechanical property.

In order to stabilize the particle size of Al(OH)₃ production in sodium aluminate solution, a systematic study of the effects and mechanism of additives on agglomeration and nucleation in seed precipitation was made. The result indicated that some appropriate additive at certain concentration could significantly decrease the fine particle content, enhance the agglomeration process, and effectively restrain the secondary nucleation process. For instance, additive I33 at 40 ml•L^-1 decreased the content of particles less than 30 μm by 26.1% and increases the mean particle size by 21.08 μm. The crystal morphology showed that the additives could accelerate the inter-growth of crystals.

Proton conductive membrane plays a decisive role in polymer electrolyte membrane fuel cell systems. To prepare polymer electrolyte membranes for direct methanol fuel cell(DMFC), a series of novel sulfonated polyimides(SPI) were synthesized from sulfonated diamine，2,5-bis(4-aminophenoxy)benzene sulfonic acid (S-TBDA) with 3,3′,4,4′- benzophenone tetracarboxylic dianhydride (BTDA) and non-sulfonated diamine(ODA) via direct polymerization in this study.The sulfonation degree of the polymers was controlled by changing the molar ratio of the monomers. The obtained SPI membrane was then characterized with FTIR and the influence of sulfonation degree on proton conductivity, methanol permeability and other properties were investigated.With the increase of sulfonation degree，the proton conductivity and methanol permeability increased gradually.The proton conductivity of the SPI membranes ranged from 3.9×10^-3 to 3.4×10^-2 S•cm^-1 and the methanol permeability was less than 1×10^-7 cm² •s^-1.The experiment result indicated the potential of such proton conductive membrane for fuel cell applications.