Chemical batch processes have become significant in chemical manufacturing.In these processes,large numbers of chemical products are produced to satisfy human demands in daily life.Recently,economy globalization has resulted in growing worldwide competitions in traditional chemical process industry.In order to keep competitive in the global marketplace,each company must optimize its production management and set up a reactive system for market fluctuation.Scheduling is the core of production management in chemical processes.The goal of this paper is to review the recent developments in this challenging area.Classifications of batch scheduling problems and optimization methods are introduced.A comparison of six typical models is shown in a general benchmark example from the literature.Finally,challenges and applications in future research are discussed.

A comprehensive three-dimensional model of droplet-gas flow was presented to study the evolution of spray in the effervescent atomization spray with an impinging plate.For gas phase,the N-S equation with the k-ε turbulence model was solved,considering two-way coupling interaction between droplets and gas phase.Dispersed droplet phase is modeled as Lagrangian entities,accounting for the physics of droplet generation from primary and secondary breakup,droplet collision and coalescence,droplet momentum and heat transfer.The mean size and statistical distribution of atomized droplets at various nozzle-to-plate distances were calculated.Some simulation results were compared well with experimental data.The results show that the existence of the impinging plate has a pronounced influence on the droplet mean size,size distribution and the droplet spatial distribution.The air-to-liquid ratio has obvious effects on the droplet size and distribution.

An experimental study was carried out to understand the phenomena of the boiling flow of liquid nitrogen in an inclined tube with closed bottom by using a high speed motion analyzer.The experimental tube is 0.018 m ID and 1.0 m in length.The range of the inclination angle is 45°-90° from the horizontal.The experiment focused on the effect of the inclination angle show that the mean liquid slug length and Taylor bubble length increase with the increasing x/D at various inclination angles.At the same x/D,the mean liquid slug length and Taylor bubble length increase first,and then decrease with decreasing inclination angles,with the maximum at 60°.In the vertical tube,standard deviation of the nitrogen Taylor bubble length increase with the increasing x/D.For the inclined tube,standard deviation of the nitrogen Taylor bubble length increases first,and then decreases with the increasing x/D.Standard deviation of the liquid slug length increases with increasing x/D for all inclination angles.

Nowadays,extractive distillation is the main technique to produce 1,3-butadiene.This study simulated the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus.The solvent ratio is the most important parameter to the extractive distillation process.The article has given out the proper solvent ratios,reflux ratios,distillate ratios,and bottom product ratios of the columns.It also discusses the thermal loads of several columns.The results of simulation are consequently compared with the plant data,which shows good accordance with each other.

Two methods of the modification of zeolite were employed:framework element modification and surface coating,and the influence of the zeolites before and after modification on the CO₂ absorption was investigated.It was found that although hydrophobicity of zeolite could be obtained by means of the surficial organic coating in the method of surface coating modification,partial channel of zeolite would be plugged,as a result,leading to the surface area reducing greatly.Distinctively,the framework element modification method could maintain not only complete lattice structure and adsorption capability of zeolite,but would also obtain a good hydrophobic property.Consequently,significant enhancement on gas absorption by this modified zeolite was achieved and up to a maxi-mum enhancement factor of 2.62.This shows that the solid particles with good enhancement role to gas absorption need not only good adsorptive capability but also certain hydrophobicity.An unsteady heterogeneous model was employed to predict enhancement factor and the calculated results agree well with the experimental data.

In this study,extractive distillation has been applied to separate catechol(CAT) from carbofuran phenol(CFP) with high purity and yield.The relative volatility of CFP to CAT was measured,and the choice of separating agents was investigated.The experimental results indicated that CFP/CAT is an azeotropic system with an azeotropic point at 93.40℃/0.400 kPa and an azeotropic mixture containing 49.96% of CFP and 50.04% of CAT.Data from the determination of the relative volatility have shown that separating agents such as diglycol and 4-butylcatechol(4-TBC) are able to increase the relative volatility up to 1.90.In one shot process batch extractive distillation of CFP mixture with 3%(by mass) diglycol as separating agent,the purity and yield of the obtained CFP was 99.0% and 95.0%,respectively,while the distillation without separating agent provided a purity and yield of only 98.0% and 90.0%,respectively.There was no residual separating agent found in the product.

Structured packing is a good candidate for CO₂ capture process because of its higher mass transfer efficiency and lower pressure drop.Now,the challenging problem of CO₂ capture and storage demands more and more efficiency equipment.The aim of the present study is to investigate the liquid film characteristics under counter current gas phase and throw some insight into the enhancing mechanism of mass transfer performance in structured packing.A high speed digital camera,non-intrusive measurement technique,was used.Water and air were working fluids.Experiments were carried out for different gas/liquid flow rates and different inclination angles.The time-average and instantaneous film widths for each set of flow parameters were calculated.It is shown that the effects of gas phase could be neglected for lower flow rate,and then,become more pronounced at higher flow rate.According to instantaneous film width,three different stages can be distinguished.One is the constant width of liquid film.The second is the slight decrease of film width and the smooth surface.This kind of character will lead to less interfacial area and deteriorate the packing mass transfer performance.For the third stage,the variation of film width shows clearly chaotic behavior.The prediction model was also developed in present work.The predicted and experimental results are in good agreement.

Ceramic ultrafiltration membranes were used to separate titanium silicalite-1(TS-1) catalysts from the slurry of catalytic ammoximation of cyclohexanone to oxime.Silica was shown to have a great effect on membrane fouling in the alkaline environment of this system.In the ammoximation system,there are three main silica sources,which are residual silica on the catalyst particles surface during preparation,silica dissolved from TS-1 catalyst particles by ammonia solvent,and silica sol added into the reaction slurry to inhibit the dissolution erosion of the TS-1 catalyst.The silica dissolved by ammonia has been proved to influence membrane fouling most among the three silica sources.This was because the amount of silica dissolved by ammonia was the largest,and the polymerization of silica monomers at high concentration caused colloid particles formation,which led to a dense cake layer depositing on the membrane surface.Meanwhile,the size reduction of catalyst particles caused by alkaline dissolution also increased specific resistances of cake layers.

In order to solve the serious leaching problem of supported heteropoly acid catalysts in polar reaction media,12-molybdophosphoric acid encapsulated in the supercage of Cs⁺-exchanged Y zeolite was prepared by the "ship in the bottle" synthesis.The influence of ion-exchange conditions and the synthesis parameters on the encapsulation of PMo₁₂ were investigated.The obtained solid sample was characterized by X-ray diffraction(XRD),³¹P magic angle spin nuclear magnetic resonance(MAS NMR) and Fourier Transform Infrared Spectroscopy(FT-IR),and its catalytic activity in the esterification of acetic acid and n-butanol was tested.The ion-exchange time,concentration of aqueous Cs⁺ solution,pH value,and amount of Mo added in the synthesis mixture were revealed to influence the encapsulation very remarkably.Under the optimal conditions,12-molybdophosphoric acid could be successfully encapsulated in the supercage of CsY zeolite,and the samples showed considerable catalytic activity and excellent reusability in the esterification reaction.

Steam reforming(SR) of dimethyl ether(DME) was investigated for the production of hydrogen for fuel cells.The activity of a series of solid acids for DME hydrolysis was investigated.The solid acid catalysts were ZSM-5 [Si/Al=25,38 and 50:denoted Z(Si/Al)] and acidic alumina(γ-Al₂O₃) with an acid strength order that was Z(25)>Z(38)>Z(50)>γ-Al₂O₃.Stronger acidity gave higher DME hydrolysis conversion.Physical mixtures containing a CuO-ZnO-Al₂O₃-ZrO₂ catalyst and solid acid catalyst to couple DME hydrolysis and methanol SR were used to examine the acidity effects on DME SR.DME SR activity strongly depended on the activity for DME hydrolysis.Z(25) was the best solid acid catalyst for DME SR and gave a DME conversion>90% [T=24℃,n(H₂O)/n(DME)=3.5,space velocity=1179 ml·(g cat)^-1·h^-1,and P=0.1MPa].The influences of the reaction temperature,space velocity and feed molar ratio were studied.Hydrogen production significantly depended on temperature and space velocity.A bifunctional catalyst of CuO-ZnO-Al₂O₃-ZrO₂ catalyst and ZSM-5 gave a high H₂ production rate and CO₂ selectivity.

In this paper,a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed.The effects of the reaction temperature,catalyst concentration and ratio of catalyst on the time evolution of the experimental concentration for the constituents including raw material,intermediates and product are investigated.The model parameters are determined in a nonlinear optimization,minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a semi-batch oxidation reactor where the gas and liquid phase were well mixed.The kinetics data demonstrate that the model is suitable to the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid.

An 8-lump kinetic model was proposed to predict the yields of propylene,ethylene and gasoline in the catalytic pyrolysis process of Daqing atmospheric residue.The model contains 21 kinetic parameters and one for catalyst deactivation.A series of experiments were carried out in a riser reactor over catalyst named LTB-2.The kinetic parameters were estimated by using sub-model method,and apparent activation energies were calculated according to the Arrhenius equation.The predicted yields coincided well with the experimental values.It shows that the kinetic parameters estimated by using the sub-model method were reliable.

The esterification of free fatty acids(FFA) in waste cooking oil with methanol in the presence of Fe₂(SO₄)₃/C(ferric sulfate/active carbon) catalyst was studied.The effects of different temperature,methanol/FFA mole ratio and amount of catalyst on the conversion of FFA were investigated.The results demonstrated that under optimal esterification conditions the final acid value of the resultant system can be reduced to ～1(mg KOH)·g^-1,which met fully the requirements in post-treatment for efficient separation of glycerin and biodiesel.The kinetics of the esterification were also investigated under different temperatures.The results indicated that the rate-control step could be attributed to the surface reaction and the esterification processes can be well-depicted by the as-calculated kinetic formula in the range of the experimental conditions.

A highly active Cu/Zn/Al/Zr fibrous catalyst was developed for methanol synthesis from CO₂ hydrogenation.Various factors that affect the activity of the catalyst,including the reaction temperature,pressure and space velocity,were investigated.The kinetic parameters in Graaf’s kinetic model for methanol synthesis were obtained.A quasistable economical process for CO₂ hydrogenation through CO circulation was simulated and higher methanol yield was obtained.

Presented is a multiple model soft sensing method based on Affinity Propagation(AP),Gaussian process(GP) and Bayesian committee machine(BCM).AP clustering arithmetic is used to cluster training samples according to their operating points.Then,the sub-models are estimated by Gaussian Process Regression(GPR).Finally,in order to get a global probabilistic prediction,Bayesian committee machine is used to combine the outputs of the sub-estimators.The proposed method has been applied to predict the light naphtha end point in hydrocracker fractionators.Practical applications indicate that it is useful for the online prediction of quality monitoring in chemical processes.

A finite horizon predictive control algorithm,which applies a saturated feedback control law as its local control law,is presented for nonlinear systems with time-delay subject to input constraints.In the algorithm,N free control moves,a saturated local control law and the terminal weighting matrices are solved by a minimization problem based on linear matrix inequality(LMI) constraints online.Compared with the algorithm with a nonsaturated local law,the presented algorithm improves the performances of the closed-loop systems such as feasibility and optimality.This model predictive control(MPC) algorithm is applied to an industrial continuous stirred tank reactor(CSTR) with explicit input constraint.The simulation results demonstrate that the presented algorithm is effective.

As a result of shortage supply of oil resources,the process for the alternative coal-based fuel,dimethyl ether(DME),has emerged as an important process in chemical engineering field.With the laboratory experiment data about DME synthesis and separation,the production process for DME with high purity is proposed when one-step synthesis of DME in slurry bed reactor from syngas is adopted.On the basis of experimental research and process analysis,the proper unit modules and thermophysical calculation methods for the simulation process are selected.Incorporated the experimentally determined parameters of reaction dynamic model for DME synthesis,regression constants of parameters in non-random two-liquid equation(NRTL) model for binary component in DME separation system with built-in properties model,the process flowsheet is developed and simulated on the Aspen Plus platform.The simulation results coincide well with data obtained in laboratory experiment.Accordingly,the accurate simulation results offer useful references to similar equipment design and process operation optimization.

A strategy for the integration of production planning and scheduling in refineries is proposed.This strategy relies on rolling horizon strategy and a two-level decomposition strategy.This strategy involves an upper level multiperiod mixed integer linear programming(MILP) model and a lower level simulation system,which is extended from our previous framework for short-term scheduling problems [Luo,C.P.,Rong,G.,"Hierarchical approach for short-term scheduling in refineries",Ind.Eng.Chem.Res.,46,3656-3668(2007)].The main purpose of this extended framework is to reduce the number of variables and the size of the optimization model and,to quickly find the optimal solution for the integrated planning/scheduling problem in refineries.Uncertainties are also considered in this article.An integrated robust optimization approach is introduced to cope with uncertain parameters with both continuous and discrete probability distribution.

The dissociation rates of methane hydrates formed with and without the presence of sodium dodecyl sulfate(methane-SDS hydrates),were measured under atmospheric pressure and temperatures below ice point to investigate the influence of the hydrate production conditions and manners upon its dissociation kinetic behavior.The experimental results demonstrated that the dissociation rate of methane hydrate below ice point is strongly dependent on the manners of hydrate formation and processing.The dissociation rate of hydrate formed quiescently was lower than that of hydrate formed with stirring;the dissociation rate of hydrate formed at lower pressure was higher than that of hydrate formed at higher pressure;the compaction of hydrate after its formation lowered its stability,i.e.,increased its dissociation rate.The stability of hydrate could be increased by prolonging the time period for which hydrate was held at formation temperature and pressure before it was cooled down,or by prolonging the time period for which hydrate was held at dissociation temperature and formation pressure before it was depressurized to atmospheric pressure.It was found that the dissociation rate of methane hydrate varied with the temperature(ranging from 245.2 to 272.2 K) anomalously as reported on the dissociation of methane hydrate without the presence of surfactant as kinetic promoter.The dissociation rate at 268 K was found to be the lowest when the manners and conditions at which hydrates were formed and processed were fixed.

Green oxidation of cyclohexene using dioxygen as oxidizing agent is highly desirable because of its environmental compatibility and economic impact.Separation of its oxidation products depends on the reliable vaporliquid equilibrium(VLE) data of relevant components,which are still lacking.The VLE data of binary system 1,2-epoxycyclohexane and 2-cyclohexen-1-one under ambient pressure were obtained using an improved VLE equipment EC-2 still in this work.The results showed that this binary system has no azeotropic point.Furthermore,the experimental VLE data were correlated with the Wilson thermodynamic model and the corresponding binary interaction parameters of the model were obtained.The results showed that the VLE data agreed well with the model and passed the thermodynamic consistency test of Herrington.

In an equilibrium vessel,the solid-liquid equilibria(SLE) for three binary mixtures of phenyl salicylate with 1-butanol,2-butanol,and 2-methyl-1-propanol,respectively,have been measured from 283.15 K to the melting temperature of the solute using a method in which an excess amount of solute was equilibrated with the alcohol solution.The liquid concentrations of the investigated phenyl salicylate in the saturated solution were analyzed by UV spectrometry.Activity coefficients for phenyl salicylate have been calculated by means of the Wilson,NRTL,and UNIQUAC equations and with them were correlated solubility data that were compared with the experimental ones.The best correlation of the solubility data has been obtained by the Wilson equation by which the average root-mean-square deviation of temperature for the three systems is 1.03 K.

In this study,double-hydrophilic hydroxylpropyl cellulose(HPC) based copolymers with poly(N-isopropylacrylamide)(PNIPAM) and poly(acrylic acid)(PAA) as graft chains were synthesized and characterized.The release behavior of drug-loaded micelles was studied.The results show that the hydrophilicity of copolymers improves as the pH increases,whereas the hydrophobicity of copolymers enhances as the temperature increases,and all the phase behaviors are reversible.The diameter of micelles decreases and then increases with pH increase.It shows different micellizing behavior under acidic and basic conditions according to the temperature increase.In vitro release experiments,which used theophylline as a model drug,show that the micelles enhance pH sensitivity in the release process.

Polyvinyl alcohol(PVA)-sodium polyacrylate(PAAS)-KOH-H₂O alkaline polymer electrolyte film with high ionic conductivity was prepared by a solution-casting method.Polymer Ni(OH)₂/activated carbon(AC) hybrid supercapacitors with different electrode active material mass ratios(positive to negative) were fabricated using this alkaline polymer electrolyte,nickel hydroxide positive electrodes,and AC negative electrodes.Galvanostatic charge/discharge and electrochemical impedance spectroscopy(EIS) methods were used to study the electrochemical performance of the capacitors,such as charge/discharge specific capacitance,rate charge/discharge ability,and charge/discharge cyclic stability.Experimental results showed that with the decreasing of active material mass ratio m(Ni(OH)₂)/m(AC),the charge/discharge specific capacitance increases,but the rate charge/discharge ability and the charge/discharge cyclic stability decrease.

The dyeability of polylactide fabric has been investigated with the substituted aminoanthraquinone hydrophobic dyes.Their application to the polylactide fabric led to good exhaustion values and good wash fastness between 4 and 5.Microscopic assessment of cross-sections of the dyed polylactide fibres confirmed that these dyes could penetrate into the fibres.The nature of the substituted amino groups showed little influence on the wash fastness,but clearly influenced the exhaustion and light fastness.

Iodine-sulfur(IS) thermochemical water-splitting cycle is the most promising massive hydrogen production process.To avoid the undesirable side reactions between hydriodic acid(HI) and sulfuric acid(H₂SO₄),it is necessary to purify the two phases formed by the Bunsen reaction.The purification process could be achieved by reverse reaction of the Bunsen reaction.In this study,the purification of the H₂SO₄ and HI Phases was studied.The purification proceeded in both batches and the continuous mode,the influences of operational parameters,including the reaction temperature,the flow rate of nitrogen gas,and the composition of the raw material solutions,on the purification effect,were investigated.Results showed that the purification of the H₂SO₄ phase was dominantly affected by the reaction temperature,and iodine ion in the sulfuric acid phase could be removed completely when the temperature was above 130℃;although,the purification effect of the HI phase improved with increasing of both the flow rate of nitrogen gas and temperature.

Diatomite is a kind of natural low-cost mineral material.It has a number of unique physical properties and has been widely used as an adsorbent in wastewater treatment.This study was conducted to investigate the aerobic biodegradation of coal gasification wastewater with and without diatomite addition.Experimental results indicated that diatomite added in the activated sludge system could promote the biomass and also enhance the performance of the sludge settling.The average mixed-liquor volatile suspended solids(MLVSS) is increased from 4055 mg·L^-1 to 4518 mg·L^-1 and the average settling volume(SV) are changed only from 45.9% to 47.1%.Diatomite additive could enhance the efficiency of chemical oxygen demand(COD) and total phenols removal from the wastewater.The COD removal increased from 73.3% to near 80% and the total phenols removal increased from 81.4% to 85.8%.The mechanisms of the increase of biomass and pollutants removal may correlates to the improvement of bioavailability and sludge settlement characteristics by diatomite added.Micrograph of the sludge in the diatomite-activated sludge system indicated that the diatomite added could be the carrier of the microbe and also affect the biomass and pollutant removal.

A rapid and continuous method for production of LiFePO₄/C nanoparticles in super heated water is described,wherein soluble starch was used as carbon precursor.The effects of pH,flow rate,temperature,and pressure on the formation of LiFePO₄/C particles were investigated.Results showed that the pH value was the key factor on the formation of phase pure LiFePO₄,which only formed at pH=7;the LiFePO₄/C occurred as particles with about 70-200 nm size and LiFePO₄ was covered by a thin carbon layer;higher flow rate,higher pressure,and lower temperature led to smaller particles of LiFePO₄/C.

Seven distributors with different configurations are designed and optimized by constructal approach.Their flow distribution performance and energy dissipation are investigated and compared by computational fluid dynamics(CFD) simulation.The reliability of CFD simulation is verified by experiments on the distributor that has all distributing rectangle channels on a plate.The results show that the symmetry of the distributing channels has decisive influence on the performance of flow distribution.Increasing the generations of channel branching will improve the flow distribution uniformity,but on the other hand increase the energy dissipation.Among all the seven constructal distributors,the distributor that has dichotomy configuration,Y-type junctions and straight interconnecting channels,is recommended for its better flow distribution performance and less energy dissipation.