乳化法分离精制对二氯苯的研究

用正交试验设计的方法，研究出可行的乳化精制对二氯苯的优化工艺，乳化剂为OP－7，浓度为0．05％，处理温度60℃。所得产品纯度为99．5％，收率97．28％。

Fuzzy Neural Network Model of 4-CBA Concentration for Industrial Purified Terephthalic Acid Oxidation Process

A fuzzy neural network (FNN) model is developed to predict the 4-CBA concentration of the oxidation unit in purified terephthalic acid process. Several technologies are used to deal with the process data before modeling.First,a set of preliminary input variables is selected according to prior knowledge and experience. Secondly,a method based on the maximum correlation coefficient is proposed to detect the dead time between the process variables and response variables. Finally, the fuzzy curve method is used to reduce the unimportant input variables.The simulation results based on industrial data show that the relative error range of the FNN model is narrower than that of the American Oil Company (AMOCO) model. Furthermore, the FNN model can predict the trend of the 4-CBA concentration more accurately.

Fuzzy Support Vector Regression Model of 4-CBA Concentration for Industrial PTA Oxidation Process

In the past few years, support vector machines (SVMs) have been applied to many fields, such as pattern recognition and data mining, etc. However there still exist some problems to be solved. One of them is that the SVM is very sensitive to outliers or noises because of over-fitting problem. In this paper, a fuzzy support vector regression (FSVR) method is presented to deal with this problem. Strategies based on k nearest neighbor (kNN) and support vector data description (SVDD) are adopted to set the fuzzy membership values of data points in FSVR.The proposed FSVR soft sensor models based on kNN and SVDD are employed to predict the concentration of 4-carboxy-benzaldehyde (4-CBA) in purified terephthalic acid (PTA) oxidation process. Simulation results indicate that the proposed method indeed reduces the effect of outliers and yields higher accuracy.

The Effect of Titania Structure on Ni/TiO_2 Catalysts for p-Nitrophenol Hydrogenation

The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma (ICP), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and temperature-programmed reduction (TPR). Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2(A) is higher than that of rutile titania supported nickel catalyst Ni/TiO2(R), possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2(A) is easier than that for Ni/TiO2(R) at similar reaction conditions.

Multi-objective Optimization of Industrial Purified Terephthalic Acid Oxidation Process

Multi-objective optimization of a purified terephthalic acid (PTA) oxidation unit is carried out in this paper by using a process modei that has been proved to describe industrial process quite well. The modei is a semi-empirical structured into two series ideal continuously stirred tank reactor (CSTR) models. The optimal objectives include maximizing the yield or inlet rate and minimizing the concentration of 4-carboxy-benzaldhyde, which is the main undesirable intermediate product in the reaction process. The multi-objective optimization algorithra applied in this study is non-dominated sorting genetic algorithm Ⅱ (NSGA-Ⅱ). The performance of NSGA-Ⅱ is further illustrated by application to the title process.

Distinct synergetic effects in the ozone enhanced photocatalytic degradation of phenol and oxalic acid with Fe^(3+)/TiO_2 catalyst

In this work. phenol and oxalic acid （OA） degradation in an ozone and photocatalysis integrated process was intensively conducted with Fe3 ＋/TiO2 catalyst. The ferrioxalate complex formed between Fe3＋ and oxalate accelerated the removal of OA in the ozonation, photolysis and photocatalytic ozonation process, for its high reactivity with ozone and UV. Phenol was degraded in ozonation and photolysis with limited TOC removal rates, but much higher TOC removal was achieved in photocatalytic ozonation due to the generation of-OH. The sequence of UV light and ozone in the sequential process also influences the TOC removal, and ozone is very powerful to oxidize intermediates catechol and hydroquinone to maleic acid. Fenton or photo-Fenton reactions only played a small part in Fe3＋/TiO2 catalyzed processes, because Fe＋ was greatly reduced but not regenerated in many cases. The synergetic effect was found to be highly related with the property of the target pollutants. Fe3 ＋/TiO2 catalyzed system showed the highest ability to destroy organics, but the TiO2 catalyzed system showed little higher synergy.

Kinetics of Burning Side Reaction in the Liquid-phase Oxidation of p-Xylene

During the liquid-phase oxidation of p-xylene,over-oxidation of reactant,intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction.Batch and semi-continuous experiments were carried out,and the experimental data of the burning side reaction were analyzed and reported in this paper.The results showed that the rates of burning side reactions were proportional to the rates of the main reaction,but decreased with the increasing concentrations of reactant and intermediates.The inter-stimulative and competitive relationship between the burning side reaction and the main reaction was confirmed,and the rates of the burning side reaction could be described with some key indexes of the main reaction.According to the mechanism of the side reactions and the kinetics model of main reaction which were proposed and tested in the previous papers,a kinetic model of the burning side reactions involving some key indexes of the main reaction was developed,and the parameters were determined by data fitting of the COx rate curves.The obtained kinetic model could describe the burning side reactions adequately.

Catalytic Conversion of Biomass-Derived Polyols into Para-xylene over SiO2-Modified Zeolites

This work proved that biomass-based polyols (sorbitol, xylitol, erythritol, glycerol and ethanediol) were able to be converted into high-value chemical (p-xylene) by catalytic cracking of polyols, alkylation of aromatics, and the isomerization of xylenes over the SiO2-modified zeolites. Compared to the conventional HZSM-5 zeolite, the SiO2-containing zeolites considerably increased the selectivity and yield of p-xylene due to the reduction of external surface acidity and the narrowing of pore entrance. The influences of the methanol additive, reaction temperature, and types of polyols on the selectivity and yield of p-xylene were investigated in detail. Catalytic cracking of polyols with methanol significantly enhanced the production of p-xylene by the alkylation of toluene with methanol. The highest p-xylene yield of 10.9 C-mol% with a p-xylene/xylenes ratio of 91.1% was obtained over the 15wt%SiO2/HZSM-5 catalyst. The reaction pathway for the formation of p-xylene was addressed according to the study of the key reactions and the characterization of catalysts.

Effect of CO2 on oxidation of p-xylene in acetic acids/CO2

The oxidation of p-xylene to terephthalic acid with molecular oxygen in acetic acids modified carbon dioxide over Co/Mn/Br catalyst was studied in a batch reactor. The results showed that the oxidation of p-xylene to terephthalic acid was severely inhibited when carbon dioxide exceeded a certain amount, the conversion of p-xylene decreased rapidly from 100.0% to 3.3% and the yield of terephthalic acid dropped from 42.6% to trace. Whereas the oxidation processes of p-Tolualdchyde to p-Toluic acid and 4-Carboxybenzaldehyde to tcrcphthalic acid were improved when a relative small amount of CO2 v/as added, Further investigation found that this negative effect may be caused by multiphase reactions emerging.

High dimension feature extraction based visualized SOM fault diagnosis method and its application in p-xylene oxidation process

Purified terephthalic acid(PTA) is an important chemical raw material. P-xylene(PX) is transformed to terephthalic acid(TA) through oxidation process and TA is refined to produce PTA. The PX oxidation reaction is a complex process involving three-phase reaction of gas, liquid and solid. To monitor the process and to improve the product quality, as well as to visualize the fault type clearly, a fault diagnosis method based on selforganizing map(SOM) and high dimensional feature extraction method, local tangent space alignment(LTSA),is proposed. In this method, LTSA can reduce the dimension and keep the topology information simultaneously,and SOM distinguishes various states on the output map. Monitoring results of PX oxidation reaction process indicate that the LTSA–SOM can well detect and visualize the fault type.

Design and control of a p-xylene oxidation process

The p-xylene(PX) oxidation process is of great industrial importance because of the strong demand of the global polyester fiber.A steady-state model of the PX oxidation has been studied by many researchers.In our previous work,a novel industrial p-xylene oxidation reactor model using the free radical mechanism based kinetics has been developed.However,the disturbances such as production rate change,feed composition variability and reactor temperature changes widely exist in the industry process.In this paper,dynamic simulation of the PX oxidation reactor was designed by Aspen Dynamics and used to develop an effective plantwide control structure,which was capable of effectively handling the disturbances in the load and the temperature of the reactor.Step responses of the control structure to the disturbances were shown and served as the foundation of the smooth operation and advanced control strategy of this process in our future work.

Multi-objective optimization of p-xylene oxidation process using an improved self-adaptive differential evolution algorithm

The rise in the use of global polyester fiber contributed to strong demand of the Terephthalic acid （TPA）. The liquid-phase catalytic oxidation of p-xylene （PX） to TPA is regarded as a critical and efficient chemical process in industry [ 1 ]. PX oxidation reaction involves many complex side reactions, among which acetic acid combustion and PX combustion are the most important. As the target product of this oxidation process, the quality and yield of TPA are of great concern. However, the improvement of the qualified product yield can bring about the high energy consumption, which means that the economic objectives of this process cannot be achieved simulta- neously because the two objectives are in conflict with each other. In this paper, an improved self-adaptive multi-objective differential evolution algorithm was proposed to handle the multi-objective optimization prob- lems. The immune concept is introduced to the self-adaptive multi-objective differential evolution algorithm （SADE） to strengthen the local search ability and optimization accuracy. The proposed algorithm is successfully tested on several benchmark test problems, and the performance measures such as convergence and divergence metrics are calculated. Subsequently, the multi-objective optimization of an industrial PX oxidation process is carried out using the proposed immune self-adaptive multi-objective differential evolution algorithm （ISADE）. Optimization results indicate that application oflSADE can greatly improve the yield of TPA with low combustion loss without degenerating TA quality.

Synergistic Catalytic Action of Cobalt(Ⅱ) Hydroxamates and N-Hydroxyphthalimide in the Aerobic Oxidation of p-Xylene

The catalytic performance of a series of cobalt(Ⅱ) hydroxamates (CoL2) and the synergistic catalytic action of the cobalt complexes combined with N-hydroxyphthalimide (NHPI) in the aerobic oxidation of p-xylene to p-toluic acid (PTA) were investigated. The results showed that the existing synergistic action in the catalytic oxidation can shorten the induction period of the radical reaction and improve the yield of PTA.

Synthesis, characterization of triphenyltin grafted on SBA-15mesoporous silica and its catalytic performance for the synthesis of 4-methylacetophenone

The production of Ph3Sn–O–SBA-15(Ph3Sn SBA)was achieved by heating triphenyltin chloride and SBA-15in N-methylpyrrolidone at 190°C for 5 h using triethylamine as a catalyst.The composition,structure,and surface physical and chemical properties of Ph3Sn SBA were characterized using inductively coupled plasma-atomic emission spectroscopy(ICP-AES),13C,119Sn and29Si solid-state nuclear magnetic resonance(NMR)spectroscopy in situ pyridine infrared spectroscopy(Py-IR),N2adsorption–desorption isotherms,X-ray diffraction(XRD)and transmission electron microscopy(TEM).The results of ICP-AES and organic elemental analysis showed that the grafting yield of Sn was 17%(by mass)for Ph3Sn SBA.The elemental analysis and solid-state NMR results for Ph3Sn SBA were consistent with grafting of triphenyltin on SBA-15.The N2adsorption–desorption,XRD and TEM analyses showed that Ph3Sn SBA retained an ordered hexagonal mesoporous structure,resulting in decreases in the surface area,pore size and mesopore volume,and an increase in acidity as compared with SBA-15.The Hammett acidity function(H0)value and the number of acid sites for Ph3Sn SBA,obtained by the Hammett methods,were 2.77–3.30 and 2.07 mmol·g-1,respectively.The Friedel–Crafts acylation of toluene and acetic anhydride over Ph3Sn SBA was investigated.The yield of methylacetophenone(MAP)and the selectivity for 4-methylacetophenone(PMAP)were 79.56%and 97.12%,respectively,when the conditions were n(toluene):n(anhydride)=2.0:1.0 with 6%(by mass)catalyst,and heating under reflux for 5 h.The PMAP selectivity still reached 93.11%when Ph3Sn SBA was used for the fifth time under the same reaction conditions.

Solar Oxidation and Removal of Arsenic from Groundwater Utilizing a Semicircular Section Tubular Photoreactor

A semicircular section tubular photoreactor has been constructed, characterized and applied to the treatment of groundwater contaminated with As（V） by means of the SORAS （solar oxidation and removal of arsenic） technique, using ferrous and citrate salts. The solar concentrator was built with recyclable waste materials： glass tubes from fluorescent lamps and 6-inch diameter PVC pipes cut in half and covered by aluminum foil. The reactor concentrates solar radiation up to 2.8 times its natural intensity. Batch irradiation experiments followed by controlled agitation （shear rate = 30-33 s^-1; 20 min agitation period） showed that the photoreactor accelerates the formation of settleable floccules （Dp 〉 0.5mm）, compared with a fluorescent lamp glass tube alone and a 2 L PET （polyethylene terephthalate） bottle. Irradiation times necessary for floccule formation in the photoreactor, the fluorescent lamp tube and the PET bottle were 15 min, 25 min and 60 min, respectively. Continuous flow experiments using a photoreactor with a photo-collection area of 0.9 m^2 and a hydraulic retention time （equal to the irradiation time） of 15 rain showed that immediate formation of floccules of good settleability occurs when the solution is subjected to moderate agitation （33 s^-1）. An efficiency of 98.36% for As（V） removal was obtained with a final concentration of 16.5 ktg/L in decanted waters. In accordance to these results, the photoreactor is able to treat approximately 130 L/m^2 within a 5-h period with UVA irradiation intensities of 50-70 W/mE.

Photochemical Degradation of Phenols in Water Using Flavin-based Photosensitizers

A slightly modified method for 10-ethyl flavin was developed in the present study. The synthetic product was characterized by nuclear magnetic resonance(NMR) and mass spectrometry, and used to catalyze the photocatalytic degradation of phenol, 2, 4-dichlorophenoxyacetic acid, p-nitrophenol, 4-chlorophenol, 4-methoxyphenol, 4-chloro-2-methyl-phenoxyacetic acid and2, 4, 5-trichloro-phenoxyacetic acid. Both HPLC(high performance liquid chromatography) and GC-MS data suggested that all phenols were degraded in the presence of either flavin at micromolar concentrations under direct sun light. A rapid breakdown of the phenols was observed. The degradation efficiency was clearly dependent on phenol type. In a decreasing order of degradation efficiency over a 2-h period, the phenols were 4-chlorophenol and 4-methoxyphenol(-80%) > phenoxyacetic acids(60%-65%) > nitrophenol and phenol(-35%).

Synthesis and Crystal Structure ofDinitratedioxobis(p-methyl Phenyl Butyl Sulfoxide)Uranium(Ⅵ)[UO_2(p-CH_3C_6H_4SOC_4H_9)_2(NO_3)_2]

The title compound [UO2 （p-CH3C6H4SOC4H9）2 （NO3 ）2] is triclinicwith space group P1. a=8. 651 （3）, b=9. 097（2）, c=9. 621 （2） A;a=92. 29（1）, β=95. 97（3）, r=98. 25（3）, V=744. 1（3） A3, Z=1, Mr=786.41, Dc=1. 425 g/cm3. u=5. 626 mm-1, F （000） =300. R=0. 030, Rw=0. 071 for 2917 reflectionswith I≥2（I）. Uranyl ion is coordinated to six oxygen atoms, of which two are fromtwo monodenate sulfoxides and the others from two nitrate groups. The coordinationPOlyhedron around U is a hexagonal bipyramid, the U atom is in the center of symmetry.

A Hybrid Dielectric Ink Consisting of up to 50 wt% of TiO2 Nanoparticles in Polyvinyl Alcohol （PVA）

PVA （Polyvinyl Alcohol） is a water soluble organic dielectric, easily solution processed to fabricate films by spin coating, dip coating or inkjet printing. It has been used as a dielectric layer in OTFTs （organic thin film transistors）, and its dielectric constant is around 3.5-10. For OTFTs operating at lower voltage, it is desirable to increase the dielectric constant. Here, we report a technique to incorporate upto 50 wt% of TiO2 nanoparticles （15-25 nm） in PVA to increase its dielectric constant. Rutile phase of TiO2 is used, because of its higher dielectric constant （e = 114） compared to anatase phase （E = 31）. We have made inks containing 10 and 50 wt% （of PVA） TiO2 nanoparticles, which is stable upto six months. PVA-TiO2 dispersions and PVA （without TiO2） were spin coated on indium tin oxide coated polyethylene terephthalate substrate. Film structure was studied using SEM （scanning electron microscopy）. Absorption study of the films confirms presence of TiO2 nanoparticles. M-I-M capacitors were fabricated by thermally evaporating aluminium on top of the dielectric films. We observed enhancement in dielectric constant by a factor of 2 for PVA containing 50 wt% TiO2 in comparison to PVA＇s dielectric constant. There is no concomitant increase in the leakage current.

Efficient aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid on Ru/C catalysts

2,5-Furandicarboxylic(FDCA) is a potential substitute for petroleum-derived terephthalic acid, and aerobic oxidation of5-hydroxymethylfurfural(HMF) provides an efficient route to synthesis of FDCA. On an activated carbon supported ruthenium(Ru/C) catalyst(with 5 wt% Ru loading), HMF was readily oxidized to FDCA in a high yield of 97.3% at 383 K and 1.0 MPa O_2 in the presence of Mg(OH)_2 as base additive. Ru/C was superior to Pt/C and Pd/C and also other supported Ru catalysts with similar sizes of metal nanoparticles(1–2 nm). The Ru/C catalysts were stable and recyclable, and their efficiency in the formation of FDCA increased with Ru loadings examined in the range of 0.5 wt%–5.0 wt%. Based on the kinetic studies including the effects of reaction time, reaction temperature, O_2 pressure, on the oxidation of HMF to FDCA on Ru/C, it was confirmed that the oxidation of HMF to FDCA proceeds involving the primary oxidation of HMF to 2,5-diformylfuran(DFF) intermediate, and its sequential oxidation to 5-formyl-2-furancarboxylic acid(FFCA) and ultimately to FDCA, in which the oxidation of FFCA to FDCA is the rate-determining step and dictates the overall formation rate of FDCA. This study provides directions towards efficient synthesis of FDCA from HMF, for example, by designing novel catalysts more efficient for the involved oxidation step of FFCA to FDCA.