SAPO-34催化剂上甲醇制烯烃反应动力学

A kinetic model of MTO process over the SAPO-34 catalyst considering the effect of water and coke deposition has been proposed.The model takes into account three steps of the MTO reaction in which the products cover 5 lumped components.The water in the feed not only reduces the concentration of methanol but also alleviates the deactivation of SAPO-34 catalyst.The kinetic parameters have been estimated by the least square method.It has been proved that the calculated values in the kinetic model are in good agreement with the experimental values.     

A pH Model for Calculating the pH Value of Mixed–Acid–Base Equilibria of Overhead Condensing Systems in Crude Distillation

A pH predictive model based on acid–base equilibria and ion equilibria was proposed to calculate the pH value of the overhead condensing system of crude distillation unit. The pH model could be used to predict the appropriate amounts of neutralizers by measuring the Cl-ion concentration of the overhead knockout drum. The pH values of various neutralized streams were estimated by this model. The results showed that the predicted pH values were in good agreement with the experimental ones. The trend of the corrosion inhibition efficiency decreases in the following order: ethylenediamine N,Ndimethylethanolamine triethylamine 3-methoxypropylamine morpholine. The difficulty in the accurate control of corrosion was solved, and a good instruction was provided for mitigating corrosion in refinery.     

Non-Darcy flow in oil accumulation （oil displacing water） and relative permeability and oil saturation characteristics of low-permeability sandstones

Hydrocarbon resources in low-permeability sandstones are very abundant and are extensively distributed. Low-permeability reservoirs show several unique characteristics, including lack of a definite trap boundary or caprock, limited buoyancy effect, complex oil-gas-water distribution, without obvious oil-gas-water interfaces, and relatively low oil (gas) saturation. Based on the simulation experiments of oil accumulation in low-permeability sandstone (oil displacing water), we study the migration and accumulation characteristics of non-Darcy oil flow, and discuss the values and influencing factors of relative permeability which is a key parameter characterizing oil migration and accumulation in low-permeability sandstone. The results indicate that: 1) Oil migration (oil displacing water) in low-permeability sandstone shows non-Darcy percolation characteristics, and there is a threshold pressure gradient during oil migration and accumulation, which has a good negative correlation with permeability and apparent fluidity; 2) With decrease of permeability and apparent fluidity and increase of fluid viscosity, the percolation curve is closer to the pressure gradient axis and the threshold pressure gradient increases. When the apparent fl uidity is more than 1.0, the percolation curve shows modified Darcy flow characteristics, while when the apparent fluidity is less than 1.0, the percolation curve is a “concaveup” non-Darcy percolation curve; 3) Oil-water two-phase relative permeability is affected by core permeability, fluid viscosity, apparent fluidity, and injection drive force; 4) The oil saturation of low-permeability sandstone reservoirs is mostly within 35%-60%, and the oil saturation also has a good positive correlation with the permeability and apparent fluidity.     

Multistring analysis of wellhead movement and uncemented casing strength in offshore oil and gas wells

This paper presents a theoretical method and a finite element method to describe wellhead movement and uncemented casing strength in offshore oil and gas wells.Parameters considered in the theoretical method include operating load during drilling and completion and the temperature field,pressure field and the end effect of pressure during gas production.The finite element method for multistring analysis is developed to simulate random contact between casings.The relevant finite element analysis scheme is also presented according to the actual procedures of drilling,completion and gas production.Finally,field cases are presented and analyzed using the proposed methods.These are four offshore wells in the South China Sea.The calculated wellhead growths during gas production are compared with measured values.The results show that the wellhead subsides during drilling and completion and grows up during gas production.The theoretical and finite element solutions for wellhead growth are in good agreement with measured values and the deviations of calculation are within 10％.The maximum von Mises stress on the uncemented intermediate casing occurs during the running of the oil tube.The maximum von Mises stress on the uncemented production casing,calculated with the theoretical method occurs at removing the blow-out-preventer （BOP） while that calculated with the finite element method occurs at gas production.Finite element solutions for von Mises stress are recommended and the uncemented casings of four wells satisfy strength requirements.     

C-Nanostructures Cluster Models in Organic Solvents： Fullerenes,Tubes, Buds and Graphenes

The existence of nanographene in cluster form is discussed in organic solvents. Theories are developed based on the columnlet, bundlet and droplet models describing the size-distribution functions. Phenomena present a unified explanation in the columnlet model in which free energy of Cgraphene involved in cluster is combined from a volume part proportional to the number of molecules n in cluster and a constant. The columnlet model enables describing distribution function of Cgraphene clusters by size. From purely geometrical considerations the columnlet （Cgraphene）, bundlet （single-wall carbon nanotube）, CNT （carbon nanotube）, SWNT （single-wall C-nanotube）, and carbon nanobud, CNB （carbon nanobud）） and droplet （fullerene） models predict dissimilar behaviours. The interaction-energy parameters of Cgraphene are taken from C60. An CNB behaviour or further is expected. The decay of solubility with rising temperature is smaller for Cgraphene than for SWNT and CNB and, furthermore, than for C60, in agreement with lesser numbers of units in Cgraphene clusters. The discrepancy between the experimental data of the heat of solution of fullerenes, CNTs, CNBs and graphenes is ascribed to the sharp concentration dependence of the heat of solution. The diffusion coefficient drops with temperature result greater for Cgraphene than CNB and SWNT than C60 corresponding to lesser number of units in clusters. The aggregates near （C60）13, SWNT/CNB7 and （Cgraphene）3 could be representative of the droplet, bundlet and columnlet models.     

Assessment of the Total Organic Carbon and Conductivity in Consecutive Dyeings with Reactive Dyestuffs Using Treated Effluent by UV/H202 Photocatalysis

The paper was monitored the conductivity （g.L＂l of NaCI）, the absorbances values （Abs） and the amount of TOC （total organic carbon）, before and after five consecutive dyeings made with reuse water, obtained from treated effluent by UV/H202 photocatalysis. All rates of decolorization were above 92%, the removal of total organic carbon was above 89% in all treatments and the economy of NaCI was from 3.10 in the first recipe, 3.17 in the second, 3.49 in the third, 3.79 in the fourth and 4.05 in the fifth recipe. The five dyeings compared with same dyeings made with deionized water presented a color deviation （AE＊） below 1. The conventional dyeings would consume 80 L/kg against 40 L/kg used in the dyeing process proposed in this study, representing a great economy of water, with no discharge of effluents.     

Study on Tribological Behaviors of Boron-Nitrogen Modified Fatty Acid as Water-Based Lube Additives

A new type of boron - nitrogen modified fatty acid as water base lube additive was prepared and the chemical structure characterized by infrared spectrum. The tribological properties of the additive in water were evaluated by friction testers. The morphographies and tribochemical species of the worn surfaces were analyzed by means of X - ray Photoelectron Spectroscope （XPS）.The results showed that the additive is excellent in increasing load - carrying capacity, anti - wear and friction - reducing abilities of water. The lubrication mechanism is inferred that a high strength adsorption film and a tribochemical reaction film are formed on the rubbing surfaces due to the carder effect of the long chain fatty acid molecules, high reaction activities of nitrogen, electron - deficient orbit of boron and their synergisms.     

Defluorination of Wet-Phosphoric Acid： Equilibrium and Kinetic Studies

This study describes the advantages of using iron-oxide-pillared MF （montmorillonite） and EDTA （ethylenediaminetetraacetic acid）-pillared MD （montmorillonite） for the removal of fluoride in the phosphoric acid. The MF and MD were characterized by using BET （Brunauer-Emmett-Teller） and SEM （scanning electron microscope） for there to appreciate their textural and structural properties and in order to appraise their capacity in the fixation of the fluorine experimental results of fluorine adsorption show a defluoration of the phosphoric acid passing beyond 90% with both clays with a light performance for the MD. The kinetics of fluorine adsorption on MF and on MD has been measured at different temperatures. Indeed, the adsorbed quantity increases more favorably to temperatures more high. This kinetics could be described by two models： pseudo-first-order or pseudo-second-order, which depends on temperature and the nature of adsorbent. At different temperatures used and with various adsorbents （MD and MF, the pseudo second order model was the most reliable to determine the order of kinetics of adsorption of fluorine, which is also reflected a good correlation coefficient （above 0.99）. The fluoride sorption was reasonably explained with Langmuir or Freundlich isotherms. Thermodynamic parameters such as AG~, AH~, AS~ and kinetic one E,, （apparent activation energy） were calculated in order to understand the nature of sorption process. Results indicate that the mechanism of adsorption of the ion of fluoride on the pillared montmorillonite is an exothermic reaction. During equilibrium conditions, both the systems showed negative Gibbs energy, which indicates stability of system. The values of apparent activation energy for the both clays show that the adsorption of F ions is easier on the MF.     

Manifestation If Substance Molecular Structure in Temperature Effects of Light Scattering

DCMSL （depolarization components of molecular scattering of light） have been studied within the wide spectral range （0-200 cm-1） and in the temperature intervals （20-200 ℃） in toluol （C6HsCH3） and aniline （C6HsNH2）. It has been shown that when a liquid is heated and temperatures approach to critical ones, a significant contribution of DCMSL is made by vibration motion of molecules. The special properties of the temperature-frequency behavior of DCMSL spectra are discussed from the view point of hindered rotation of liquid molecules with consideration of intermolecular interaction.     

Syntheses of Coumarins in Environmentally Friendly Ionics Liquids

Syntheses of 3-substituted coumarins by the condensation reaction of salicylaldehyde with activated methylene compounds （ethyl cyanoacetate, malonic acid） are discussed in media of ionic liquids--（2-hydroxyethyl）ammonium carboxylates （formates, acetates, lactates） without utilization of any other catalysts. The dependence of yields of the reaction product is investigated on the structure of ionic liquids （their cations, anions, total polarity and pseudo-pH values）. 3-Substituted coumarins are prepared in high yields in media of these environmentally friendly ionic liquids which serve simultaneously as reaction media and as catalysts. The mentioned ionic liquids are prepared by reactions of corresponding hydroxyethyl-amines with carboxylic acids, and their quantitative analyses being made by potentiometric titration of ionic liquids with perchloric acid in 100% acetic acid.     

Formation of fine crystalline dolomites in lacustrine carbonates of the Eocene Sikou Depression,Bohai Bay Basin,East China

The genesis of the fine crystalline dolomites that exhibit good to excellent reservoir properties in the upper fourth member of the Eocene Shahejie Formation(Es_4~s)around the Sikou Sag, Bohai Bay Basin, is uncertain. This paper investigates the formation mechanisms of this fine crystalline dolomite using XRD, SEM, thin section analysis and geochemical data. The stratigraphy of the Sikou lacustrine carbonate is dominated by the repetition of metre-scale, high-frequency deposition cycles, and the amount of dolomite within a cycle increases upward from the cycle bottom. These dolomite crystals are 2–30 μm in length, subhedral to anhedral in shape and typically replace both grains and matrix. They also occur as rim cement and have thin lamellae within ooid cortices. Textural relations indicate that the dolomite predates equant sparry calcite cement and coarse calcite cement. The Sr concentrations of dolomites range from 900 to 1200 ppm. Dolomite δ~(18)O values(-11.3 to-8.2 ‰ PDB) are depleted relative to calcite mudstone(-8.3 to-5.4 ‰ PDB) that precipitated from lake water, while δ~(13)C values(0.06–1.74 ‰ PDB) are within the normal range of calcite mudstone values(-2.13 to 1.99 ‰ PDB). High~(87)Sr/~(86)Sr values(0.710210–0.710844) indicate that amounts of Ca~(2+) and Mg~(2+)have been derived from the chemical weathering of Palaeozoic carbonate bedrocks. The high strontium concentration indicates that hypersaline conditions were maintainedduring the formation of the dolomites and that the dolomites were formed by the replacement of precursor calcite or by direct precipitation.     

Studies on the Authenticity of Local Wines by Spectroscopic and Chemometric Analysis

The authenticity of 91 wines produced in Cyprus from both indigenous and other vine varieties were investigated by a holistic approach, using, advanced technology such as SNIF-NMR （site-specific natural isotopic fractionation-nuclear magnetic resonance） and 1R-MS （isotope ratio-mass spectrometry） for the determination of the stable isotopes and ICP （inductively coupled plasma spectroscopy） for some heavy metals. The spectroscopic characteristics were evaluated statistically using different chemometric methods. The dependency of the D/H （deuterium/hydrogen） ratio of the methylene site in the ethanol molecule （D/H）ll and also theδ ^18O values of the wine water, were the most useful discriminators. Isotopic results allow us to have a complete idea about the regional variability of the isotopes. Among the metals, Ni followed by Pb was the ones with the highest discrimination value. The determined concentrations of Pb, Ni, Cr and Cd that are related to the safety of wines were within the acceptable limits that have been established by the OIV （international organization of vine and wine） or comparable with the results of the wines of other European countries. The study of the correlation between the load of heavy metals and isotopes in wines showed a dependence on the grape variety but not the geographical location of the vineyard. This is probably due to the close proximity of wine regions in Cyprus.     

Corrosion behaviour of 6061 Al-15vol. Pct. SiC composite and its base alloy in sulphuric acid medium

In this paper the corrosion characteristics of Silicon carbide particulate-reinforced 6061 aluminum composite （ 6061 AI/SiCp composite ） and the base alloy are experimentally assessed. The corrosion tests are carried out at different temperatures in the concentration range of 0.01N to 1N sulphuric acid as corrosion media using Tafel extrapolation technique and Electrochemical Impedance Spectroscopy （EIS）. The results obtained from Tafel extrapolation technique and Electrochemical Impedance Spectroscopy are in good agreement. The results show an increase in the corrosion rate with increase in temperature as well as with increase in the concentration of the corrosion media. The thermodynamic parameters like energy of activation are calculated using Arrhenius theory equation and, enthalpy of activation and entropy of activation are calculated using transition state theory equation.     

Prognostication of Wood Properties Alteration with Modification and Impregnation

The effects of wood roughness, modification and sanding on the water contact angle values of pine spruce and aspen wood surfaces were evaluated. Contact angle values set by time linear part extrapolation give increased values in comparison with ones obtained after water drop spreading on the surface. Water drop side-view contact angle along wood fiber directions is less influenced by surface roughness. Wood water activity （aw） can be used to ascertain available water content on surface.     

Water Quality Monitoring of the Bezerra River （Cascavel,Brazil） Using SR-TXRF Technique

The present study aims to monitor and assess the water quality of the Bezerra River located in the Western Brazilian Parana state. For the monitoring of river waters, six samplings were established per month during one year. As indicators of the water quality, physico-chemical parameters such as water temperature, pH, turbidity, dissolved oxygen and COD （chemical oxygen demand） were chosen, as well as trace and majority element concentrations. It is noteworthy that the mean annual values of conductivity, turbidity and COD have progressively increased along the river with maximum values after the Cascavel western sewage treatment plant. Only 13 elements were found in the six collection points, but the metallic elements Cr, Mn, Fe, Cu and Zn have shown concentrations above the maximum limits recommended by Brazilian environmental legislation, suggesting the presence of highly polluting anthropogenic sources. Correlation analyses were used to determine the spatio-variability of water quality variables. The six collection sites were grouped into two clusters, with the element composition in the first cluster （sites 1, 2 and 6） being due to strong anthropogenic activities. The study of the Bezerra River water quality could help to develop municipal environmental policies and help with the management of water conservation in the Bezerra River basin.     

New Environmental Friendly Yellow Ceramic Pigments of the Type （Fe^ⅢM^Ⅴ）-TiO2

The family of Cr（Ⅲ） and Fe（Ⅲ）-doped rutile pigments of nominal composition （M^ⅢM^V）xTi1-2xO2, with M^Ⅲ = Cr（Ⅲ） or Fe（Ⅲ） and M＇（V） = Sb, Nb, Ta, with x = 0.03, 0.15 and 0.25 were investigated as ceramic pigments covering the yellow-ochre-brown palette. The formulations containing Fe（Ⅲ） are novel compositions not included in the commercial rutile pigments. The materials were characterized by XRD （X-ray diffraction） analysis and FTIR （Fourier transformed infrared spectroscopy）. The transition temperature from anatase-to-rutile was estimated by the evolution of the spectral patterns. This crystal phase transition is responsible of the color formation. A higher distortion of TiO6 octahedra is observed in the case of （FeSb） containing cells which contribute to the enhancement of the light absorption. The coloring performance of all the formulations were evaluated by enameling the mixtures containing 5% pigments and commercial frits representative of single and double firing industrial processes. The chromatic values obtained are in the yellow to brown domain of the chromatic plot, depending on the composition of the pigment-frit batch. In the case of the Fe-glazes, and particularly the combination （FeNb）, the chromatic values are close to the best yellow tinting. This new FeNb-rutile pigment could be a more benign substitute of Cr-yellow pigments. The homogeneity of the enamels was confirmed by SEM （scanning electron microscopy）-EDAX （energy dispersive X-ray analysis） microscopy.     

Proficiency Testing in Analysis of Wine Products

The quality variety wines which are produced in specified regions of Slovakia are mostly watched category of wine in European Union. Quality of the measurement for appropriate parameter in wine sample is given by uncertainty. Therefore, protocol of analysis has to have an uncertainty of measurement and should be made in accredited laboratory. In Slovakia, there are six wine growing regions （Tokaj, east Slovakia region, south Slovakia region, middle Slovakia region, Nitriansky region and Little-Carpathian region） where the quality wines with protected designation of origin are produced. Central Controlling and Testing Institute in Agriculture in Bratislava is a state organization, which has an accredited laboratory for testing wine products before introduction into the market. This article presents the results of the authors＇ measurements in proficiency testing FAPAS （food analysis performance assessment scheme） which were organized by Central Science Laboratory in York （England） in 2011. The authors add also interlaboratory comparison in 2012 between Slovak accredited laboratories. The results show very good agreement. Quality control in the wine sector presents very important feature in the market, therefore, using certified reference materials and checking the accredited laboratories with interlaboratory comparisons is very helpful. Testing of wine in the authors＇ laboratory is performed by EN ISO/IEC： 17025. The results show that z-score lies not outside the range ±2 and this is a chance that the authors＇ results are actually acceptable.     

Representation of phase behavior of associating fluids using EOS

Associating fluids containing water and alkanols show a strong non-ideal behaviour on thermodynamic properties Simple cubic equations of state （EOS）. such as the Peng-Robinson （PR） equation, with conventional mixing rules are popular lbr its simplicity and eas3＇ implementation. However it is incapable of reliably representing the phase behaviour of associating mixtures. An effort has been made in this study to develop a new model in which the non-densit3＇-dependent mixing rules are applied to the PR EOS to represent the phase behaviour of associating fluids. The proposed model takes into account of the polarity in the attractive term of the EOS by including both the conventional random mixing term and the asymmetric interaction term. The proposed model has been successfully applied to the calculation of the vapor-liquid equilibrium （VLE） and liquid-liquid equilibrium （LLE） of fluids containing water, alkanols, acid gases, and hydrocarbons. A satisfactory agreement between the predictions of the proposed model and the experimental data in the literature is reached.     

Burial and thermal maturity modeling of the Middle Cretaceous–Early Miocene petroleum system, Iranian sector of the Persian Gulf

The Cretaceous Kazhdumi and Gurpi formations, Ahmadi Member of the Sarvak Formation, and Paleogene Pabdeh Formation are important source rock candidates of the Middle Cretaceous–Early Miocene petroleum system in the Persian Gulf. This study characterizes generation potential, type of organic matter, and thermal maturity of 262 cutting samples(marls and argillaceous limestones) from these rock units taken from 16 fields in the Iranian sector of the Persian Gulf. In addition, the burial and thermal histories of these source rocks were analyzed by one-dimensional basin modeling. Based on the total organic carbon and genetic potential values, fair hydrocarbon generation potential is suggested for the studied samples. Based on T max and vitrinite reflectance values, the studied samples are thermally immature to mature for hydrocarbon generation. The generated models indicate that studied source rocks are immature in central wells. The Gurpi and Pabdeh formations are immature and the Ahmadi Member and Kazhdumi Formation are early mature in the western wells. The Pabdeh Formation is within the main oil window and other source rocks are at the late oil window in the eastern wells. The hydrocarbon expulsion from the source rocks began after deposition of related caprocks which ensures entrapment and preservation of migrated hydrocarbon.     

Study on Novel HIGEE Technology for Synthesis of Overbased Petroleum Sulfonate Detergent

An innovative idea was proposed to prepare the overbased nano-sized calcium carbonate-calcium petroleum sulfonate in-situ the HIGEE reactor. The test sample prepared by this technology could meet the requirement of the industry standard SH0042-91 for the first-grade product on a par with similar overseas product. The test results obtained upon observation under microscope after freezing etching of specimen revealed that the crystal size of colloidal calcium sulfonate was in the range of 10-30 nm with an average size of 20 nm. The size of the detergent additive was uniform with good transmittance and fluidity. The HIGEE technology possesses five specific features as shown below: Firstly, the carbonation reaction is completed in one step with the reaction time reduced by more than 50% as compared to traditional batch reactor process along with enhanced reaction efficiency, good operability of the process and stabilized product quality. Secondly, ammonia emitted from the reaction is used as the co- promoter without the need for adding ammonia and water as promoters to simplify the promoter system along with effective and strong coupling of reactions. Thirdly, the utilization rate of Ca(OH)2 and CO2 is increased by 15% and 30%, respectively, with product yield increased by 15%, and calcium residue decreased by 65%. Fourthly, the HIGEE technology is environmental benign because of gasoline is used in this technology instead of toxic toluene and xylene. Fifthly, the dimension of HIGEE reactor is reduced by above two-thirds. The success in development of this new technology will offer new ideas and technology platform for the synthesis of metal detergent additive to lubricating oils in China.