Molecular Dynamics Simulation on Characteristics of Decomposition of Methane Hydrate in the Presence of Hydrogen Peroxide Solution

In this work, the characteristics of the decomposition of methane hydrate Structure I (SI) in the presence of hydrogen peroxide solution is investigated using the molecular dynamics simulation. The mechanism of the transformation process from the solid hydrate to the liquid is analyzed with the effect of hydrogen peroxide (HP) solution. In addition, the effect of ethylene glycol (EG) with the same molar concentration with HP on the methane hydrate dissociation is also studied. The results illustrate that both HP and EG promote well the hydrate dissociation. The work provides the important reference value for the experimental investigation into the promotion effect of HP on the hydrate dissociation.

Synthesis Gas Generation by Chemical-Looping Reforming Using Ce-Based Oxygen Carriers Modified with Fe, Cu, and Mn Oxides

Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.

Production and characterization of biodiesel from tung oil

The feasibility of biodiesel production from tung oil was investigated. The esterification reaction of the free fatty acids of tung oil was performed using Amberlyst-15. Optimal molar ratio of methanol to oil was determined to be 7.5:1, and Amberlyst-15 was 20.8wt% of oil by response surface methodology. Under these reaction conditions, the acid value of tung oil was reduced to 0.72mg KOH/g. In the range of the molar equivalents of methanol to oil under 5, the esterification was strongly affected by the amount of methanol but not the catalyst. When the molar ratio of methanol to oil was 4.1:1 and Amberlyst-15 was 29.8wt% of the oil, the acid value decreased to 0.85mg KOH/g. After the transesterification reaction of pretreated tung oil, the purity of tung biodiesel was 90.2wt%. The high viscosity of crude tung oil decreased to 9.8mm(2)/s at 40 degrees C. Because of the presence of eleostearic acid, which is a main component of tung oil, the oxidation stability as determined by the Rancimat method was very low, 0.5h, but the cold filter plugging point, -11 degrees C, was good. The distillation process did not improve the fatty acid methyl ester content and the viscosity.

BIODIESEL PRODUCTION FROM DIFFERENT FEEDSTOCKS IN PILOT SCALE SYSTEM

In this study, the preparations of biodiesel from three different feedstocks, including rapeseed oil, high acidified Chinese wood oil and trap grease, were carried out in a pilot scale of 200 t yr(-1) biodiesel production system. The optimum operating conditions for transesterification of rapeseed oil in plug flow reactor were found to be as follows: the catalyst dosage is 1.2 wt%; the retention time is about 17 min; the bed temperature is 65 degrees C; the oil/methanol ratio is 1:6; the content of methyl ester is 96.33% under these conditions. A kind of ion exchange resin, a solid acid catalyst, filled in the fixed bed reactor was used as the esterification catalyst for the pretreating of high acidified oil. The acid value of Chinese wood oil could be reduced from 7 to 0.8 mg KOH.g(-1) after 88 min, the optimum operating conditions were obtained as follow: molar ratio of methanol to oil is about 6:1, the temperature of the fixed bed, 65 degrees C and the retention time, about 88 min. Also a kind of acidified oil, namely trap grease, with the acid value being 114 mg KOH.g(-1) could be equally converted to a good biodiesel product through this system. Generally, the refined biodiesel product generated through this system could meet China #0 Biodiesel Standard, as well as Germany Biodiesel Standard for most indexes. It indicates that the designed process in this system has a good adaptability for different kinds of oil.

Optimization of biodiesel production from trap grease via acid catalysis

As a kind of waste collected from restaurants, trap grease is a chemically challenging feedstock for biodiesel production for its high free fatty acid (FFA) content. A central composite design was used to evaluate the effect of methanol quantity, acid concentration and reaction time on the synthesis of biodiesel from the trap grease with 50% free fatty acid, while the reaction temperature was selected at 95 degrees C. Using response surface methodology, a quadratic polynomial equation was obtained for ester content by multiple regression analysis. Verification experiments confirmed the validity of the predicted model. To achieve the highest ester content of crude biodiesel (89.67%), the critical values of the three variables were 35.00 (methanol-to-oil molar ratio), 11.27 wt% (catalyst concentration based on trap grease) and 4.59 h (reaction time). The crude biodiesel could be purified by a second distillation to meet the requirement of biodiesel specification of Korea.

The role of CeO2-ZrO2 as support in the ZnO-ZnCr2O4 catalysts for autothermal reforming of methanol

Autothermal reforming of methanol for hydrogen production was investigated over ZnO-ZnCr2O4 supported on a series of metal oxides (Al2O3, CeO2, ZrO2 and CeO2-ZrO2)CeO2-ZrO2 mixed oxides with Ce /Zr molar ratio of 4/1 was found to be the optimal support which showed significant effect on the catalytic activity and selectivity. The ZnO-ZnCr2O4/CeO2-ZrO2 and ZnO-ZnCr2O4 catalysts were characterized by XRD, TEM, H-2-TPR and XPS. The results show that CeO2-ZrO2 mixed oxides have significant effect on the catalytic performance and the supported catalyst shows more uniform temperature distribution in the catalyst bed which was mainly due to its reasonable redox properties.

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO2 sol-gels with various Ag/TiO2 molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO2 thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO2 nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO2 sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO2 sol-gel, four types of the TiO2 thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO,), TA (bottom layer was pure TiO,, surface layer was Ag modified), TT (pure TiO, thin film) and AA (TiO, thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I-ph). LSV confirmed the existence of Ago state in the TiO, thin film. SEM and XRD experiments indicated that the sizes of the TiO,, nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO2 thin film.

Preparation and luminescence properties of Eu2+ in SiO2 xerogels

Al-doped and B, Al co-doped SiO2 xerogels with Eu2+ ions were prepared only by sol-gel reaction in air without reducing heat-treatment or post-doping. The luminescence characteristics and mechanism of europium doping SiO2 xerogels were studied as a function of the concentration of Al, B, the europium concentration and the host composition. The emission spectra of the Al-doped and B, Al codoped samples all show an efficient emission broad band in the blue violet range. The blue emission of the Al-doped sample was centered at 437 nm, whereas the B, Al co-doped xerogel emission maximum shifted to 423 nm and the intensity became weaker. Concentration quenching effect occurred in both the Al-doped and B, Al co-doped samples, which probably is the result of the transfer of the excitation energy from Eu2+ ions to defects. The highest Eu2+ emission intensity was observed for samples with the Si(OC2H5)(4):C2H5OH:H2O molar ratio of 1:2:4. (c) 2006 Elsevier B.V. All rights reserved.

METAL-ORGANIC CHEMICAL-VAPOR-DEPOSITION GROWTH OF GAN

Single-crystal GaN films have been deposited on (01 (1) over bar 2) sapphire substrates using trimethylgallium (TMGa) and NH3 as sources. The morphological, crystalline, electrical and optical characterizations of GaN film are investigated. The carrier concentration ofundoped GaN increases with decreasing input NH3-to-TMGa molar flow ratio.

Microorganisms linked to Neoproterozoic microspar carbonate sedimentation in the Jilin-Liaoning area

Molar-tooth carbonate refers to a sort of rock that has ptygmatical folded structure comparable to the ivory. This kind of carbonate exists in a special time range (from Middle to Neoproterozoic). Its origin and the possibility to use it in stratigraphic correlation of the paleocontinent is the key task of the IGCP447, a project on Proterozoic molar tooth carbonates and the evolution of the earth (2001-2005). The importance lies in that the molar-tooth structure is the key to solving problems related to Precambrian biological and global geochemical events. The molar-tooth structure is associated with microorganisms. Development and recession of such carbonates have relations with the evolution process of early lives and abrupt changes in sea carbonate geochemistry. In recent years, based on researches on petrology, geochemistry and Sr isotope of molar-tooth carbonate in the Jilin-Liaoning and Xuzhou-Huaiyang area, the authors hold that it can be used as a marker for stratigraphic sequence and sedimentary facies analyses.

Nano-size Effect of Interface Energy and Its Effect on Interface Fracture

An analytical model about size-dependent interface energy of metal/ceramic interfaces in nanoscale is developed by introducing both the chemical energy and the structure stain energy contributions. The dependence of interface energy on the interface thickness is determined by the melting enthalpy, the molar volume, and the shear modulus of two materials composing the interfaces, etc. The analytic prediction of the interface energy and the atomic scale simulation of the interface fracture strength are compared with each other for Ag/MgO and Ni/Al2O3 interfaces, the fracture strength of the interface with the lower chemical interface energy is found to be larger. The potential of Ag/MgO interface related to the interface energy is calculated, and the interface stress and the interface fracture strength are estimated further. The effect of the interface energy on the interface strength and the behind mechanism are discussed.

PEGylated Phospholipid Membrane on Polymer Cushion and Its Interaction with Cholesterol

By employing poly(ethylene glycol) (PEG) shielding and a polymer cushion to achieve air stability of the lipid membrane, we have analyzed PEG influence on dried membranes and the interaction with cholesterol. Small unilamellar vesicles (SUVs) formed by the mixture of 1,2-dimyristoylphosphatidylcholine (DMPC) with different molar fraction of 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(poly(ethylene glycol))-2000] (DSPE-PEG(2000)) adsorb and fuse into membranes on different polymer-modified silicon dioxide surfaces, including chitosan, poly(L-lysine) (PLL), and hyaluronic acid, Dried membranes arc further examined by ellipsometer and atomic force microscopy (AFM). Only chitosan can support a visible and uniform lipid array. The thickness of dry PEGylated lipid membrane is reduced gradually as the molar fraction of PEG increases. AFM scanning confirms the lipid membrane stacking for vesicles containing low PEG, and only a proper amount of PEG can maintain a single lipid hi lover; however, the air stability of the membrane will be destroyed if overloading. PEG. Cholesterol incorporation can greatly improve the structural stability of lipid membrane, especially for those containing high molar fraction of PEG. Different amounts of cholesterol influence the thickness and surface morphology of dried membrane.

钻井废水可生化性研究及处理技术探索

钻井废水是油气井开采钻探过程中产生的废水，钻井废水成分复杂，有机物浓度高、色度高、悬浮物浓度高，水质变化大，排放点分散，不经处理排放会污染环境，破坏生态。随着石油工业的不断发展和国家环保法律法规的日益严格，钻井废水的治理也越来越受到重视。如何采用经济有效的方法处理废弃钻井液，对油气井开采业的可持续发展具有重要意义。本论文以遂宁磨153 井的钻井废水为主要研究对象，在对废水进行絮凝沉降预处理和生物法处理探索的基础上，针对钻井废水可生化性差的特点，采用水解酸化和Fenton 试剂改善钻井废水的可生化性，对反应过程进行了比较详细的考察，对可生化性改善的机理进行了探索。主要研究结论如下：1 用PFS 和PAC 配制的混合混凝剂对钻井废水COD 的去除效果比较显著，在最佳条件下COD 的去除率可达75%，且絮体沉降速度较快，出水pH 保持中性；2 水解酸化法处理钻井废水可显著改善废水的可生化性。经48 小时水解酸化处理，钻井废水的理论BOD5可提高约22 倍，表观BOD5/COD值由0.004 提高到0.034。用接触氧化反应器处理经水解酸化处理后的废水，处理效果比较稳定，COD平均去除率达35.5%；3 研究了Fenton反应中各影响因子对废水COD去除率、BOD5/COD的影响并分析其作用机制，确定了最佳条件：初始pH为4.0，H2O2/Fe2+(摩尔浓度比)为20，H2O2/COD（质量浓度比）为1，反应时间为2 个小时。此条件下，废水的COD去除率约为40%，BOD5/COD值从0.002～0.003 提高至0.15～0.2，可生化性得到很大提高。本论文的主要创新点在于：1 以成分复杂、水质变化大的气井钻井废水为研究对象，从理论BOD 和表观BOD 两方面对水解酸化过程中废水可生化性的变化进行了分析；2 对Fenton 试剂改善钻井废水可生化性的过程、主要影响因素进行了比较详细的考察。本论文的研究成果，可为生物法处理钻井废水的深入研究提供理论依据。Drilling wastewater is produced in the process of oil-gas well drilling,because of its complicated composition, high concentrate of organic compound andsuspended solid, high chroma, levity of water quality and decentralization ofdischarge point, it pollutes environment seriously if discharged without treatment.With the development of petroleum industry and the issuing of more strict laws forenvironmental protection, it has been paid more and more attention on drillingwastewater treatment. It is of great importance for the sustainable development ofoil-gas well drilling to treat drilling wastewater by economical and effective methods.In this paper, drilling wastewater of Mo No.153 well in Suining was studied asthe main object. On the basis of research on pre-treatment with flocculant andbiological treatment, and according to the character of poor biodegradability, thedrilling wastewater was treated by hydrolytic acidification and Fenton’s reagent toimprove its biodegradability. The process and mechanism of biodegradabilitychanging were investigated. The primary conclusions are:1 It is effective to treat drilling wastewater with mixing PFS and PAC asflocculant. The removal rates of COD came up to 75% under optimal conditions, thesedimentation rate of flocculation is rapid, and the pH value of treated water remainedneutral;2 The biodegradability of drilling wastewater was highly improved afterhydrolytic acidification process. The theoretic BOD5 of drilling wastewater increasedby 22 times and its detected BOD5/COD ratio increased from 0.004 to 0.034 afterhydrolytic acidification for 48 hours. The wastewater after hydrolytic acidificationwas treated by biological contact oxidation reactor. Stable treatment performance was achieved, and the average removal rates of COD came up to 35.5%;3 The effects of various affection factors on the removal efficiency of COD andBOD5/COD radio in treating drilling wastewater by Fenton’s reagent wereinvestigated and the mechanism was analyzed. The optimal conditions were: initialpH of solution was 4.0, the molar ratio of H2O2 and Fe2+ was 20, the concentrationratio of H2O2 and COD was 1 and the reaction time was 120 min. Under the aboveconditions, the removal efficiency was about 40% and the ratio of BOD5 and CODincreased from 0.002 ¡« 0.003 to 0.15 ¡« 0.2. The biodegradability of drillingwastewater was greatly improved.The innovations of this thesis are:1 The drilling wastewater was taken as the research object which hascomplicated composition and variational water quality, and the changes ofbiodegradability were analyzed from theoretic BOD and detected BOD aspects duringhydrolytic acidification process;2 The biodegradability changing process and primary affection factors of drillingwastewater treating by Fenton’s reagent were investigated.The results of this study could provide theoretic foundation for further researchon biological treatment of drilling wastewater.

Ammonia-treated activated carbon as support of a Ru-Ba catalyst for ammonia synthesis

Ammonia-treated activated carbon has been studied as a support of Ru-Ba catalyst for ammonia synthesis. It is shown that the introduction of nitrogen leads to a decrease of ammonia synthesis activity for the catalysts with a low Ba/Ru molar ratio, while no significant changes are obtained for the catalysts with a high Ba/Ru molar ratio, confirming that electronegative impurities suppress the activity in ammonia synthesis and consume part of the promoters.