0℃以下含SDS的甲烷水合物生成方式及过程对其分解速率的影响

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.     

Synthesis of nearly spherical AlN particles by an in-situ nitriding combustion route

Spherical AlN powders with micrometer size have attracted great attention owing to their good fluidity and dispersity. However, the industrial preparation methods usually require high temperature and long soaking time, which lead to the high cost and limit the wide application of the products. Herein, nearly spherical AlN particles with the average size of 2.5 μm were successfully synthesized via an in-situ combustion synthesis method. The effect of N₂ pressure, NH₄Cl content, and Al particle size on the combustion reaction procedure, phase composition, and microstructure of the products was systematically investigated. The results showed that the decreased N₂ pressure, increased NH₄Cl content, and Al particle size led to the decreasing of combustion temperature and speed, which further affected the morphology of the products. As a result, low N₂ pressure(0.2 MPa), a small amount of NH4Cl(0.5 wt%), and fine Al particles(~2.5 μm) contributed to a moderate combustion temperature and facilitated the formation of nearly spherical AlN particles. In addition, based on the gas-releasing assisted quenching experiments and thermo-kinetic analysis, a two-step growth mechanism for the nearly spherical AlN particles was rationally proposed. The present method shows the advantages of low cost and high efficiency for preparing nearly spherical AlN particles, which can be used as raw materials for electronic substrates and fillers for packaging materials.     

Thermodynamic analysis of steam reforming of glycerol for hydrogen production at atmospheric pressure

Thermodynamic chemical equilibrium analysis of steam reforming of glycerol(SRG)for selective hydrogen production was performed based on the Gibbs free energy minimisation method.The ideal SRG reaction(C₃H₈O₃+3H₂O→3CO₂+7H₂)and a comprehensive set of side reactions during SRG are considered for the formation of a wide range of products.Specifically,this work focused on the analysis of formation of H₂,CO₂,CO and CH4 in the gas phase and determination of the carbon free region in SRG under the conditions at atmospheric pressure,600 K–1100 K and 1.013×10⁵–1.013×10⁶ Pa with the steam-to-glycerol feed ratios(SGFR)of 1:5–10.The reaction conditions which favoured SRG for H₂ production with minimum coke formation were identifies as:atmospheric pressure,temperatures of 900 K–1050 K and SGFR of 10:1.The influence of using the inert carrier gas(i.e.,N₂)in SRG was studied as well at atmospheric pressure.Although the presence of N₂ in the stream decreased the partial pressure of reactants,it was beneficial to improve the equilibrium yield of H₂.Under both conditions of SRG(with/without inert gas),the CH4 production is minimised,and carbon formation was thermodynamically unfavoured at steam rich conditions of SGFR>5:1.     

Intrinsic kinetics and external diffusion of catalytic steam gasification of fine coal char particles under pressurized and fluidized conditions

Catalytic steam gasification of fine coal char particles was carried out using a self-made laboratory reactor to determine the intrinsic kinetics and external diffusion under varying pressures (0.1-0.5 MPa) and superficial gas flow velocities (GF Vs) of 13.8- 68.8 cm· s^-1. In order to estimate the in-situ gas release rate at a low GFV, the transported effect of effluent gas on the temporal gasification rate pattern was simulated by the Fluent computation and verified experimentally. The external mass transfer coefficients(kmam) and the effectiveness factors were determined at lower GF Vs, based on the intrinsic gasification rate obtained at a high GFV of 55.0 cm·s^-1. The kmamwas found to be almost invariable in a wider carbon conversion of 0.2-0.7. The variations of kmam at a median carbon conversion with GFV, temperature and pressure were found to follow a modified Chilton-Colburn correlation:Sh=0.311Re^2.83Sc1/3(P/P0)^-2.07 (0.04相似文献   

CO2压缩与卸压速率对微生物生理的影响

The influence of compression and decompression rates of carbon dioxide on the physiology of Absidia coerulea and Saccharomyces cerevisiae was investigated. Besides parameters such as pressure, temperature, exposure time, water content, and initial pH, the influence of either compression or decompression rate on the biological behavior of microorganisms was quite essential. For both microorganisms studied, an optimal rate for either compression or decompression process exists due to the integrated effect of pressure, exposure time as well as compression or decompression speed. The decompression rate has no significant effect on cell‘s viability after 180 min exposure in compressed CO2 because almost all the microorganisms were died before decompression.     

Synthesis of Si_3N_4 Powder Using Sawdust as Carbon Source

Si_3N_4 powder was synthesized by carbothermal reduction nitridation reaction using sawdust as carbon source and introducing SiO_2 by silica sol immersion.Effects of Si O2 content of silica sol,molding pressure,reaction temperature,reaction duration,and N_2 flow rate on phase compositions and microstructure of resultants were studied. The results show that using7. 5 mass% SiO_2 containing silica sol immersed sawdust as raw materials,the prepared Si3N4 powder is featured with high α-Si_3N_4 content,few impurities,etc. in the conditions of 1 450 ℃ of reaction temperature,9h of reaction duration,400 m L·min- 1of N_2 flow rate and 10 MPa of molding pressure.     

Preparation of Aluminium Oxynitride by Carbothermal Reduction of Aluminium Oxide in a Flowing N2 Atmosphere

Carbothermal reduction of alumina into aluminium oxynitride(AlON) spinel in a flowing nitrogen atmosphere was studied.The effects of Al2O3/C ratio temperature,soaking time,heating rate molding pressure of samples,and nitrogen flow rate on reactions were investigated.Then the stability of AlON was elucidated and AlON wa confirmed as an intermediate compound in reduction of alumina.     

Interactive Oxidation of Photocatalysis and Electrocatalysis for Degradation of Phenol in a Photoreactor

TiO2/C particles as photocatalyst were prepared by dipping TiO2 suspension solution with activated carbon and were applied in the photocatalytic-electrocatalytic degradation of phenol, the Ti/SnO2+Sb2O3/PbO2 electrode and oxygen diffusion electrode were used as anode and cathode respectively, and a 250 W ultraviolet lamp (365 nm) as side light source. The SEM results of TiO2/C and Ti/SnO2+Sb2O3/PbO2 anode indicated that the TiO2 on carbon particles was uniform and PbO2 film on the surface of anode was in cauliflower form, the XRD result of oxygen diffusion electrode showed that only crystalline graphite was found. The influential parameters of degradation process such as applied cell voltage (E), initial concentration of phenol (C0), amount of TiO2 catalyst and air flow rate (v) were discussed. Under the following experimental conditions of C0=50 mg/L, pH=6, E=2 V, TiO2 0.98 mg/mL, v=382.2 mL/min, and light intensity I=10.5 mW/cm2, phenol could be entirely degraded, and about 89% of total organic carbon (TOC) was removed after 3 h degradation.     

碘硫循环中硫酸相与氢碘酸相的纯化过程

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.     

Solubility of the silver nitrate in supercritical carbon dioxide with ethanol and ethylene glycol as double cosolvents: Experimental determination and correlation

Solubility of the silver nitrate in the supercritical carbon dioxide containing ethanol and ethylene glycol as double cosolvents was measured under certain pressure and temperature range(10–25 MPa, 323.15–333.15 K). The impact of the pressure and temperature on the solubility was also investigated. Based on the experiment data,a correlation model concerning solid's solubility in supercritical fluids was established by combining the solubility parameter with the thermodynamic equation when a binary interaction parameter and a mixed solvent solubility parameter were defined. Experiments show the solubility of AgNO_3 increases with the pressure at a certain temperature. However, the influence of temperature is related to a pressure defined as the turnover pressure(12.3 MPa). When the pressure is higher(or lower) than this turnover pressure, silver nitrate's solubility shows increasing(or decreasing) trend as the temperature rises. Satisfactory accuracy of our presented model was revealed by comparing experimental data with calculated results.     

葡萄糖的含量对LiFePO_4性能的影响

以葡萄糖为表面活性剂,采用水热法制备LiFePO4正极材料,并且考察了葡萄糖加入量对LiFePO4正极材料性能的影响。用XRD、SEM及电池测试系统对LiFePO4材料进行了研究。结果表明:葡萄糖不仅能够有效的对颗粒进行分散;而且还能够在高温高压下,裂解为碳,提高了材料的比容量;当葡萄糖含量为4%时在0.1C倍率下放电容量达到129.7mAh/g,体现良好的倍率放电特性。     

PVA析出法包覆LiFePO4正极材料的研究

利用聚乙烯醇(PVA)在水和乙醇中溶解度的不同使PVA均匀析出,可同时使PVA和超细导电碳(SP)均匀包覆在水热合成的LiFePO4表面。该方法不仅在LiFePO4颗粒之间形成三维网状碳结构,而且在LiFePO4颗粒表面形成均匀的无定形碳包覆层。碳包覆后的磷酸铁锂0.2 C首次放电容量由120 mAh/g提高到140 mAh/g,5 C放电容量由10 mAh/g提高到100 mAh/g。     

碳源对碳热法制备LiFePO4/C复合电极材料性能的影响

以廉价的Fe2O3为铁源,(NH4)H2PO4为磷源,Li2CO3为锂源,分别以乙炔黑、葡萄糖、PEG6000为还原剂和碳源,采用碳热还原法制备了LiFePO4/C复合材料。X射线衍射(XRD)分析表明用三种碳源都合成了橄榄石结构的LiFePO4。扫描电子显微镜(SEM)分析显示,以PEG6000为碳源合成的LiFePO4/C复合材料粒径较小,较均匀,且有较好的碳包覆。以充放电曲线、循环性能和交流阻抗等测试研究了材料的电化学性能,结果表明,以PEG6000为碳源合成的材料的电化学性能较好,0.1C、1C下首次放点比容量分别为144.7 mAh/g、132 mAh/g。     

Ag、C共包覆对LiFePO_4材料电化学性能的影响

采用葡萄糖还原法在固相法制备的LiFePO4基础上合成了Ag包覆的LiFePO4/Ag材料;同时采用一步法合成了碳银共包覆的LiFePO4/(Ag+C)材料。结果表明,Ag包覆将LiFePO4材料的首次放电容量由80mAhg-1提高到121mAhg-1;而碳银共修饰的LiFePO4/(Ag+C)材料具有更高的放电容量(132mAhg-1),并且具有更好的循环性能。此外,Ag包覆也大幅度降低了材料的电阻,电极的电荷转移电阻由253.5Ω降低到了54.8Ω。     

有机碳源包覆磷酸铁锂正极材料改性研究

以Fe2O3为Fe源、LiH2PO4为Li源和P源、分别以聚乙烯醇(PVA)、淀粉、柠檬酸为碳源,采用液相分散混合、雾化造粒及高温固相处理工艺制备得到碳包覆的磷酸铁锂正极材料(LiFePO4/C),考察不同有机碳源包覆改性对磷酸铁锂正极材料物理及电化学性能的影响。结果表明:以聚乙烯醇包覆制备的LiFePO4/C材料的首次放电比容量为153.8 mAh/g,首次效率大于90%,材料物相纯正,颗粒呈类球形均匀分布、无团聚现象;淀粉包覆的样品的比容量稍低,为144.4 mAh/g,柠檬酸包覆的产物的比容量最低,为139.4 mAh/g。     

超临界水快速连续制备纳米磷酸铁锂正极材料

建立了超临界水快速连续合成磷酸铁锂纳米颗粒的工艺。研究了反应物浓度、反应温度和反应压力等因素对磷酸铁锂颗粒的大小、结晶度和形貌的影响并解释了相关机理,采用扫描电镜（SEM）、动态光散射（DLS）粒度分析和X射线衍射（XRD）等手段表征了目标产物的颗粒大小、形貌和结晶度。结果表明,在所研究的过程参数范围内,均获得了纳米尺度的磷酸铁锂。在超临界范围内,提高反应温度会使颗粒尺寸变大,但粒度分布更加均匀;预热温度对磷酸铁锂的结晶度有明显的影响,升高预热温度有利于提高磷酸铁锂纳米颗粒的结晶度;较高的反应压力、较低的反应物浓度有利于得到更小的纳米颗粒。在反应温度为380 ℃、预热温度为405 ℃、反应压力为27 MPa、二价铁离子浓度为0.015 mol/L条件下,获得了平均粒度为105 nm的高结晶度、橄榄石状的球形磷酸铁锂颗粒。     

铜掺杂碳包覆磷酸铁锂的微波合成及性能研究

研究了铜掺杂碳包覆磷酸铁锂（LiFePO₄）的微波合成。通过X射线衍射（XRD）表征了样品的化学组成和晶体结构,通过扫描电镜（SEM）考察了样品的微观形貌。分别用铜掺杂磷酸铁锂、碳包覆磷酸铁锂、铜掺杂碳包覆磷酸铁锂作为锂离子电池正极材料,进行了电化学性能测试比较。充放电测试表明,微波合成的铜掺杂碳包覆磷酸铁锂具有良好的充放电性能和循环寿命,首次放电比容量达到145 mA•h/g,循环30次后比容量仍然有143.5 mA•h/g,为初始容量的98.96%,容量几乎无衰减。     

前驱体FePO_4的制备工艺及其对流变相法合成LiFePO_4/C正极材料的影响

以FeSO4·7H2O,NH4H2PO4,H2O2和NH3·H2O为原料,采用均相沉淀法制备前驱体FePO4·2H2O,再通过流变相法制得LiFePO4/C复合材料,研究了反应温度、搅拌速度和pH值等反应条件对合成LiFePO4/C的影响。采用XRD、SEM和恒流充放电方法表征了材料的结构、形貌和电化学性能。结果表明:当反应温度为60℃,搅拌速度为800 r/min,pH值为2.5时,合成的LiFePO4/C为纯相,且粒度均匀,粒径约为200 nm,在0.1 C充放电倍率下,其首次放电比容量达137 mAh/g。     

Ni-Rh/Al2O3催化剂上甲烷-氘化氢间的氢氘交换性能

采用Ni-Rh/Al₂O₃催化剂,在固定床微型反应器上考察了Ni-Rh/Al₂O₃催化剂对甲烷的氢氘交换的催化性能。结果表明,在进料组成不变的条件下,当温度低于692K时,甲烷的转化率随温度的升高而快速升高,当温度高于692K时,甲烷的转化率不随温度的升高而变化;当温度低于692K时,甲烷的转化率随反应物流量的增加而明显减小,当温度高于692K时,甲烷的转化率基本不随温度和反应物流量的变化而变化;在反应物总流量不变的条件下,当HD/CH₄流量比为1.1～2.5时,甲烷的转化率随着HD/CH₄流量比增加而减小。     

Effect of complexing agents on the electrochemical performance of LiFePO4/C prepared by sol-gel method

ABSTRACT: LiFePO4/C is synthesized via sol-gel method using Fe3+ as iron sources and different complexing agents, followed by sintering at high temperature for crystallization. The amount of carbon in these composites is less than 6.8 wt.%, and the X-ray diffraction experiment confirms that all samples are pure single phase indexed with the orthorhombic Pnma space group. The particle size of the LiFePO4/C synthesized by acetic acid as a complexing agent is very fine with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, is better than those of LiFePO4/C synthesized by other complexing agents. The cell of this sample can deliver a discharge capacity of 161.1 mAh g-1 at the first cycle. After 30 cycles, the capacity decreases to 157.5 mAh g-1, and the capacity fading rate is 2.2%. The mechanism is studied to explain the effect of a complexing agent on the synthesis of LiFePO4/C by sol-gel method. The results show that the complexing agent with a low stability constant may be proper for the synthetic process of LiFePO4/C via sol-gel method.