Influence of torrefaction pretreatment on biomass gasification technology

Torrefaction is a slow pyrolysis process that is carried out in the relatively low temperature range of 220–300°C. The influence of torrefaction as a pretreatment on biomass gasification technology was investigated using a bench-scale torrefaction unit, a bench-scale laminar entrained-flow gasifier, and the analysis techniques TGA-FTIR and low temperature nitrogen adsorption. A series of experiments were performed to examine the characteristics of the torrefaction process, the properties of torrefaction products, and the effects of torrefaction on gas composition, cold gas efficiency and gasification efficiency. The results showed that during the torrefaction process the moisture content of biomass were reduced, and the wood fiber structure of the material was destroyed. This was beneficial to storage, transport and subsequent treatments of biomass in large scale. For solid products, torrefaction increased the energy density, decreased the oxygen/carbon ratio, and created a more complex pore structure. These improved the syngas quality and cold gas efficiency. Combustible gases accounted for about 50% of non-condensable gaseous torrefaction products. Effective use of the torrefaction gases can save energy and improve efficiency. Overall, biomass torrefaction technology has good application prospects in gasification processes.     

含氧气氛下的稻杆低温烘焙研究

以稻杆为原料考察了不同温度和含氧量下生物质的低温烘焙过程,研究了有氧烘焙的机理。对含氧气氛下不同停留温度时的质量残留率和微分热重分析（DTG）曲线进行分析发现,停留温度对质量残留率影响较大,是烘焙过程的主导因素。对6个不同含氧量下的质量残留率和DTG曲线分析可知,氧气加快了反应的进行,且随着含氧量上升发生分解的组分有所增加。建立了6个含氧量下稻杆低温烘焙的动力学模型并计算了动力学参数,发现稻杆表观活化能在1.33 kJ/mol到2.01 kJ/mol之间,且氧浓度与活化能的线性拟合度较好。     

Synthesis of glass ceramics from kaolin and dolomite mixture

Cordierite-and anorthite-based binary glass ceramics of the CaO-MgO-Al₂O₃-SiO₂ (CMAS) system were synthesized by mixing local and abundant raw minerals (kaolin and doloma by mass ratio of 82/18). A kinetics study reveals that the activation energy of crystallization (Ea) calculated by the methods of Kissinger and Marotta are 438 kJ·mol-1 and 459 kJ·mol-1, respectively. The Avrami parameter (n) is estimated to be approximately equal to 1, corresponding to the surface crystallization mechanism. X-ray diffraction (XRD) analysis shows that the anorthite and cordierite crystals are precipitated from the parent glass as major phases. Anorthite crystals first form at 850℃, whereas the μ-cordierite phase appears after heat treatment at 950℃. Thereafter, the cordierite allotropically transforms to α-cordierite at 1000℃. Complete densification is achieved at 950℃; however, the density slightly decreases at higher temperatures, reaching a stable value of 2.63 kg·m-3 between 1000℃ and 1100℃. The highest Vickers hardness of 6 GPa is also obtained at 950℃. However, a substantial decrease in hardness is recorded at 1000℃; at higher sintering temperatures, it slightly increases with increasing temperature as the α-cordierite crystallizes.     

Kinetics of thermal decomposition of hydrated minerals associated with hematite ore in a fluidized bed reactor

The kinetics of removal of loss on ignition (LOI) by thermal decomposition of hydrated minerals present in natural iron ores (i.e., kaolinite, gibbsite, and goethite) was investigated in a laboratory-scale vertical fluidized bed reactor (FBR) using isothermal methods of kinetic analysis. Experiments in the FBR in batch processes were carried out at different temperatures (300 to 1200℃) and residence time (1 to 30 min) for four different iron ore samples with various LOIs (2.34wt% to 9.83wt%). The operating velocity was maintained in the range from 1.2 to 1.4 times the minimum fluidization velocity (U_mf). We observed that, below a certain critical temperature, the FBR did not effectively reduce the LOI to a desired level even with increased residence time. The results of this study indicate that the LOI level could be reduced by 90% within 1 min of residence time at 1100℃. The kinetics for low-LOI samples (<6wt%) indicates two different reaction mechanisms in two temperature regimes. At lower temperatures (300 to 700℃), the kinetics is characterized by a lower activation energy (diffusion-controlled physical moisture removal), followed by a higher activation energy (chemically controlled removal of LOI). In the case of high-LOI samples, three different kinetics mechanisms prevail at different temperature regimes. At temperature up to 450℃, diffusion kinetics prevails (removal of physical moisture); at temperature from 450 to 650℃, chemical kinetics dominates during removal of matrix moisture. At temperatures greater than 650℃, nucleation and growth begins to influence the rate of removal of LOI.     

Oil cracking to gases： Kinetic modeling and geological significance

A Triassic oil sample from LN14 of Tarim Basin was pyrolyzed using the sealed gold tubes at 200-620℃under a constant pressure of 50 MPa. The gaseous and residual soluble hydrocarbons were analyzed. The results show that the cracking of oil to gas can be divided into two distinct stages: the primary generation of total C1-5 gases from liquid oil characterized by the dominance of C2-5 hydrocarbons and the secondary or further cracking of C2-5 gases to methane and carbon-rich matters leading to the progressive dryness of gases. Based on the experimental data, the kinetic parameters were determined for the primary generation and secondary cracking of oil cracking gases and extrapolated to geological conditions to predict the thermal stability and cracking extent of crude oil. Finally, an evolution model for the thermal destruction of crude oil was proposed and its implications to the migration and accumulation of oil cracking gases were discussed.     

CeO2 thin films grown on biaxially textured nickel (001)

CeO\-2 films have been grown on biaxially textured Ni substrates at various temperatures. The results show that CeO\-2 films without IBAD are dominated by (111) orientation from room temperature to 800℃ while the preferential orientation of CeO\-2 films with IBAD is (001) at lower deposition temperature and (111) at deposition temperature higher than 450℃. CeO\-2 films with better in_plane texture and out_of_plane orientation can be grown at 360℃ with 240 eV ion energy and 200 μA/cm\+2 ion current density.     

Isothermal Kinetics of the Pentlandite Exsolution from mss/Pyrrhotite Using Model-Free Method

Introduction Pyrrhotite(Fe,Ni)1?xS and pentlandite(Fe,Ni)9S8areimportant constituents of primary nickel sulfide oredeposits.Pentlandite is invariably associated with pyr-rhotite.At high temperatures(above610℃)(Fe,Ni)1?xS has the NiAs structure and is kno…     

Effects of homogenization on the dissolution and precipitation behaviors of intermetallic phase for a Zr and Er containing Al-Zn-Mg-Cu alloy

The effects of homogenization on dissolution and precipitation behaviors of intermetallic phase in a novel Zr and Er containing Al-Zn-Mg-Cu alloy were investigated.In this work,single-stage(SS:475℃/24 h) and doublestage(DS:400℃/12 h+475℃/24 h) homogenization treatments were carried out for the ingots with the heating rates of 300℃/h,50℃/h and 25℃/h,respectively.It was found that Er tended to segregate at the grain boundary in the form of Al_8Cu_4Er,and the formation mechanism was determined to be the eutectic reaction in the front of the solid/liquid interface during solidification.Also,Al_8Cu_4Er phase was detected to possess high melting point(～573.8℃),which fully remained after the homogenization.Meanwhile,a significant impact of heating rate on the dissolution of intermetallic phases for the studied alloy under the DS homogenization was determined,but little impact was observed under the SS homogenization.Morever,the size and distribution of the dispersoids after homogenization were fully analyzed.It was found that slow heating rates was helpful to refine the particles size,and increase the density as well as volume fraction of the precipitation under both SS and DS homogenization.However a higher density and volume fraction of the precipitated particles,and a relatively larger average particle size were gained with DS homogenization.     

Kinetic study of the hydrocarbon generation from marine carbonate source rocks characterization of products of gas and liquid hydrocarbon

The kinetic parameters of hydrocarbon generation from the marine carbonate source rocks were determined and calibrated through kinetic simulating experiment. The kinetic parameters of hydrocarbon generation then were extrapolated to geological condition by using the relative software. The result shows that gaseous hydrocarbons (C_1, C_2, C_3, C_(4-5)) were generated in condition of 150℃相似文献   

Synthesis of antiferroelectric (Bi0.534Na0.5)0.94Ba0.06TiO3 ceramics with high phase transition temperature and broad temperature range by a solid-state reaction method

Antiferroelectric 0.94(Bi 0.534 Na 0.5 )TiO 3 -0.06BaTiO 3 ceramics were prepared using a solid-state reaction method, involving the addition of excessive amounts of Bi2O3 . The resulting ceramics featured a very high phase transition temperature (Tm～330°C), from the antiferroelectric to the paraelectric phase, and a low depolarization temperature (Td<25°C). The broad temperature range, within which antiferroelectric properties are retained, of the prepared materials indicates their higher potential over lead-based antiferroelectric ceramics such as PZT-based materials that exhibit a lower T m ≤170°C. The lower Td and higher T m obtained val- ues, relative to those reported in the literature, are believed to be due to the formation of A-site vacancies originating from the incorporation of excess Bi into the perovskite structure of the studied sample. In addition, the synthesized sample shows a high dielectric constant of ～1460, in a temperature range of 50-150°C at 1 kHz, and a high energy storage density of 0.71 J/cm 3 , which is an asset in energy storage capacitor applications.     

Novel sintering behavior of polystyrene nano-latex particles in filming process

Filming process of polystyrene nano-latex (NPS) particles was studied by a combination of various methods. For a constant annealing time of 1 h, the AFM images showed that the deformation and sintering temperatures for NPS particles were ca. 90℃ and 100℃ respectively. In spin-lattice relaxation measurements of solid state NMR, it is found that T_1L, T_1S and I_1L/I₀ increased significantly after annealing at 90℃ and above. DSC results showed that there was an exothermic peak near T_g after annealing for 1 h at the selected temperatures below 95℃; otherwise, the exothermic peak disappeared after annealing at 100℃ or above. The apparent density of NPS increased suddenly in the temperature range. The results implied that the macromolecules in NPS particles are in a confined state with higher conformational energy and less cohensional interactions which are the drive force for the sintering at a lower temperature compared with the multichain PS particles and the bulk polymer.     

Emission inventories of primary particles and pollutant gases for China

Detailed high-resolution emission inventories of primary particles(PM2.5,BC and OC) and pollutant gases(SO2,NOx,NH3,CO and VOCs) for China in 2007 were constructed on the basis of the latest fuel consumption data,mostly at the county level,and from socio-economic statistics and data on fossil and biomass fuels obtained from government agencies.New emission factors reflecting local features were also used.The calculated emissions were 13.212 Mt PM2.5,1.4 Mt BC,2.946 Mt OC,31.584 Mt SO2,23.248 Mt NOx,16.017 Mt NH3,164.856 Mt CO and 35.464 Mt VOCs.The national and regional emissions were gridded with 0.5°× 0.5° resolution for use in air quality models.Larger emissions were found in eastern and central China than in western China.The emissions estimated here are roughly equal to those obtained in previous studies,but with different contributions from because of seasonal changes in residential heating and biomass combustion.Finally,uncertainties in inventories were analyzed.     

Temperature characteristics of electrical behavior of W-Bi-Ti-O ceramics at low field

Bi2WTi3O12 ceramics are fabricated by the conventional solid-state reaction process. With increasing temperature the sample first has metallic behavior, then strong electrical fluctuations above 100℃, and finally exhibits stable nonlinear properties characterized by semiconductivity above 300℃ at low field (E≤100 V/mm). The Arrhenius law for electrical conductivity by thermal activation is not suitable to explain the anomalous results. XRD analysis reveals that Bi2WO6 is the main phase and Bi4Ti3O12 is the second phase. Based on the phase transition of tungsten trioxide from room temperature to about 300℃, the electrical properties of Bi2WTi3O12 ceramics can be explained.     

Investigation of solvent extraction with GC/MS and residue with TG-FTIR from high-temperature coal tar

A high-temperature coal tar(HTCT) was sequentially extracted with petroleum ether(PE),ethyl acetate(EA),and acetone with ultrasonic irradiation to afford extracts 1 to 3(E_1 to E_3),respectively,and acetone residue.The gas chromatography/mass spectrometry(GC/MS) analysis of all extracts show that E_1 is mainly composed of di- and tricyclic arenes such as naphthalenes,phenanthrene,anthracene,etc.,whereas high contents of heteroatomic compounds and four or more ring arenes were found in E_2 and E_3,respectively.The pyrolysis process of acetone residue was studied with a thermogravimetric(TG) analyzer equipped with Fourier transform infrared(FTIR) spectrometer.The results indicate that volatiles were mainly released at 380-560 ℃,and the maximum mass loss rate occurred at 492 ℃.     

杨晓智 郭建华* 于凯川 王树谦

为了探究重金属胁迫下生物炭对玉米幼苗生长的影响,采用盆栽水培玉米幼苗,在无Pb2+和含Pb2+对照下观察不同裂解温度制备的生物炭对玉米幼苗生长的影响。研究结果表明：生物炭滤出液对玉米种子的萌发影响不显著, WS300(300℃生物炭)促进玉米幼苗的干物质量增加了27%, WS500(500℃生物炭)促进玉米幼苗的干物质量增加了35%。在Pb2+胁迫下,不同裂解温度生物炭对培养液中的Pb2+去除率达到了25%-30%,其中PWS300(含Pb2+的300℃生物炭)促进玉米幼苗茎长增加了25%、干物质量增加了30%。由此可见,生物炭在Pb2+胁迫下对玉米幼苗生长的促进作用有虽所减弱,但依然能明显促进玉米幼苗的早期生长。     

Formation mechanism of calcium hexaluminate

To investigate the formation mechanism of calcium hexaluminate (CaAl₁₂O₁₉, CA₆), the analytically pure alumina and calcia used as raw materials were mixed in CaO/Al₂O₃ ratio of 12.57:137.43 by mass. The raw materials were ball-milled and shaped into green specimens, and fired at 1300–1600°C. Then, the phase composition and microstructure evolution of the fired specimen were studied, and a first principle calculation was performed. The results show that in the reaction system of CaO and Al₂O₃, a small amount of CA₆ forms at 1300°C, and greater amounts are formed at 1400°C and higher temperatures. The reaction is as follows: CaO·2Al₂O₃ (CA₂) + 4Al₂O₃ → CA₆. The diffusions of Ca2+ in CA₂ towards Al₂O₃ and Al3+ in Al₂O₃ towards CA₂ change the structures in different degrees of difficulty. Compared with the difficulty of structural change and the corresponding lattice energy change, it is deduced that the main formation mechanism is the diffusion of Ca2+ in CA₂ towards Al₂O₃.     

Reaction condition optimization and kinetic investigation of roasting zinc oxide ore using (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript>

An orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore using (NH₄)₂SO₄. The optimized reaction conditions are defined as an (NH₄)₂SO₄/zinc molar ratio of 1.4:1, a roasting temperature of 440°C, and a thermostatic time of 60 min. The molar ratio of (NH₄)₂SO₄/zinc is the most predominant factor and the roasting temperature is the second significant factor that governs the zinc extraction. Thermogravimetric–differential thermal analysis was used for (NH₄)₂SO₄ and zinc mixed in a molar ratio of 1.4:1 at the heating rates of 5, 10, 15, and 20 K·min-1. Two strong endothermic peaks indicate that the complex chemical reactions occur at approximately 290°C and 400°C. XRD analysis was employed to examine the transformations of mineral phases during roasting process. Kinetic parameters, including reaction apparent activation energy, reaction order, and frequency factor, were calculated by the Doyle–Ozawa and Kissinger methods. Corresponding to the two endothermic peaks, the kinetic equations were obtained.     

Carbothermal synthesis of Si3N4 powders using a combustion synthesis precursor

Si₃N₄ powders were synthesized by a carbothermal reduction method using a SiO₂ + C combustion synthesis precursor derived from a mixed solution consisting of silicic acid (Si source), polyacrylamide (additive), nitric acid (oxidizer), urea (fuel), and glucose (C source). Scanning electron microscopy (SEM) micrographs showed that the obtained precursor exhibited a uniform mixture of SiO₂ + C composed of porous blocky particles up to ～20 μm. The precursor was subsequently calcined under nitrogen at 1200–1550°C for 2 h. X-ray diffraction (XRD) analysis revealed that the initial reduction reaction started at about 1300°C, and the complete transition of SiO₂ into Si₃N₄ was found at 1550°C. The Si₃N₄ powders, synthesized at 1550°C, exhibit a mixture phase of α- and β-Si₃N₄ and consist of mainly agglomerates of fine particles of 100–300 nm, needle-like crystals and whiskers with a diameter of about 100 nm and a length up to several micrometers, and a minor amount of irregular-shaped growths.     

Anomalies in mid-high-temperature linear thermal expansion coefficient of the closed-cell aluminum foam

Low-density closed-cell aluminum foam is promising to be used as load-bearing and thermal insulation components. It is necessary to systematically study its thermal expansion performance. In this work, linear thermal expansion coefficient(LTEC) of the closed-cell aluminum foam of different density was measured in the temperature range of 100–500 °C. X-ray fluorescence was used to analyze elemental composition of the cell wall material. Phase transition characteristics were analyzed with X-ray diffraction and differential scanning calorimetry. LTEC of the closed-cell aluminum foam was found to be dominated by its cell wall property and independent of its density. Particularly, two anomalies were found and experimentally analyzed. Due to the release of the residual tensile stress, the LTEC declined and even exhibited negative values. After several thermal cycles, the residual stress vanished. With temperature higher than 300 °C,instantaneous LTEC showed hysteresis, which should result from the redistribution of some residual hydrogen in the Ti2Al20 Ca lattice.     

Low temperature hydrothermal synthesis and electrochemical performances of LiFePO4 microspheres as a cathode material for lithium-ion batteries

Mesoporous LiFePO4 microspheres were simply synthesized by a low temperature(130℃),template-free hydrothermal route using low cost LiOH,Fe(NO3)3 and NH4H2PO4 as starting raw materials.These microspheres are composed of densely aggregated LiFePO4 nanoparticles and filled with interconnected mesochannels,which demonstrates not only a high tap density(≥1.4 g cm-3),a high capacity of 150 mAh g-1(～90% of its theoretical capacity) at 0.5 C rate,but also a ≥ 80% utilization of its theoretical capacity at a high rate of 1 C.In addition,the hydrothermal synthesis developed in this work is simple and cost-effective,it may provide a new route for production of the LiFePO4 material in battery applications.