An experimental investigation into the gasification reactivity of chars prepared at high temperatures

The gasification activities of three kinds of Binxian chars with carbon dioxide were studied at 1000–1300 °C and under atmospheric pressure in self-made thermal balance. The specific surface area of coal or chars was determined with BET methods during gasification. The results showed that the reaction rate of two rapid pyrolysis chars increases at the beginning and decreases subsequently with increasing carbon conversion at relatively high temperatures. The heating rate of coal has a significant effect on the gasification process. The activation energy of slow pyrolysis char varies between 160 kJ/mol and 180 kJ/mol during gasification. The activation energy of the two rapid pyrolysis chars displays a linear trend when the carbon conversion is less than 40% and decreases slowly afterwards.     

Reactivity study of combustion for coals and their chars in relation to volatile content

To determine the effect of volatile matter on combustion reactivity, the pyrolysis and combustion behavior of a set of four (R, C, M and K coals) coals and their chars has been investigated in a TGA (SDT Q600). The maximum reaction temperatures and maximum reaction rates of the coals and their chars with different heating rates (5–20 °C/min) were analyzed and compared as well as their weight loss rates. The volatile matter had influence on decreasing the maximum reactivity temperature of low and medium rank coals (R, C and M coals), which have relatively high volatiles (9.5–43.0%), but for high rank coal (K coal) the maximum reactivity temperature was affected by reaction surface area rather than by its volatiles (3.9%). When the maximum reaction rates of a set of four coals were compared with those of their chars, the slopes of the maximum reaction rates for the medium rank coals (C and M coals) changed largely rather than those for the high and low rank coals (R and K coals) with increasing heating rates. This means that the fluidity of C and M coals was larger than that of their chars during combustion reaction. Consequently, for C and M coals, the activation energies are lower (24.5–28.1 kcal/mol) than their chars (29.3–35.9 kcal/mol), while the activation energies of R and K coals are higher (25.0-29.4 kcal/mol) than those of their chars (24.1–28.9 kcal/mol).     

Study on CO2 gasification reactivity of chars obtained from Soma-Isıklar lignite (Turkey) at various coking temperatures

A kinetic study on the gasification of char with CO₂ is presented in this paper. The chars from different coking temperatures show a different reactivity, which can be mostly attributed to kinetic parameters (E_A, k_m, η) and the specific surface area values. The kinetic analysis results with CO₂ gasification of chars from the Soma-Isıklar lignite present that CO₂ gasification rates for chars are controlled by chemical reaction at experimental gasification temperature range. Therefore, the specific surface area and kinetic parameters of prepared chars from Soma-Isıklar lignite should be considered as a very important factor for the gasification reactivity and rates.     

A TPD study of coal chars in relation to the catalysis of mineral matter

The steam gasification mechanism of brown coal was studied by a temperature-programmed desorption (TPD)technique. A Morwell coal was devolatilized in N₂ and then gasified in steam at 1100 K. During the TPD of a partially gasified char, H₂O, CO₂ and CO evolved approximately at 640, 870 and 1020 K, respectively. The presence of mineral matter was found to be responsible for these gas evolutions, since essentially no gas evolution was observed during the TPD of the demineralized coal char. The comparison of the above TPD pattern with those determined for the cation-exchanged samples revealed which inorganic species is responsible for each TPD peak: H₂O evolution was due to Ca; CO₂ evolution to Ca and Mg; CO evolution to Na and/or Fe. The exchanged metal species like Ca and Na significantly catalysed the gasification reaction. The relation between the catalytic activity and TPD pattern was discussed in terms of surface oxygen complexes.     

Investigation of combustion reactivity and NO emission characteristics of chars obtained from the devolatilization of raw and partially dried lignite

In an attempt to achieve the clean and efficient utilization of lignite, drying pre-treatment was performed in this study before lignite combustion. The combustion reactivity and NO emission characteristics of the partially dried lignite samples in the char combustion stage were investigated by means of TG and isothermal combustion tests, and the reactivity could be summarized as the following order: L1>L0.5>raw>L3>LT>L5 (chars obtained from the devolatilization of the raw and partially dried coals at 378 K for 0.5, 1, 3, 5, and 120 minutes) and the NO conversion ratio of L1 was the lowest. When the moisture content in the coal particles was relatively high (19.68%-35.84%), the drying treatment could increase the combustion reactivity and inhibit NO emission in the char combustion stage; When the moisture content was within a relatively low range (0.17%-19.68%), the moisture removal had negative effects on the reactivity and NO emission in the char combustion stage. The surface behaviour and microstructure of the raw coal char and chars derived from the partially dried coals were clarified by temperature programmed desorption/reduction (TPD/TPR) and Raman spectroscopy. The results illustrated that L1 derived from L_c1 (19.68%) was the most reactive sample with the largest amount of C(O) on the particle surface. There were also more reactive aromatic structures in L1 than other samples. Compared with direct combustion or excessive drying treatment, lignite should be dried to a certain degree (19.68%) for optimized lignite combustion.     

A simple kinetic analysis to determine the intrinsic reactivity of coal chars

The intrinsic oxidation reactivity in air of an activated carbon char derived from bituminous coal was investigated using a new thermogravimetric analysis (TGA) method. Applying the new method, values of the Arrhenius activation energy E and pre-exponential factor A were estimated from TGA data obtained via heating samples at different constant rates. A novel statistical criterion was subsequently used to determine the heating rate at which optimum values of E and A were obtained. This is a valuable development, for in conventional non-isothermal TGA, while it is accepted that Arrhenius parameters vary with heating rate, there is no formal method for selecting one rate (and hence one set of values of E and A) over another. Using this new method, the following optimum values were obtained for the carbon at a heating rate of 25 °C min⁻¹: E=129.4 kJ mol⁻¹ and ln(A/s⁻¹)=10.4. These results are very similar to those calculated for the same material using more time consuming and less accurate isothermal TGA methods. It is therefore proposed that this new analysis method might be an improvement on conventional techniques to determine the intrinsic oxidation reactivity in air of coal chars.     

Microstructure and reactivity evolution of colloidal silica binder in different systems at elevated temperatures

Colloidal silica as nanostructured binder for refractory castables has attracted many attentions in recent years. In the present study, phase composition, microstructure and reactivity evolution of silica gel at different heating conditions were investigated to find suitable system for colloidal silica application. The results showed that atmosphere and carbon slightly affected phase composition of the silica gel at elevated temperatures, and the crystalline phases were composed of major α-cristobalite and minor α-tridymite. The morphology and particle size of the silica gel were greatly affected by atmosphere and carbon during heating. The spherical nano-silica particles with sizes of 40–50 nm rapidly grew into macroscale rod-like particles with temperature increasing from 800-1000 °C to above 1200 °C in air, and sintering of silica particles was observed. However, the size and morphology of the spherical nano-silica particles retained at high temperature in a reducing atmosphere, and many well developed columnar mullite crystals and some SiC whiskers formed on heating silica gel, alumina fines and carbon at 1500 °C, which was due to carbon inclusions retarding the growth of nano-silica particles and the nano silica remained high reactivity at high temperature. Thus, colloidal silica was suitable for application in carbon-containing refractory castables.     

Ambient-pressure thermogravimetric characterization of four different coals and their chars

Ambient-pressure thermogravimetric characterization of four different coals and their chars was performed to obtain fundamental information on pyrolysis and coal and char reactivity for these materials. Using a Perkin-Elmer TGS-1 thermobalance, weight loss as a function of temperature was systematically determined for each coal heated in helium at 40 and 160 °C/min under various experimental conditions, and for its derived char heated in air over a temperature range of 20 to 1000 °C. The results indicate that the temperature of maximum rate of devolatilization increases with increasing heating rate for all four coals. However, heating rate does not have a significant effect on the ultimate yield of total volatiles upon heating in helium to 1000 °C; furthermore, coupled with previous data⁹ for identical coal samples, this conclusion extends over a wide range of heating rate from 0.7 to 1.5 × 10⁴ °C/s. Using the temperature of maximum rate of devolatilization as an indication of relative reactivity, the devolatilization reactivity differences among the four coals tested that were suggested by this criterion are not large. For combustion in air, the overall coal/char reactivity sequence as determined by comparison of sample ignition temperature is: N. Dakota lignite coal ≈ Montana lignite coal > North Dakota lignite char > III. No. 6 bituminous coal ≈ Pittsburgh Seam bituminous coal > Montana lignite char > III. No. 6 bituminous char > Pittsburgh Seam bituminous char. The reactivity differences are significantly larger than those for devolatilization. The reactivity results obtained suggest that coal type appears to be the most important determinant of coal and char reactivity in air. The weight loss data were fitted to a distributed-activation-energy model for coal pyrolysis; the kinetic parameters so computed are consistent with the view that coal pyrolysis involves numerous parallel first-order organic decomposition reactions.     

Physicochemical properties and structural evolutions of gas-phase carbonization chars at high temperatures

The gas-phase carbonization chars from hydrocarbons with low molecular weight (anthracene oil and petroleum ether) were prepared using a drop tube reactor at 1000-1200 °C, and their physicochemical properties and structural evolutions (elemental composition, carbon crystallite structure, surface morphology, pore structure and chemical composition of volatile matters) were mainly investigated. The chars obtained in the high temperature region, which appeared with high C/H atomic ratio and poor carbon crystallite structure far from natural graphite, could be used as high carbonaceous materials. The chars were composed of uniform spherical particles with a continuous pore size distribution. The average pore diameters of the chars were much smaller and in the rage of 5.0-8.7 nm. The increasing carbonization temperature led to an initial increasing and a sequent decreasing of specific surface areas from mico-meso-pores and an increasing of those from meso-macro-pores in the chars. The volatile matters in the chars were composed of an easily-extracted fraction (CS₂-soluble compounds with three to six aromatic rings) and a hard-extracted fraction (CS₂-insoluble compounds with higher aromaticity). The elevated carbonization temperature led to diminish the two volatile fractions. A liquid core formation mechanism was proposed to explain the gas-phase carbonization process of hydrocarbons.     

Critical phenomenon during photoinitiated gelation at different temperatures: A Photo-DSC study

The behaviour of photoinitiated radical polymerization of an 80 wt% epoxy diacrylate (EA) and 20 wt% tripropyleneglycoldiacrylate (TPGDA) mixture with 2-mercaptothioxanthone (TX-SH) photoinitiator was studied at different temperatures by using photo-differential scanning calorimetric (Photo-DSC) technique. All photopolymerization reactions were carried out under the same conditions. It was observed that all conversion curves during gelation at different temperatures present nice sigmoidal behaviour which suggests the application of the percolation model. Observations around the critical time, called the glass transition point (t_g), taken to reach the maximum rate of polymerization (Rp_max) show that the gel fraction exponent (β) obeyed the percolation model. The produced β values were found to be around 0.50, predicting that the system under consideration belongs to the same universality class. However, Rp_max and the final conversion (C_s) values were found to increase when the temperature was increased up to a certain value. On the other hand, t_g values decreased and became saturated as the temperature was increased.     

Critical phenomenon during photoinitiated gelation at different temperatures: A Photo-DSC study

The behaviour of photoinitiated radical polymerization of an 80 wt% epoxy diacrylate (EA) and 20 wt% tripropyleneglycoldiacrylate (TPGDA) mixture with 2-mercaptothioxanthone (TX-SH) photoinitiator was studied at different temperatures by using photo-differential scanning calorimetric (Photo-DSC) technique. All photopolymerization reactions were carried out under the same conditions. It was observed that all conversion curves during gelation at different temperatures present nice sigmoidal behaviour which suggests the application of the percolation model. Observations around the critical time, called the glass transition point (t_g), taken to reach the maximum rate of polymerization (Rp_max) show that the gel fraction exponent (β) obeyed the percolation model. The produced β values were found to be around 0.50, predicting that the system under consideration belongs to the same universality class. However, Rp_max and the final conversion (C_s) values were found to increase when the temperature was increased up to a certain value. On the other hand, t_g values decreased and became saturated as the temperature was increased.     

Effect of pre-oxidation on reactivity of chars in steam

The effects of pre-oxidation of char from Taiheiyo coal, a non-caking bituminous coal, in the 400–550 °C temperature range on its gasification reactivity with N₂-H₂O at 0.1 MPa (steam partial pressure of 13.2 kPa) have been investigated. The pre-oxidation of char markedly enhances gasification rates at temperatures between 800 and 900 °C. Reactivity is found to parallel the burn-off level during preoxidation at low temperatures (400–430 °C), whereas at relatively high temperatures (480–550 °C), the burn-off level only affects the reactivity slightly. The amount of CO and CO₂ evolved from the preoxidized char by heat treatment is proportional to the burn-off level at low temperatures (400–430 °C), being closely related to the enhancement of the gasification reactivity in steam.     

概述离子交换膜的发展及前景应用

离子交换膜因其在节能、环保方面的巨大优势,已经发展为未来研究的主要方向。离子交换膜的分类方法已经完善,但在制备方法、改性以及应用方面的研究一直是研究的重点方向,对阴离子交换膜、阳离子交换膜及其制备过程、表面改性和掺混改性过程的研究具有巨大经济价值,离子交换膜在水处理、电渗析和冶金方面的应用可以极大的节约能源,在环境保护方面也具有巨大应用前景。     

不同温度下微生物燃料电池的运行特性

实验采用双室型微生物燃料电池（MFC）,以生活废水中厌氧菌作为生物催化剂,葡萄糖为燃料,通过5个不同温度条件下的间歇运行,应用循环伏安、交流阻抗、极化测试等电化学方法考察温度对电池产电性能的影响。结果表明,一定温度范围内,提高温度有助于增强微生物的电化学活性,降低传荷阻抗,提高电池输出功率密度和交换电流密度。32 ℃时,电池产电效能最佳,电池功率密度和交换电流密度分别达到156.2 mW/m2和8.02×10?5 mA/m2,温度太低或太高均不利于细菌的电化学活性。体系温度为18 ℃、25 ℃、32 ℃、39 ℃、46 ℃时,传荷阻抗Rct在阳极内阻中占的比例分别为97.99%、84.02%、47.36%、91.30%、99.61%,说明传荷阻抗在阳极内阻中占绝对份额,MFC是传荷过程控制下的电化学反应体系。     

无烟粉煤的岩相组成对成型特性的影响

煤岩组分特征及成型试验研究表明 ,古书院矿无烟煤属于成型难度较大的煤种 ,适宜与有关粘结剂或其他煤种配合成型。根据当地条件选择配煤或试制适合该粉煤成型的粘结剂 ,是将粉煤成型利用的关键和前提。     

不同温度下空气-聚醚多元醇的搅拌特性

在直径为0.28 m椭圆底搅拌釜内,以空气-聚醚多元醇为实验物系,对20～120℃范围内不同温度下两种三层组合桨的搅拌功率及气含率特性进行了实验研究,并获得了不同组合桨的相对功率消耗及气含率关联式。结果表明：随着通气流量和搅拌转速的增大,两种组合桨的气含率均升高,相对功率消耗均减少;随着温度的升高,两种组合桨的气含率和相对功率消耗均减小。但组合桨Ⅰ（底HEDT＋中WHu＋上WHu）的综合性能要优于组合桨Ⅱ（底6XYK＋中6XDT＋上HEDT）,有利于获得较高的气含率和通气搅拌功率,更适合用于聚合体系气-液两相混合操作过程中。     

A novel methodology to model the creep behavior of polymers at different temperatures

A new methodology for modeling the creep behavior of polymers at different temperatures, by using phenomenological constitutive models, is presented in this paper. The viscoelastic model is given by a combination of springs and dashpots and is used to describe the nonlinear response of polymers, and the viscoplastic formulation is given by a power-law equation. The approach proposed in this work is based on building master curves for different stress levels, and finding the dependency of the constitutive parameters with the temperature. After fitting the equations to the tensile creep tests at different temperatures, the final constitutive formulation is capable of modeling the behavior of polymers at any stress level and temperatures. Poly methyl metacrytale (PMMA) was used to investigate the accuracy of this proposal, and the results showed good agreement with the experimental data.