光谱分析在煤结构研究中的进展

煤结构是各类煤相关研究的微观基础,光谱分析作为煤结构研究的重要方法被广泛应用,其在煤结构研究中的进展对光谱分析方法的普及、应用和发展有重要意义.光谱分析方法研究煤结构已成为煤化工领域使用的常规方法,能够快速无损检测,对煤分子结构的破坏小,可为不同环境条件下煤物理化学性质的变化提供有效的检测手段.从光谱分析在煤质、大分子...     

Study of the correlation between the coal calorific value and coal ash content using X-ray fluorescence analysis

In this paper we have studied the possibility of determining the chemical elements in coal samples using X-ray fluorescence analysis and have found a relationship between the coal calorific value and its ash content with the coal moisture accounting. The amount of coal ash can be determined by the content of the basic chemical elements, such as Si, Sr, Fe, and Ca. It was concluded that the calorific value of coal can be estimated from the ash content in coal without the calorimetric measurements. These correlation coefficients were calculated for coal from several coal mines in Mongolia. The results are in good agreement with the results of chemical analysis.     

Chemical transformation of iron compounds during the process of coal pyrolysis in steam

When the content of sulphur in hard coal is higher than 1.5% weight, such coal cannot be used as fuel in thermal-electric power stations due to environmental protection. Such coal can be used as a raw product in various chemical processes in which many valuable substances are obtained. This study is a small part of a major project looking for improved ways of utilizing sulphur-rich coals. Mössbauer measurements were carried out for semi-cokes obtained from sulphur-rich coal in the pyrolysis process in a steam atmosphere in the temperature range of 300–800 °C. Results of these measurements showed that during the pyrolysis process, pyrite transformed completely into iron oxides (magnetite and hematite), whereas illite transformed only partly even at the highest temperatures. Unfortunately, it was not possible to identify some products of the illite transformation.     

An investigation of the effect of ultrasonic waves on the efficiency of silicon extraction from coal fly ash

Burning of coal accounts for an enormous proportion of the current energy supply, especially in developing countries. Burning of coal produces large amounts of coal fly ash, which causes serious environmental problems unless it is managed properly. Using chemical analysis, we found that coal fly ash could be a promising source of Si, Al, Ca and some rare earth elements, especially with the assistance of some measures such as ultrasound. In this study, we extracted silicon from coal fly ash using an alkaline dissolution strategy and investigated the effects of temperature and ultrasonic power on the efficiency of silicon extraction. During a 70 min reaction, the efficiency of silicon extraction increased markedly, from 9.41% to 34.96%, as the reaction temperature increased from 70 °C to 110 °C. With ultrasound assistance, ultrasonic waves enhanced the extraction of silicon at both 80 °C and 110 °C at 720 W ultrasound, increasing the efficiency of silicon extraction from 6.01% to 15.36% and from 34.96% to 54.42%, respectively. However, at 900 W ultrasonic power, extraction was slightly inhibited at both temperatures, causing a little decrease in efficiency.     

ICP-OES分析低钙粉煤灰在NaOH溶液中离子浸出规律

低钙粉煤灰潜在的火山灰活性释放缓慢限制了其大规模利用,通过碱激发提高粉煤灰中Si4+,Al3+和Ca2+等离子浸出率对于加快低钙粉煤灰活性释放具有积极作用。采用电感耦合等离子体发射光谱、傅里叶变换红外光谱、X射线衍射和扫描电子显微镜分别测试和分析了5种浓度NaOH溶液对低钙粉煤灰激发过程中Si4+,Al3+和Ca2+的浸出规律、化学基团变化、水化产物生成及微观形貌演化。结果表明：碱激发作用显著提高了低钙粉煤灰中Si4+,Al3+和Ca2+浸出率,三种离子浸出率大小为：Si4+＞Al3+＞Ca2+,其中Si4+和Al3+浸出率随NaOH浓度增加而增加,随浸出时间延长呈对数规律升高;Ca2+由于在NaOH溶液中生成Ca(OH)₂沉淀,其浸出率大小表现为在水中高,在NaOH溶液中低。红外光谱清晰地表征出低钙粉煤灰受碱激发作用后化学基团在指纹区(波数1 300 cm-1以下)的变化,且随碱激发时间的延长和碱浓度的增加变化愈加明显。水化产物和微观形貌的结果显示出粉煤灰颗粒表面受到碱侵蚀发生解聚,在OH-催化下,硅铝单体分子重新排列形成硅酸盐和铝酸盐低聚络合物,通过亲核取代反应形成铝硅酸盐的低聚态溶胶,并进一步与碱金属阳离子通过配位键或静电键的作用缩聚形成水化凝胶类产物。采用ICP-OES测试粉煤灰中离子浸出率可作为评价粉煤灰火山灰活性的一种快速和准确的方法。     

Sono-leather technology with ultrasound: a boon for unit operations in leather processing - review of our research work at Central Leather Research Institute (CLRI), India

Ultrasound is a sound wave with a frequency above the human audible range of 16Hz to 16kHz. In recent years, numerous unit operations involving physical as well as chemical processes are reported to have been enhanced by ultrasonic irradiation. There have been benefits such as improvement in process efficiency, process time reduction, performing the processes under milder conditions and avoiding the use of some toxic chemicals to achieve cleaner processing. These could be a better way of augmentation for the processes as an advanced technique. The important point here is that ultrasonic irradiation is physical method activation rather than using chemical entities. Detailed studies have been made in the unit operations related to leather such as diffusion rate enhancement through porous leather matrix, cleaning, degreasing, tanning, dyeing, fatliquoring, oil-water emulsification process and solid-liquid tannin extraction from vegetable tanning materials as well as in precipitation reaction in wastewater treatment. The fundamental mechanism involved in these processes is ultrasonic cavitation in liquid media. In addition to this there also exist some process specific mechanisms for the enhancement of the processes. For instance, possible real-time reversible pore-size changes during ultrasound propagation through skin/leather matrix could be a reason for diffusion rate enhancement in leather processing as reported for the first time. Exhaustive scientific research work has been carried out in this area by our group working in Chemical Engineering Division of CLRI and most of these benefits have been proven with publications in valued peer-reviewed international journals. The overall results indicate that about 2-5-fold increase in the process efficiency due to ultrasound under the given process conditions for various unit operations with additional benefits. Scale-up studies are underway for converting these concepts in to a real viable larger scale operation. In the present paper, summary of our research findings from employing this technique in various unit operations such as cleaning, diffusion, emulsification, particle-size reduction, solid-liquid leaching (tannin and natural dye extraction) as well as precipitation has been presented.     

Low frequency ultrasound-assisted leaching of sewage sludge for toxic metal removal,dewatering and fertilizing properties preservation

The aim of this research was to evaluate the efficiency of an ultrasonication process in combination with METIX-AC technology, a chemical process, for metal removal and dewatering ability, with preservation of fertilizing properties of sewage sludge. Waste activated sludge samples having a total solids concentration of 4 and 20 g L^?1, were enriched with Cu and Zn in order to exceed the limiting values recommended by Québec regulation for sludge valorization. Ultrasonication was applied at low frequency (22 kHz) at specific energies ranging from 180 to 66,000 kJ kg^?1 of dry sludge. Ultrasound-assisted leaching rates and yields were similar to chemical leaching alone for Zn, whereas solubilisation was reduced for Cu, regardless the specific energy. Fertilizing properties preservation and dewatering ability were similar in ultrasound-assisted leaching, compared to chemical leaching alone. These trends were mainly attributed to the changes of metal speciation, particle size and morphology during ultrasonication, in addition to untreated sludge properties.     

江西乐平晚二叠世煤成烃机理红外光谱研究

应用显微红外光谱技术,对江西乐平晚二叠世煤矿B₃煤层煤样在不同热模拟温度下的结构组成变化特征及规律进行了研究,结合镜下显微组分的观察和统计结果,剖析了乐平晚二叠B₃煤层煤的生烃机理,对该区煤成烃资源进行了初步评价。研究表明：煤化学结构主要由杂原子基团、脂族结构和芳香结构三部分组成,其活化能依次增加;煤成烃过程,是一种随着热演化程度的加深, 脂族侧链不断脱落,芳香结构不断缩聚,含氧基团逐渐断裂的过程;该煤层中含有的B型基质镜质体和树皮体都是很好的生烃显微组分,是该树皮煤生烃潜力巨大的主要原因。此特点对在华南地区寻找与富含“树皮体”煤系地层有关的油气资源并使“煤变油”产业化具有重要的意义。     

An In Situ Testing Method for Analyzing the Changes of Active Groups in Coal Oxidation at Low Temperatures

This study details an in situ Fourier transform infrared spectroscopy analytical system that was employed to follow chemical variations in the functional groups on coal surface during the oxidation process at low temperatures. In the reported in situ Fourier transform infrared spectroscopy system, a special chamber was used to contain the coal powders, and a gas inlet tube and a programmable heater were used to simulate different reaction atmospheres and temperatures. The comparisons between in situ and ex situ Fourier transform infrared spectroscopy spectra indicate that the in situ Fourier transform infrared spectroscopy data offer a more accurate reflection of changes in the functional groups. The real-time changes of aliphatic hydrocarbon groups and oxygen-containing groups in a lignite coal sample were analyzed from 30°C to 220°C using in situ Fourier transform infrared spectroscopy. The experimental results indicate that the chemical variations in the functional groups are affected by their relative chemical activities. The results show that the presence of aliphatic groups on the coal surface varies with temperature. Over the range of 30–70°C the presence of these groups decreases, but then their abundance increases over the range of 70–180°C and finally decreases again when the temperature is increased to between 180°C and 220°C. With respect to oxygen-containing functional groups, three various trends were observed as the test temperature was varied. Our conclusion was that these variations are a function of the reaction activities of the various oxygen-containing functional groups.     

红外光谱定量研究不同煤阶煤的化学结构

为定量研究不同煤阶煤的化学结构,借助傅里叶红外光谱,对河曲长焰煤、柳林焦煤及晋城无烟煤进行了化学结构表征。从红外的四个谱段来看,每一谱段都发生了一定的变化。在芳香结构中,河曲煤有5个峰位,柳林煤减小为3个峰位,而后至晋城煤又增加到5个峰位。在含氧官能团中,随着煤阶的升高,波数在1 100~1 350 cm^-1的峰面积逐渐减小,峰形变得平缓,这说明煤化作用是富碳、脱氧的过程。在脂肪烃中,谱图中波数在2 952 cm^-1附近的肩峰加宽,说明甲基的含量增加。波数在2 895 cm^-1附近的峰形逐渐变缓,说明次甲基的含量减小。在氢键范围内,随着煤阶的增高,谱图先变缓后变陡,波数在3 400 cm^-1附近变化尤为突出,说明煤中自缔合羟基的含量先减小后增加。并运用Origin7.5软件对所得到的红外谱图进行分峰拟合及归属。结果表明:苯环的取代方式主要以三取代为主,随着煤阶的增高,苯环三、四取代含量下降,二、五取代含量升高;其中苯环三取代的含量由63%降至32%,苯环四取代由17.21%降至12.86%,而苯环二取代则由12.36%增至24.44%,苯环五取代由6.55%增至26.58%。红外归属中,不同煤阶煤灰分的百分含量,与其工业分析中灰分含量有很好地对应。随着煤阶的增高,碳氧单键的比例由37.22%降至27.83%;碳碳双键含量由31.02%升高到36.86%,而后又降至25.42%;碳氧双键含量有微小变化,由13.07%降到13.02%,然后又升至13.81%。脂肪烃中,随着煤化程度的加深,甲基对称伸缩振动占比分别为11.67%, 11.81%和12.92%,甲基反对称伸缩振动占比分别为18.74%, 18.94%, 24.76%,而次甲基的伸缩振动占比分别为17.38%, 12.53%, 11.57%,亚甲基对称伸缩振动占比分别为18.09%, 18.14%和15.43%,亚甲基的反对称伸缩振动占比分别为34.41%, 38.58%和35.32%。亚甲基的对称与反对称的比例都出现先增加后减小的趋势;甲基的对称与反对称伸缩振动的比例则呈增加趋势;次甲基的含量呈降低趋势。羟基-N氢键存在于河曲煤与柳林煤中,晋城煤无此类氢键;煤阶越低,其百分含量越大。随着煤阶的增高,环状缔合氢键由19.03%降至12.71%,羟基-醚氢键由27.20%降至16.89%;这是由于低煤阶煤中羧酸、羟基等含氧官能团的含量高。自缔合羟基含量先由39.63%减小到34.78%,而后又增加至37.88%;而羟基-π氢键的含量由9.84%上升至27.77%。这些变化揭示了煤化作用是一个富碳、去氢、脱氧、去除杂原子的复杂演化过程;对探索煤大分子结构演化特征及控制机理有借鉴意义。     

Influencing factors and kinetics analysis on the leaching of iron from boron carbide waste-scrap with ultrasound-assisted method

In this paper, the ultrasound-assisted leaching of iron from boron carbide waste-scrap was investigated and the optimization of different influencing factors had also been performed. The factors investigated were acid concentration, liquid-solid ratio, leaching temperature, ultrasonic power and frequency. The leaching of iron with conventional method at various temperatures was also performed. The results show the maximum iron leaching ratios are 87.4%, 94.5% for 80 min-leaching with conventional method and 50 min-leaching with ultrasound assistance, respectively. The leaching of waste-scrap with conventional method fits the chemical reaction-controlled model. The leaching with ultrasound assistance fits chemical reaction-controlled model, diffusion-controlled model for the first stage and second stage, respectively. The assistance of ultrasound can greatly improve the iron leaching ratio, accelerate the leaching rate, shorten leaching time and lower the residual iron, comparing with conventional method. The advantages of ultrasound-assisted leaching were also confirmed by the SEM-EDS analysis and elemental analysis of the raw material and leached solid samples.     

燃煤过程痕量元素动力学机理的研究进展

由于痕量元素在煤中的含量低微、检测困难,加之其原子量一般较大,可能的反应途径多,使得相关的反应机理研究难度极大。本文结合作者的研究成果,介绍了煤燃烧过程中痕量元素化学反应动力学的国内外研究进展,包括痕量元素化学动力学机理的建立;相关的典型实验、计算模拟及其实验验证、动力学机理模型的简化;痕量元素反应动力学机理的完善和发展,包括采用简单碰撞理论、活化络合物理论(亦称过渡态理论,或绝对反应速率理论)对痕量元素化学反应动力学机理的修正;最后指出煤燃烧过程中痕量元素动力学研究的若干方向是: (1)痕量元素反应动力学模型数据库的建立;(2)煤燃烧过程中,主量元素和次量元素的动力学机理的完善; (3)各痕量元素之间动力学研究的开展; (4)实际燃烧过程中痕量元素动力学行为的研究。     

Mössbauer study on iron in marine sediments and manganese nodules

The chemical states of iron in a deep-sea sediment, a manganese nodule and a nearshore sediment are studied before and after chemical leaching. The Mössbauer spectra of the manganese nodule after chemical leaching clearly revealed the presence of a ferrous component not identified in previons studies. The ferrous component in the deep-sea sediment and the manganese nodule are shown to originate in terrigenous materials transported from lands through the atmosphere.     

Spectroscopic observations of methane-pulverized coal flames

A premixed laminar flame burner was used to study physical and chemical effects of burning methane and pulverized coal simultaneously. Spectral emissions obtained as a function of height in the flame, for OH, CH, C₂, and CO were used to calculate excited state species number densities. Premixed methane-air flames with a number of equivalence ratios and methane-air-coal dust flames with three equivalence ratios were studied and differences were noted. Spatial temperatures were measured in all flames by means of a thermocouple probe.The introduction of a pulverized coal additive (30mg/min) leads to changes in OH, Ch, C₂, and CO number densities and temperature at various heights, which depend on the stoichiometry of the methane-air flame. Possible chemical and physical mechanisms responsible for these changes are discussed qualitatively. The data pose a severe test for any quantitative model which includes the fluid dynamics, gas-phase chemistry, heterogeneous processes, and radiation transport.     

A Combined FTIR and Textural Study of the Oxidation of a Bituminous Coal

A FTIR study to detect the chemical modifications involved during the oxidation of a Spanish coal from the Central Asturian Basin (Spain) has been carried out. The coal was oxidized at 473 K for periods of 3, 7, 14 and 42 days, and at 543 K for 1, 2, 3, 4 and 14 days. Results show that at each temperature there was an increase in oxygenated functions (carboxyls, esters, anhydrides, ethers) and a gradual decrease in aliphatic and aromatic structure. There are remarcable differences at the two temperatures. Intermediate states of oxidation, less condensated structures and an appreciable proportion of the aliphatic C-H groups are predominant in coal samples oxidized at 473 K. When oxidation is carried out at 543 K, more oxidized forms, a more marked process of decarboxylation and more condensated structures appear, also aliphatic groups disappears almost totally. Chemical analysis and textural properties of each oxidized coal sample have been carried out, and a correlation between chemical changes detected by FTIR and textural properties has been attempted.     

Sonic and ultrasonic removal of chemical contaminants from soil in the laboratory and on a large scale

Power ultrasound can be used for the rehabilitation of industrial sites or the reclamation of polluted land by the removal of chemical and biological contamination from soil. In this paper some current laboratory research and the potential for the scale-up of chemical decontamination is reviewed. Two basic mechanisms for acoustically enhanced soil cleaning have been suggested (a). an increase in the abrasion of suspended soil in slurries leading to the removal of contaminated material from the surface of particles and (b). an improvement in leaching out of more deeply entrenched materials.     

New Fillers for PBI-Based Composite Electrolytes in Polymer Fuel Cells

Nafion and derived perfluorinated polymers seem to be the most reliable materials in PEMFCs, despite a number of disadvantages, such as low operation conditions (T < 100°C) and high cost. In recent years, new classes of proton conducting membranes have been investigated. PBI membranes showed some advantages: high working temperatures; good chemical resistance; promising durability. Proton carriers are supplied by the presence of phosphoric acid in the membranes. Despite the good conductivity (about 0.1 S/cm at 80°C and RH = 80%) one of the main drawbacks is the leaching of the phosphoric acid under working conditions. In this work two different silica-based fillers, derivatised with phosphoric acid and imidazole-containing units, respectively, were prepared via sol–gel route and characterised from a thermal analyses (TGA-DTA), structural (XRD, IR and solid state NMR) and microstructural (BET) point of view. Impedance spectroscopy scans were carried out on PBI-based membranes filled with derivatised silica up to a content of 30 wt% in order to evaluate the role of the filler in the free phosphoric acid retention capability. The best scores in terms of permanent proton conductivity and acid doping level after leaching were obtained in case of imidazole-functionalised silica, which improves the basicity of the doped polymer system.     

基于光谱分析的砷黄铁矿生物浸出过程中铁/砷/硫形态转化研究

基于同步辐射装置的As/S的K边及Fe的L边X射线吸收近边结构光谱(XANES)和X射线衍射(SR-XRD),结合扫描电镜(SEM)、傅里叶红外光谱(FTIR)、电感耦合等离子体发射光谱(ICP-AES)及各项浸出参数的测定,系统研究了(中度嗜热菌、嗜热硫化杆菌)浸出砷黄铁矿过程中铁、砷、硫的形态转化。结果表明,在生物作用下,砷黄铁矿的溶解速率明显高于化学浸出体系,伴随矿物溶解释放到溶液中的砷和铁在生物浸出体系中主要为As(Ⅴ)和Fe3+,而在无菌化学浸出体系则主要为As(Ⅲ)和Fe2+;细菌胞外多聚物(EPS)在细菌与硫化矿物的相互作用过程中起着至关重要的作用, FTIR的结果表明,生物浸出体系中吸附在矿物表面的吸附菌的EPS中蛋白质和多糖的含量均高于游离菌EPS;SEM的结果表明,砷黄铁矿表面在生物浸出过程中逐渐被腐蚀,且有浸出产物覆盖,而化学浸出10 d后,矿物表面依旧比较光滑;SR-XRD的结果表明,元素硫(S0)、黄钾铁矾和砷酸铁在生物浸出第4 d生成,并随时间延长逐渐累积,最终成为浸出渣中的主要成分。Fe的L边XANES结果表明,在细菌作用下矿物表面逐渐被Fe(Ⅲ)浸出产物覆盖;As的K边XANES结果表明,浸出渣中砷的价态包括As(-Ⅰ), As(Ⅲ)和As(Ⅴ),拟合结果表明,经过10 d的生物浸出,砷黄铁矿、雌黄(As2S3)和砷酸铁在矿渣中所占的比例分别为18.6%, 23.5%和57.9%,化学浸出10 d后,矿渣中除未溶解的砷黄铁矿外,仅有少量砷酸铁(6.2%)形成;S的K边XANES拟合结果表明,经过10 d的生物浸出,砷黄铁矿、 S0、硫代硫酸盐、施氏矿物和黄钾铁矾在矿渣中所占的比例分别为15.3%, 23.7%, 3.5%, 11.3%和46.2%,而在化学浸出10 d后的矿渣中,仅拟合到少量S0(7.8%)。基于上述结果可以得出,铁、砷、硫在砷黄铁矿生物作用下的形态转化过程分别为:Fe(Ⅱ)-Fe(Ⅲ), As(-Ⅰ)-As(Ⅲ)-As(Ⅴ), S-→S0→S2O■→SO■。结合溶液中的浸出参数发现,随着S0、黄钾铁矾、砷酸铁和雌黄的大量累积,砷黄铁矿的生物浸出严重受阻。硫代硫酸盐的生成表明砷黄铁矿的溶解途径与黄铁矿相似。     

煤粉燃烧火焰辐射光谱实验研究

针对煤粉燃烧辐射光谱问题,利用光纤光谱仪对煤粉平面火焰炉实验装置煤粉燃烧火焰辐射光谱进行了测量,详细分析了煤粉辐射光谱特征,并基于普朗克辐射传热定律,通过对光谱仪波长响应特性的标定,得到火焰绝对辐射强度随波长的分布情况,进而利用最小二乘法获得火焰温度与辐射率参数,由此提出基于煤粉燃烧火焰辐射光谱测量的火焰参数测量方法。利用该方法对不同燃烧条件下煤粉燃烧参数进行测量,开展了不同燃烧参数下煤粉火焰辐射光谱实验研究,研究结果表明：煤粉燃烧火焰辐射在200～1 100 nm波段具有较强且连续的光谱特征,基于普朗克辐射定律与最小二乘法可实现煤粉燃烧火焰温度与辐射率的测量;煤粉燃烧火焰辐射光谱在590,766,769和779 nm附近可见明显的Na和K等碱金属痕量元素原子光谱发射谱线,并且这些原子谱线的出现与火焰温度有关;随着煤粉浓度的提高,虽然燃烧温度变化不大,但由于火焰辐射率的增加,造成辐射光谱强度的大幅提升。这对锅炉煤粉燃烧优化具有重要参考价值。     

化学浸提法研究中药赤石脂中活性铝的溶出及形态分布

利用KCl,NH_4Ac,HCl,NaOH4种化学浸提液将中药赤石脂中活性铝溶出,根据不同的溶出机理,得到赤石脂中铝的不同化学形态,采用分光光度法进行定量测定,得到中药赤石脂中活性铝的形态分布,并对影响铝溶出的若干因子进行了探讨。