褐煤脱水提质及其物化结构演变的研究进展

深入分析了褐煤中水分的赋存形态,提质过程中褐煤孔结构和含氧官能团的变化及其与提质褐煤水分复吸行为之间的关联,同时对现有的褐煤脱水提质技术进行了总结和对比。结果显示,微波辐照能有效脱除褐煤中极性含氧官能团,机械热压能显著减小褐煤孔体积和比表面积,含氧官能团、孔体积和表面积的减小是有效抑制提质褐煤水分复吸的主要原因,将微波干燥与机械热压脱水技术耦合是褐煤有效脱水提质的可能发展方向。     

煤中水分的存在形式及与煤结构的作用机理探究

为了探究褐煤中水分的存在形式及其水分对煤物理化学特性的影响,开发高效节能的提质技术。通过褐煤DSC热分析及傅里叶变换红外光谱的测定,分析了原煤加湿、干燥褐煤及碱洗褐煤后水分和热量的变化。实验结果表明,两种褐煤具有相似的DSC热分析行为特征,且煤中含氧官能团和孔隙结构对褐煤水分的含量起到关键的影响;完全干燥和碱洗过程会破坏褐煤的孔隙结构,降低孔隙水的含量,同时碱洗过程生成的沉淀占据了孔隙的体积,也降低了褐煤的含水量。     

印尼褐煤无黏结剂型煤自燃与燃烧特性研究

在内辊式高压型煤机上将一种印度尼西亚褐煤压制成高强度的无黏结剂型煤,对其比表面积、孔容积和表面官能团进行分析,测定了型煤的相对着火温度和绝热氧化升温速率,研究了其热解和燃烧行为特性.结果表明,印尼褐煤在干燥和高压成型过程中,发生了孔的收缩和崩塌,特别是微孔收缩程度要更大一些;干燥和成型过程中有羟基、羰基和羧基含氧官能团的分解;经过提质处理后,褐煤的自燃着火倾向降低,热解和燃烧反应性降低.     

褐煤润湿性及水分复吸的量热法研究

利用量热法分别对褐煤、脱灰褐煤和常见矿物质的润湿热进行测定,考察水分复吸对褐煤润湿性的影响,并对干燥褐煤水分复吸动力学进行分析.结果表明:褐煤中有机质的润湿热远大于其矿物质的润湿热,是褐煤润湿放热的主体.褐煤中含氧官能团越多,润湿热值越大.酸洗脱灰降低了褐煤的亲水性.芒来褐煤脱灰后,润湿热由101.61J/g降至66.79J/g,褐煤矿物质中高岭石的润湿热高于方解石和石英的润湿热;干燥褐煤的水分复吸符合二级动力学模型,相关系数大于0.99;褐煤复吸水分越多,其润湿热越小,芒来褐煤复吸水分增加到28.76%(质量分数)时,其润湿热由101.61J/g降至5.04J/g.水分复吸过程中,在表面形成的单层吸附或团簇吸附是褐煤润湿热降低的主要影响因素,而孔隙吸附或毛细凝聚吸附对其润湿热影响较小.     

低温干燥对褐煤含氧基团及其吸水性能的影响

采用红外光谱法确定褐煤中含氧官能团的种类,利用化学法分析干燥前后褐煤表面含氧官能团的变化,吸水性能用最高内在水分来表征,研究低温干燥过程中温度、干燥程度和干燥气氛对褐煤含氧基团及其吸水性能的影响.结果表明,褐煤中羧基和酚羟基含量较高;惰性气氛低温干燥时,酚羟基含量基本不变,羧基发生少量分解;空气下干燥时,羧基含量先减小,之后在氧化作用下,羧基和酚羟基含量同时增大.随着干燥程度的加深,煤样最高内在水分先减小后增大.     

芒来煤矿褐煤改性提质试验研究

利用带式炉改性提质工艺，脱除影响芒来褐煤热值的水和部分含氧官能团，使褐煤的发热量组分富集，热值提升，达到中高热值燃料煤（≥20．9MJ／kg）指标。     

褐煤干燥特性及产品特性研究

通过对内蒙古锡林浩特褐煤的热重分析可知,褐煤干燥过程约30 min,干馏过程约1.5 h。对不同粒径褐煤进行了干燥特性研究,说明+100,100～50,-50 mm原煤完全干燥分别需要4.0,1.0,0.5 h,粒径越小,煤样失重率越大,干燥速度越大,达到相同干燥效果所需的干燥时间也越短。最后分析了干燥温度对产品特性的影响,同时测试了干燥、干馏提质产品的自燃特性和复吸水特性,结果表明:与原煤相比,150,200℃产品挥发分分别提高了33.72%和31.13%,更易发生自燃,而550℃干馏过程中挥发分降低了30.89%,热稳定性大幅增加;150,200,550℃产品吸氧量分别提高了0.43,0.65,0.72 cm3/g;干燥产品燃点要低于原煤,而干馏产品燃点则高于原煤;干馏煤因改变了孔隙结构,最高内在水分降低,即复吸水的能力降低。因此,干燥提质产品与褐煤性质基本一致,而干馏提质产品性能则获得较大改善。     

蒙东褐煤干燥特性实验研究

研究了蒙东地区两种不同煤化程度褐煤的干燥过程,并对干燥至不同程度的褐煤进行分析.在干燥过程中不同煤化程度褐煤干燥速率变化趋势较为一致,煤化程度对干燥速率有一定的影响.煤化程度较低的乌拉盖褐煤其平均干燥速率较高,达到最大干燥速率的时间点较早.干燥过程改变了褐煤的微观结构,干燥后水分较低的褐煤其比表面积与原煤相比有所增加.随着干燥后水分的不断降低,褐煤中的含氧官能团表现为先减少后增加的趋势.与宝日希勒褐煤相比,乌拉盖褐煤中含氧官能团开始增加的时间点较早,更容易被氧化.     

褐煤干燥后水分复吸的实验研究

空气湿度是产生复吸的重要条件,湿度越高复吸的程度越高;自然条件下,温度越高复吸速度越快;产物粒度越小复吸速度和复吸程度越大。深度干燥煤的复吸水主要发生在煤堆表面。研究了高温烟气干燥褐煤的水分复吸性能,结果表明,在6％～11％的全水含量范围内,干燥煤复吸后水分升高幅度基本一致。在此全水范围内干燥煤全水高低不会影响复吸结果。     

褐煤腐植酸的抽提及其对褐煤吸水性能的影响

褐煤腐植酸含量高,腐植酸中含有多种活性基团,在工业、农业、畜牧业等领域有多种用途。褐煤直接燃烧利用率不大,因此在开发利用褐煤资源前对其进行腐植酸抽提是一种较好的提质方式。本文采用碱浸法对褐煤进行腐植酸的抽提,研究了煤样粒度、抽提条件等因素对腐植酸抽提率的影响,以及干燥的原煤、腐植酸抽提残煤和脱灰煤的水分复吸性能。结果表明:粒度在0.2mm以下的煤样,在超声波条件下抽提腐植酸效果较好;抽提残煤水分复吸率明显高于原煤,但将抽提残煤脱灰处理后,水分复吸率有明显下降,且与原煤脱灰后吸水性能相近,说明抽提残煤的吸水性与煤的孔隙率及表面的极性官能团有关,特别是碱浸法抽提腐植酸时生成的强吸水性羧酸盐类对抽提残煤吸水性有显著影响。     

Transformation of the reabsorption characteristics of lignite treated by low and high temperature drying process

Abstract

The reabsorption characteristics of the lignite treated by low and high temperature drying process were addressed in the paper. The information about the moisture form, functional groups, effective water-filled porosities and equilibrium moisture content of the lignite before and after the drying process was investigated using Differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and a self-made reabsorption device, respectively. The results show that the low drying temperature (140, 190, 230?°C, 10?min, N₂) has little impact on the effective water-filled porosities of the resulted samples, whereas it has a great influence on the main oxygen-containing functional groups, which amount firstly decreases and then increases with the drying temperature increasing. In the case of the lignite samples dried under high-temperature (600, 700, 800?°C, 30?s, N₂), the amount of the effective water-filled porosity of the sample decreases and the amount of oxygen-containing functional groups increases as the temperature increasing. The reabsorption capability of the high temperature dried sample is much lower than that of the sample treated under low drying temperature. The reabsorption characteristics of the low-temperature dried samples are affected by the amount of the oxygen-containing functional groups, while the effective water-filled porosity is main factor for the lignite samples derived from high temperature drying process. Moreover, the work gives a good evidence that the high-temperature drying process is an effective choose for lignite upgrading.     

Efficient drying and oxygen-containing functional groups characteristics of lignite during microwave irradiation process

To remove the high moisture of ZhaoTong lignite, the efficient drying characteristics and oxygen-containing functional groups changes in lignite during microwave irradiation process were highlighted in this study. As the microwave absorbers, lignite char and NaNO₃ were added to microwave drying of ZhaoTong lignite. The minimum chemical oxygen demand of waste water generated from microwave drying process of lignite was 99.89?mg?O₂?L^?1. The effects of microwave power, lignite mass, the weight ratio of lignite char to lignite and NaNO₃ content on the drying rate, and moisture diffusion coefficient of lignite were investigated during lignite microwave irradiation process. It was found that the drying rate and moisture diffusion coefficient of lignite increased with increasing microwave power, the weight ratio of lignite char to lignite and NaNO₃ content, but decreased with increasing lignite mass. Lignite char and NaNO₃ were mixed with lignite that can enhance the instantaneous surface temperature of lignite sample under microwave irradiation. Compared with addition of lignite char to lignite, the addition of NaNO₃ to lignite can decrease the unit electric power consumption of moisture evaporating. And the minimum unit electric power consumption of moisture evaporating was 9.44?Wh?g^?1. The FTIR technology was used to investigate the oxygen-containing functional groups changes in lignite during microwave drying process. The oxygen-containing functional groups of lignite were effectively removed with increasing microwave power.     

Structure characteristics of dewatered lignite from different drying temperature and time and effects on its behaviors of re-adsorbing moisture

By changing the drying temperature and residence time, a series of different degree dewatered lignite samples were prepared in the fixed-bed reactor under inert gas and their adsorbing moisture behaviors were investigated under certain re-adsorption conditions. Using SEM, nitrogen adsorption and in-situ FTIR analysis methods, the structure changes of dewatered lignite were measured and associated with the drying and re-adsorption behaviors. The results show that the higher the drying temperature, the higher the drying efficiency and the more obvious structure change of dewatered lignite. But the moisture re-adsorption amount of dewatered lignite showed different changing trends. Under the drying condition of 140°C and 50min, the total moisture content of coal after moisture re-adsorption was the lowest. Most pores are mesoporous in lignite and the macropore structure collapsed into mesopore during drying. When the drying temperature was higher than 120°C, oxygen-containing functional groups began to decompose; with the increase of drying temperature and time, decomposition rate increased. The hydrophilic strengths of -OH and COOH groups are stronger than that of others.     

Effect of Drying Conditions on Moisture Re-Adsorption Performance of Dewatered Lignite

In order to improve the drying efficiency of lignite and restrain the moisture re-adsorption of dewatered coal, the drying characteristics of typical Chinese lignite, the re-adsorption performances of dewatered samples and the change in pore structure throughout the entire processes were investigated in this study. Lignite samples with four different particle size fractions were dried in a fixed-bed reactor in the temperature range 60–160°C. The re-adsorbing moisture behaviors of dewatered coal samples containing different water contents were investigated at temperatures of 20–40°C and humidities of 55–95%. The changes in the pore structure of raw coal and different dried samples were measured by mercury intrusion porosimetry (MIP) and the relations between their re-adsorption performance and change in pore structure were explored. The moisture removal yields of lignite increased with an increase in drying time and temperature and was close to 100% above 120°C and over 100% after holding 40 and 15 min at temperatures of 140 and 160°C due to the release of CO₂ from the decomposing carboxyl group in the coal matrix. The re-adsorbed moisture content in dewatered coal was influenced by drying temperature and coal particle size through varying pore structure. The temperature and relative humidity in the re-adsorbing process were the main factors that influenced the moisture re-adsorption capacity of dewatered lignite, in which the re-adsorbing temperature mainly operated by varying the bonding ability of water on the surface of dewatered coal, and the relative humidity was connected with the pore structure as well. The mesopore was the main factor that influenced the re-adsorption of dewatered coal and the re-adsorption of moisture in dewatered coal at 100°C was highest due to the narrow range of the pore radius and because the relative volume ratio of 5 to 50 nm mesopore (above 91%) was high. The water loss yield of lignite with smaller particle size was higher due to its larger pore volume and surface area, but its re-adsorption capacity was lower because of lower volume ratio of 5 to 50 nm mesopore volume in dewatered coal obtained from the smaller size lignite.     

Changes of oxygen-containing groups during thermal treatment and their influences on moisture readsorption of lignite

The changes in oxygen-containing groups in the thermal treatment process of lignite were analyzed and the moisture readsorption amounts of upgraded coals were related in this study. A chemical titration method was applied to determine the types and contents of oxygen-containing groups in raw lignite and upgraded coals obtained in the temperature range of 353–633 K under atmospheres of argon, air, and carbon dioxide. Experimental results showed that the oxygen-containing groups mainly involved carbonyl, phenolic hydroxyl, and carboxylic groups (including carboxyl and carboxylate), among which phenolic groups were dominant. These different oxygen-containing groups decomposed discriminatingly with temperature according to thermal stability. The removal of oxygen-containing groups proceeded more easily in a CO₂ atmosphere compared to in Ar. The oxidation reaction occurring on the surface of lignite exposed to air led to an increase in oxygen-containing groups. The different types of oxygen-containing groups possessed various combining abilities with water, among which carboxyl was considered the most important group for the moisture readsorption. Decomposition of oxygen-containing groups in the thermal treatment process of lignite mainly caused a reduction in monolayer water adsorption and further decreased the multilayer water.     

Evolution of microstructure and combustion reactivity of lignite during high-temperature drying process

The evolutions of the microstructure characteristics and the combustion reactivity of lignite during high temperature drying process at 600–800°C were addressed in the paper. The information about the oxygen functional groups, carbon skeleton, pore structure, and combustion reactivity of the lignite before and after the drying treatment was obtained by Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller technique, Raman spectroscopy and thermogravimetric analyzer, respectively. The results show that a different evolutionary trend of the chemical structure of the lignite appears at the high drying temperature of 700°C at which the carbonyl, carboxyl, and carboxylate significantly decomposed and the treatment gave a slight elimination of structural imperfections and the formation of new cross-linking structures. Then, at the drying temperature of 800°C, a slight increase of the oxygen functional groups was found. The break of the aromatic ring or heterocycle contributed to the rapid increase of amorphous carbon to some extent. During the drying process, the surface area of the resulted lignite gradually increased until 700°C and then decreased. The evolution may be attributed to the decomposition of organic compounds, shrinkage forces, and thermal relaxation effect. The investigation indicates that the change in chemical nature of the coal had a greater impact on the combustion reactivity than the internal pore structure did. In addition, the combustion intensity and performance of the treated lignite was enhanced by the drying process.     

Evolvement behavior of microstructure and H2O adsorption of lignite pyrolysis☆

The effect of pyrolysis on the microstructure and moisture adsorption of lignite was investigated with low field nuclear magnetic resonance spectroscopy. Changes in oxygen-containing groups were analyzed by Fourier transform infrared spectroscopy(FTIR), and H2 O adsorption mechanism on the surface of lignite pyrolysis was inferred. Two major changes in the pore structure of lignite char were observed as temperature increased in 105–200 °C and500–700 °C. Pyrolysis temperature is a significant factor in removing carboxyl and phenolic hydroxyl from lignite.Variation of ether bond content can be divided into three stages; the content initially increased, then decreased,and finally increased. The equilibrium adsorption ratio, content of oxygen-containing groups, and variation of pore volume below 700° were closely correlated with each other. The amount of adsorbed water on char pyrolyzed at700 °C increased. Moreover, the adsorption capacity of the lignite decreased, and the adsorption state changed.     

Effect of mechanical thermal expression drying technology on lignite structure

Mechanical thermal expression (MTE) is a developing nonevaporative lignite dewatering technology. It has been proved to be effective to dewater high moisture content in low-rank coals via the application of mechanical force and thermal energy at elevated temperatures. In this paper, the dewatering behavior of the Xiaolongtang lignite in Yunnan province, China during the MTE process was studied with three process parameters: time, temperature, and pressure. Meanwhile, the mechanism was also explored of how variations in temperature and pressure during the MTE process affect the surface oxygen functional groups and pore structure, which was mainly conducted by means of Fourier transform-infrared spectrometer (FTIR) and mercury intrusion porosimetry (MIP). Increases in MTE temperature and pressure resulted in significant reductions in residual moisture content and moisture-holding capacity, along with the increase in fixed carbon content and content reductions of other elements, especially oxygen content, this could be largely attributed to the destruction of the surface oxygen functional groups and porosity in the lignite. Technologically, the optimal conditions for temperature and pressure are 150–220°C and 6–10?MPa. The residual moisture content of the lignite treated by MTE at 200°C, 10?MPa is lower than 8%; the dewatering rate reaches over 76% with the calorific value being approximately 22?MJ/kg. Carboxyl and hydroxyl groups break down at drying temperatures above 120°C and constant applied pressure 10?MPa; with the pore volume significantly reduced, only few pores (diameter?相似文献   

褐煤低温干燥特性的实验研究

中国褐煤储量丰富,但较高水分极大地限制了其开采和利用,对其进行脱水提质是解决褐煤高效利用的关键。通过热重分析仪（TGA）对HL和YN的不同粒径褐煤,分别在50,80和110℃等温干燥2h。结果表明：在每个干燥温度下煤样都能达到恒重,随着温度的升高煤样总失重增加,说明煤中水分与煤表面之间具有不同的结合强度;随着水分的降低,水分蒸发所需能量增加,煤水之间的相互作用加强,其中包括氢键和微孔对水的束缚力。粒径0．250～0．150mm、水分26．61％的HL褐煤在50c（二干燥后,水分降至6．96％,此时水分以分子层水的形式存在;干燥温度升至110℃时,煤中水分并未明显降低,说明煤中官能团与水分子间形成的氢键对水分有强烈的吸附作用。HL褐煤50℃干燥后,0．150～0．074mm和0．074～0．038mm煤样残留水分分别为6．52％和3．93％,均低于0．250～0．150mm煤样的6．96％,说明0．250～0．150mm煤样中不能脱除的残留水是孔隙水,被禁锢在狭小空间内。