A novel high polymer nanocomposite inhibitor for coal gangue spontaneous combustion prevention: A case study of Yangquan coal gangue in China

Coal gangue spontaneous combustion produces toxic and harmful gases. This research aims to study a new type of polymer nanocomposite inhibitor to prevent and control coal gangue spontaneous combustion. Nanomodification of montmorillonite (MMT) was carried out on high polymer emulsion inhibitor polyacrylamide (PAM) to improve its thermal stability and overcome the short inhibition duration problem. First, through scanning electron microscope (SEM), energy-dispersive spectrometer (EDS), and proximate analysis experiments, it was found that the coal gangue in the Yangquan mining area was prone to spontaneous combustion. Then, PAM/MMT was produced by an intercalation method. The results of X-ray diffraction (XRD) and differential scanning calorimetry (DSC) showed that the interval spacing of MMT increased, which was sufficient for the insertion of acrylamide monomer. The vitrification temperatures of PAM and PAM/MMT prove that PAM/MMT exhibited higher thermal stability. The results of Fourier transform infrared spectroscopy (FTIR) experiments indicated that the PAM/MMT composite inhibitor agent effectively inhibited the oxidative activity of reactive groups on the coal gangue surface. As a result, PAM/MMT could suppress coal gangue oxidative spontaneous combustion, so as to reduce environmental problems caused by coal gangue spontaneous combustion. Furthermore, a spraying process is designed for the application of the inhibitor.     

Preparation of a Novel Coal Gangue-Polyacrylamide Hybrid Flocculant and Its Flocculation Performance

A novel flocculant based on hybrid coal gangue-polyacrylamide (HCGPAM) has been prepared by using modified coal gangue and polyacrylamide. Factors related to the preparation such as reaction time, temp...     

A comparison of spontaneous combustion susceptibility of coal according to its rank

This study investigated spontaneous combustion susceptibility of coal according to the rank. To estimate the spontaneous combustion susceptibility of coal, both crossing-point temperature (CPT) measurement and gas analysis by using gas chromatography (GC) were performed. For the experiment, Eco coal and Kideco coal, Indonesian lignite, and Shenhua coal that is Chinese bituminous coal were used. The lignite such as Eco coal and Kideco coal contains more functional groups that easily react to oxygen more so than Shenhua coal. For this reason, the lignite is more easily oxidized than bituminous coal at low temperature, which results in high O₂ consumption, increase in CO and CO₂ generation, and low CPT. Although the CPT of Eco coal and Kideco coal is identical to each other as they are the lignite, Kideco coal has a lower initial oxidation temperature (IOT) and maximum oxidation temperature (MOT) than those of Eco coal. This means that although each coal has the same rank and CPT, spontaneous combustion susceptibility of coal may vary because the initial temperature of the coal at which oxidation begins may be different due to the substances that participate in oxidation.     

Influence of HCl on CO and NO emissions in combustion

The influence of HCl on CO and NO emissions was experimentally investigated in an entrained flow reactor (EFR) and an internally circulating fluidized bed (ICFB). The results in EFR show the addition of HCl inhibits CO oxidation and NO formation at 1073 K and 1123 K. At the lower temperature (1073 K) the inhibition of HCl becomes more obvious. In ICFB, chlorine-containing plastic (PVC) was added to increase the concentration of HCl during the combustion of coal or coke. Results show that HCl is likely to enhance the reduction of NO and N₂O. HCl greatly increases CO and CH₄ emission in the flue gas. A detailed mechanism of CO/NO/HCl/SO₂ system was used to model the effect of HCl in combustion. The results indicate that HCl not only promotes the recombination of radicals O, H, and OH, but also accelerates the chemical equilibration of radicals. The influence of HCl on the radicals mainly occurs at 800-1200 K.     

回填矸石的粒度分布的分形结构与自燃特性的关系

应用分形几何理论对破碎矸石样品进行了粒度分析,研究表明,破碎矸石具有分形结构特征。通过矸石样品的H2O2氧化升温速率实验,研究了不同粒度分布的矸石自燃特性,并分析了自燃特性与粒度分布分维的关系,结果显示,矸石的氧化速率随着粒度分布分维的增大而增大。进而,提出了矸石氧化速率与粒度分布分维之间的数学定量关系式。     

自燃煤矸石复合活化的正交试验研究

在对辽宁阜新高德矿自燃煤矸石进行了基本性质检测的基础上,采用物理和化学的激活方法,研究了自燃煤矸石胶结料的力学性能.物理研究表明该矸石易磨性较好;对以自燃煤矸石为主要材料的胶结料进行了正交试验研究,分析了矿粉、生石灰、二水石膏及水玻璃掺量对胶结料强度的影响.化学研究表明自燃煤矸石在复合激发剂的共同作用下,高掺量(74%)仍可配制出满足42.5强度等级的水泥.根据正交设计方差分析结果给出了胶结料的最佳配合比,为利用自燃煤矸石开发地聚物水泥提供了有益的技术参考.     

Interactions of CO, HCl, and SOx in pulverised coal flames

The effect of HCl and SO₂ on CO oxidation in pulverised coal flames was investigated experimentally and kinetically in an entrained flow combustion reactor. Two bituminous coals (German ‘Goettelborn’ and a Polish coal) were used as fuels with a feeding rate of 1 or 1.5 kg/h. HCl or SO₂ is introduced into the reactor premixed with the primary air. Experimental results indicate that HCl addition may inhibit CO oxidation in coal flames and increases CO emission. Reducing temperature in the reactor will enhance the inhibitory effect of HCl on CO oxidation. The measured CO profiles along the reactor height clearly show that the addition of HCl may inhibit CO oxidation. In the experimental range of SO₂ addition, the inhibiting effect of SO₂ on CO oxidation is less significant than HCl. A detailed kinetic mechanism is used to model the reactions, and the controlling reactions are analysed.     

Hydrogen production from coal by separating carbon dioxide during gasification

Hydrogen generation during the reaction of a coal/CaO mixture with high pressure steam was investigated using a flow-type reactor. Coal, CaO and CO reactions with steam, and CO₂ absorption by Ca(OH)₂ or CaO occurred simultaneously in the experiment. It was found that H₂ was the primary resultant gas, comprising about 85% of the reaction products. CO₂ was fixed into CaCO₃ and CO was completely converted to H₂. Pyrolysis of the coal/CaO mixture carried out in N₂ was also examined. The pyrolysis gases were compared with gases produced by general coal pyrolysis. While general coal pyrolysis produced about 14.7% H₂, 50.5% CH₄, 12.0% CO and 12.0% CO₂, the gases produced from coal/CaO mixture pyrolysis were 84.8% H₂, 9.6% CH₄, 1.6% CO₂ and 1.1% CO.     

A novel sodium carboxymethyl ellulose/aluminium citrate gel for extinguishing spontaneous fire in coal mines

Spontaneous combustion of coal is one of the main disasters affecting safe production in mines. A sodium carboxymethyl cellulose/aluminium citrate gel for prevention and extinguishing of mine fires was prepared. Based on a temperature‐controlled experiment, the authors studied the influences of the gel on indicator gases generated in the spontaneous combustion of coal, crossing point temperature, and activation energy. The results showed that the crossing point temperature of coal samples treated by the gel increased by more than 13.9°C and the activation energy rose by 7.17 to 16.34%. Moreover, the indicator gases, such as CO and C²H⁴ generated in the oxidation, decreased significantly. After treatment with the gel, the weight loss rate of the coal samples was reduced, and less energy was released. By using the self‐developed test platform (coal capacity of 2 m³), the spontaneous combustion of coal on the roof of a roadway was simulated, and the carboxymethyl cellulose/aluminium citrate gel was used for fire extinguishing. After injecting the gel, the temperature in the furnace rapidly decreased, and the concentration of O² remained at less than 3%, without showing any after‐combustion effects.     

EFFICIENT DESULFURIZATION IN O2/CO2 COMBUSTION: DEPENDENCE ON COMBUSTION CONDITIONS AND SORBENT PROPERTIES

Based on experiments on desulfurization, CaSO₄ decomposition, and a system approach using theoretical analysis, efficient in-furnace desulfurization in O₂/CO₂ combustion was investigated. The influence of combustion conditions and sorbent properties on system desulfurization efficiency was clarified. The global desulfurization efficiency was found to increase with O₂ purity. The global desulfurization efficiency in a dry recycle was higher than that in a wet recycle. The global efficiency of in-furnace desulfurization decreased with initial O₂ concentration. As the temperature increased, the global desulfurization efficiency increased first and then decreased due to the decomposition of CaSO₄. In the temperature range investigated, the global desulfurization efficiency in O₂/CO₂ coal combustion was much higher than that of conventional coal combustion in air. The global desulfurization efficiency decreased with sorbent size. When the particle radius decreased to one quarter, the global desulfurization efficiency doubled, becoming as high as 80%. The global desulfurization efficiency was very different among the three sorbents investigated, whether in O₂/CO₂ combustion or in conventional air combustion. The global desulfurization efficiency increased in the order of Ca(OH)₂, scallop, and limestone in O₂/CO₂ combustion, but in the order of scallop, Ca(OH)₂, and limestone in conventional air combustion. Nevertheless, all three sorbents demonstrated much higher desulfurization efficiency in O₂/CO₂ combustion than in conventional air combustion.     

Fe2O3/粉煤灰载氧体化学链燃烧实验与机理研究

提出了一种以粉煤灰为载体制备的新型铁基载氧体。采用同步热重分析仪、小型流化床以及DFT分别研究了新型载氧体的活性与热稳定性,发泡剂含量与反应温度以及粉煤灰主要组分之间的协同作用对新型载氧体性能的影响。研究结果表明,新型载氧体在以CO为燃料的化学链系统中具有较高的活性;新型载氧体较大的孔隙率以及粉煤灰多组分间的协同作用促使850℃下发泡剂含量为10.0%(质量)的新型铁基载氧体的最大转化率(84.9%)比Fe₂O₃/Al₂O₃的最大转化率(54.3%)高30%,且新型铁基载氧体在30个循环测试中表现出良好的热稳定性。载体制备采用的发泡剂含量以及反应温度对新型铁基载氧体性能影响很大,适当的发泡剂含量(约10%(质量))可提高新型载氧体性能。此外,高温下会造成载氧体的烧结现象。最后,采用密度泛函理论(DFT)研究了粉煤灰与载氧体之间的界面作用以及协同氧化CO的电子特性。计算结果表明,粉煤灰和Fe₂O₃之间的界面电荷转移使Fe₂O₃为电正性,促使CO在表面的相互作用,载体和活性组分之间的协同作用降低了载氧体与CO前线轨道能量差,进而促进了CO与Fe₂O₃的反应。     

CO〈sub〉2〈/sub〉抑制煤氧吸附过程的实验研究

煤对CO2的吸附能力较强,CO2分子会优先吸附在煤表面,减少O2的吸附量,抑制煤氧吸附过程。通过程序升温实验,研究CO2对煤氧吸附的抑制作用,测定煤样在不同CO2浓度下产生O2、CO、CH4的浓度值,分析CO2浓度对耗氧速率、CO产生率的影响规律。结果表明,37%～50%浓度的CO2对煤体耗氧速率的抑制效果明显,对煤样的CO产生率及甲烷浓度有降低作用,说明CO2能够有效抑制煤氧吸附过程,防止煤炭氧化自燃的发生。研究结果对CO2防灭火技术的开发与应用具有指导作用。     

In situ diagnostics of Victorian brown coal combustion in O2/N2 and O2/CO2 mixtures in drop-tube furnace

Experimental investigation of the combustion of an air-dried Victorian brown coal in O₂/N₂ and O₂/CO₂ mixtures was conducted in a lab-scale drop-tube furnace (DTF). In situ diagnostics of coal burning transient phenomena were carried out with the use of high-speed camera and two-colour pyrometer for photographic observation and particle temperature measurement, respectively. The results indicate that the use of CO₂ in place of N₂ affected brown coal combustion behaviour through both its physical influence and chemical interaction with char. Distinct changes in coal pyrolysis behaviour, ignition extent, and the temperatures of volatile flame and burning char particles were observed. The large specific heat capacity of CO₂ relative to N₂ is the principal factor affecting brown coal combustion, which greatly quenched the ignition of individual coal particles. As a result, a high O₂ fraction of at least 30% in CO₂ is required to match air. Moreover, due to the accumulation of unburnt volatiles in the coal particle vicinity, coal ignition in O₂/CO₂ occurred as a form of volatile cloud rather than individual particles that occurred in air. The temperatures of volatile flame and char particles were reduced by CO₂ quenching throughout coal oxidation. Nevertheless, this negative factor was greatly offset by char-CO₂ gasification reaction which even occurred rapidly during coal pyrolysis. Up to 25% of the nascent char may undergo gasification to yield extra CO to improve the reactivity of local fuel/O₂ mixture. The subsequent homogeneous oxidation of CO released extra heat for the oxidation of both volatiles and char. As a result, the optical intensity of volatile flame in ∼27% O₂ in CO₂ was raised to a level twice that in air at the furnace temperature of 1273 K. Similar temperatures were achieved for burning char particles in 27% O₂/73% CO₂ and air. As this O₂/CO₂ ratio is lower than that for bituminous coal, 30-35%, a low consumption of O₂ is desirable for the oxy-firing of Victorian brown coal. Nevertheless, the distinct emission of volatile cloud and formation of strong reducing gas environment on char surface may affect radiative heat transfer and ash formation, which should be cautioned during the oxy-fuel combustion of Victorian brown coal.     

冻融作用下活化煤矸石粉混凝土损伤劣化规律

为促进寒冷地区煤矸石在混凝土中的应用,通过机械-微波方式对煤矸石进行复合活化,从表观形貌、质量损失率、相对动弹性模量、抗压强度和劈裂抗拉强度等方面对煤矸石粉混凝土的损伤劣化规律进行了研究,并使用扫描电子显微镜、核磁共振波谱仪和X射线衍射仪等研究了活化煤矸石粉对混凝土抗冻性能的改性机理。结果表明:20%(质量分数)掺量下活化煤矸石粉对混凝土抗冻性能改善效果最好,且经300次冻融循环后,质量损失率和相对动弹性模量分别为2.32%和91.32%,抗压强度和劈裂抗拉强度分别下降了16.40%和26.12%;活化煤矸石粉能填充、细化孔隙,且其二次水化能消耗水泥水化产物Ca(OH)₂,产生C-S-H和C-A-S-H,提升水泥石密实程度,改善孔结构,使大孔占比减少。     

Effects of Ca-based additives on desulfurization during coal pyrolysis

The effects of different Ca-based additives on the sulfur removal of coals during pyrolysis up to 900 °C have been studied in a fixed-bed reactor. It was found that Ca(OH)₂ and CaO were quite effective to capture the sulfur-containing gases, 95% of the sulfur evolved from untreated coal was retained in the char by the use of additives. Both the tar yield and the sulfur content of the tar decreased with addition of Ca-based additives. The effect of Ca(OH)₂ was better than that of CaO due to its higher activity, but CaCO₃ had little effect because of its higher decomposition temperature (−900 °C) than the peak temperature range (400–500 °C) of sulfur-containing gases emission. There is remarkable sulfur retention effect with Ca(OH)₂ prepared by impregnation and ultrasonic treatment due to the higher dispersion in coal particles than by simple mechanical mixing. The ultrasonic treatment is the best method with regard to the lowest SO₂ release during the char combustion. XRD results showed that the sulfur captured by Ca-based additives during pyrolysis turned into CaS. FeS detected in pyrolysis char without additives disappeared in chars with additives, which indicated that CaO could react with FeS through solid-solid reaction. When the chars with calcium-additives were burned in fixed bed reactor, they gave out less SO₂ than the raw coal added with same additives. The best total desulfurization efficiency could reach to about 85%.     

Gelation performance of poly(ethylene imine) crosslinking polymer–layered silicate nanocomposite gel system for potential water‐shutoff use in high‐temperature reservoirs

Polymer gels have been widely used for water shutoff in mature oil fields. In this paper, polyacrylamide (PAM)–montmorillonite (MMT) nanocomposites (NC) were prepared through in situ intercalative polymerization. Fourier transform infrared spectroscopy and X‐ray diffraction were conducted to characterize the prepared PAM/MMT nanocomposites. The gelation performance of poly(ethylene imine) (PEI) crosslinking PAM/MMT nanocomposite gel system (NC/PEI gel system) was systematically investigated by bottle testing and viscosity measurement methods. The results showed that the gelation performance of the NC/PEI gel system was greatly affected by the total dissolved solids, PAM/MMT nanocomposite concentration, and PEI concentration. The NC/PEI gel system exhibited much better thermal stability and gelation performance than the PAM/PEI gel system at the same conditions. The gelation performance after flowing through porous media of the NC/PEI gel system before injection and that of the subsequently injected gel system was different. The gel strength decreased and the gelation time was delayed after the gel system before injection was flowed through porous media. However, the gel strength of the subsequently injected gel system did not decrease, and only the gelation time was delayed after flowing through porous media. This study suggests that the NC/PEI gel system can be used as a potential water‐shutoff agent in high‐temperature reservoirs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44243.     

Catalytic effect of biomass ash on CO, CH4 and HCN oxidation under fluidised bed combustor conditions

In fluidised bed combustion heterogeneous reactions catalysed by the bed material, CaO, and char are significant for the emission levels for instance of NO, N₂O, and CO. The catalysts present in the bed affect significantly the selectivity of HCN and NH₃ oxidation, which are known as precursors of NO_x (i.e. NO and NO₂) and N₂O emissions from solid fuel combustion. Thus the catalytic activity of biomass ashes may also be responsible for the negligible N₂O emissions from biomass combustion due to the presence of a large amount of solids in fluidised bed combustion, homogeneous oxidation may be suppressed within the bed by the quenching of the radicals. For this reason the catalytic oxidation of hydrocarbons and CO on the bed material may be of significance for the total burnout within the fluidised bed combustor.Within this study the effect of different ashes from spruce wood, peat, and for comparison bituminous coal on the oxidation of CH₄, CO, and HCN was studied. The different ashes were shown to have a strong catalytic activity for the oxidation of CH₄, CO, and HCN. In HCN oxidation the selectivity towards NO is high, whereas very little N₂O is formed. The activity of the ashes is strongly dependent on the fuel, which may be explained by their composition.The kinetics of the oxidation of CO and HCN in the temperature range relevant for fluidised bed combustion, i.e. 800-900 °C, has been evaluated for spruce wood ash.     

烟气气相组分及Ca(OH)_2对KMnO_4氧化NO的影响机理

在固定床反应器中考察了KMnO₄氧化烟气中NO的过程,分析了烟气组分H₂O、O₂及SO₂对NO氧化过程的影响规律,得到了Ca（OH）₂对KMnO₄氧化NO的影响机理。实验结果表明,H₂O是KMnO₄氧化NO的必要条件;在含H₂O条件下,O₂可以提高NO氧化率。SO₂与氧化剂反应生成无水钾镁钒类复盐K₂Mn₂（SO₄）₃对NO氧化具有负面作用;Ca（OH）₂的加入提高了氧化剂表面的固体碱度从而促进氧化过程进行;通过添加Ca（OH）₂可以降低SO₂对NO氧化过程的负面影响。根据气体成分和产物分析可知,KMnO₄在钙基吸收剂表面氧化烟气中NO的机理可能是KMnO₄以离子态将吸附在氧化剂表面的NO和SO₂氧化为NO₂和SO₃,生成的NO₂、SO₃再传递到氧化位临近的碱性位被吸收。     

热活化煤矸石—水泥复合体系水化性能分析

采用比强度法对活化煤矸石的火山灰效应进行评定,通过Ca(OH)2剩余量和化学结合水量的测定,分析活化煤矸石-水泥体系的水化程度,并采用X射线衍射分析,差热分析对其水化过程进行研究。结果表明:煅烧温度为750℃,保温时间为4h的热活化煤矸石对水泥体系的火山灰贡献率较高;该体系Ca(OH)2剩余量较少,化学结合水量较多,其水化产物主要以C-S-H凝胶,Ca(OH)2和钙矾石为主。     

PE/OMMT nanocomposites prepared by in situ polymerization approach: Effects of OMMT‐intercalated catalysts and silicate modifications

In this article, the surfactants, (2‐hydroxylethyl) octadecyl dimethylammonium nitrate (OH‐C18), hexadecyltrimethylammonium bromide(C16), and mixture of trimethylchlorosilane (TM) and OH‐C18 were ion‐exchanged with cations in the montmorillonite (MMT) to generate three organic MMTs (named as OH‐C18‐MMT, C16‐MMT, and MMMT), leading to different environments of catalyst species in MMT interlayer gallery. Et[Ind]₂ZrCl₂ (abbreviated as EI) was supported on the above three types of OMMTs to prepare the PE/OMMT nanocomposites via in situ polymerization. By contrast, EI/MMMT showed higher activity than EI/OH‐C18‐MMT and EI/C16‐MMT under the same polymerization conditions. The other two types of catalysts, such as [(tert‐Bu)NSi(Me₂)C₅Me₄]TiCl₂ (CGCT) and Bis[N‐(3‐tert‐butylsalicylidene)anilinato] titanium (IV) dichloride (FI) were also supported on the OH‐C18‐MMT for in situ ethylene polymerization. It was found that the activity of FI/OH‐C18‐MMT for ethylene polymerization was much lower than the other two corresponding catalysts under the similar reaction conditions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012