生物质与烟煤灰的理化特性及混合灰熔融特性研究

文章利用扫描电子显微镜(SEM)、X射线荧光光谱仪(XRF)、X射线荧光衍射仪(XRD)、灰熔融特性分析仪对4种生物质(海草、梨木、榛子壳、稻秆)灰与神木烟煤灰的混合灰的熔融特性进行了研究。研究发现:水生生物质(海草)灰的掺混使混合灰的熔融特性温度先升高再降低;两种木本生物质(梨木和榛子壳)灰的掺混使混合灰的熔融特性温度逐渐升高;草本生物质(稻秆)灰的掺混对混合灰熔融特性温度的影响与水生生物质灰类似。由XRF分析可知:Na2O和CaO对于混合灰的熔融特性温度有更明显的影响,随着混合灰中Na2O含量的逐渐增加,混合灰的熔融特性温度逐渐下降;随着混合灰中CaO含量的逐渐增加,混合灰的熔融特性温度逐渐上升。由XRD结果可知:水生生物质灰在高温下容易形成熔点较低的碱金属硅酸盐,使混合灰的熔点降低;木本生物质灰中的CaCO3含量较高,能够提高混合灰的熔点;草本生物质灰与水生生物质灰类似,含有的低熔点碱金属硅铝酸盐使混合灰的熔点降低。     

Effects of oxy-fuel condition on morphology and mineral composition of ash deposit during combustion of Zhundong high-alkali coal

Zhundong coalfield is a super-large coal reserve, with high-alkali feature exacerbating ash deposition. Oxy-fuel combustion technology could propel the clean utilization of Zhundong high-alkali coal. While the ash deposition behavior of high-alkali coal under oxy-fuel condition has yet to be sufficiently investigated. The present study compared the differences of ash deposits between oxy-fuel and air combustion, and also examined the effects of oxygen content on ash deposition mechanism, employing a drop-tube furnace equipped with a specially designed sampling probe and some analysis methods, such as X—ray diffraction equipment, simultaneous thermal analyzer, etc. Experimental results indicated that ash deposition was weaker, with fewer contents of sodium chloride, calcium sulphate and less agglomeration ash in oxy-fuel atmosphere compared to the air case with same oxygen content. The content of the ash particle distributed in the range of 0–40 μm was up to 60% under oxy-fuel condition. The first weight loss of ash deposits, around 850 °C, was put down to the decomposition of carbonate and the second one, about 1150 °C, was ascribed to the decomposition of the sulphate minerals in the thermal process. Ash deposition worsened with more large particles (>120 μm), as the oxygen content rose. Sodium chloride content reached 9.7% with 50% oxygen content. The present study not only focuses on the morphology and chemical components, but also probes into the thermal volatility of ash deposits, which benefits the further understanding of the ash deposition mechanism and utilization of Zhundong high-alkali coal during oxy-fuel combustion.     

Experimental study of the high-temperature slagging characteristics of coal ash-biomass ash blends under different atmospheres

The blends of coal ash and straw ash with the proportion of 50%, 30% and 10% were selected for high-temperature slagging experiments under different atmospheres (Air/N₂/CO₂). The main components of the slags were the mixtures of Si-Al-Ca-O. The straw ash in low proportion was first to melt and then bonded slags. The eutectic reaction of blend ashes were facilitated by increasing the proportion of straw ash, which enhanced the effect of slagging. Slagging in oxygen-containing atmospheres (Air, CO₂) was much more serious than that in N₂ atmosphere. The formation of iron glass was promoted under air atmosphere, and K, Na, Cl elements in straw ash volatilized significantly while few of them existed in the form of feldspar compounds or sulfates. Mullite in coal ash was consumed and then produced calcium feldspar because of the eutectic reaction with CaO. However, the slagging characteristics were not the same in reducing atmospheres. In CO₂ atmosphere, the surface was eroded into gully apertures because of the gasification, and Fe₂O₃ was reduced to FeO which enhanced slagging. But the effect of N₂ atmosphere on the blend ashes was weak. The mineral decomposition and reorganization made the slag present fragmented, while the element Fe was present in the form of Fe₂O₃ under N₂ atmosphere. In this case, the strong polarity of Fe³⁺ weakened the melting of the slag.     

Effect of high silicon-aluminum coal ashes on sintering and fusion characteristics of a potassium-rich biomass ash

The effects of high silicon-aluminum coal ashes (Shajuzi coal ash (SJZA) and Pingshuo coal ash (PSA)) on the sintering and fusion behaviors of a potassium-rich biomass ash (cotton stalk ash (CSA)) were investigated by a horizontal tube furnace and an ash fusion temperature (AFT) analyzer. X-ray diffraction (XRD), thermogravimetry and differential scanning calorimetry (TG-DSC) techniques were applied to analyze the mineral transformations and thermal behaviors of the ash samples. As the coal ash mass ratio varied from 0 to 50%, the sintering degree of CSA/SJZA and CSA/PSA mixtures gradually mitigated. The AFTs of the two groups of mixtures all presented parabolic with respect to coal ash ratio. The potassium content in CSA was very high (K₂O, 39.55%), and K-containing minerals mainly existed as low melting point (MP) matters, i.e., sylvite (KCl), arcanite (K₂SO₄), potassium carbonate (K₂CO₃), and fairchildite (K₂Ca(CO₃)₂). The mitigation of sintering degree was ascribed to a decrease in KCl content with increasing coal ash ratio. When the coal ash ratio was less than 20%, the decrease in AFT was due to the consumption of alkaline earth metal oxide and the formation of K silicate. The conversions of low MP K salts to high MP K–Al silicates (kalsite (KAlSiO₄) and nepheline (KNa₃Al₄Si₄O₁₆)) and the formations of other high MP minerals increased the AFTs after adding 20% coal ash. The thermogravimetric analysis showed that the endothermic peak of KCl evaporation weakened to disappear and the exothermic peaks of some reactions enhanced with rising coal ash ratio.     

中频无芯感应熔炼炉熔炼过程中断后的温度特性数值模拟

对中频无芯感应熔炼炉内钢料在熔化过程中断后的降温和凝固过程进行了数值模拟。研究了熔化过程中突然断电后熔炼炉内钢料的相界面变化、温度分布及变化的规律。讨论了正常熔化时间即断电前炉内状态对断电后钢液凝固和炉内温度变化的影响。结果表明：正常熔化中突然断电后,熔化仍将进行,但相界面移动速度变小,熔化逐渐终止;正常熔化时间越长后,断电后继续熔化的钢量越多。     

Structural characteristics and flammability of low-order coal pyrolysis semi-coke

This study focused on the effects of pyrolysis temperature on the structural characteristics and combustion properties of low rank coal. The combustion performance of semi-coke at different temperatures was studied by using low-temperature pyrolysis technology and non-isothermal thermogravimetric analysis. The variation of functional groups and carbon structure was quantitatively analyzed. The results show that the temperature has a significant effect on the semi-coke structure and flammability. In the middle and low temperature pyrolysis stage, the removal of water, volatile matter and functional groups is mainly carried out, and the degree of condensation and graphitization of carbon atoms is not obvious. The semi-coke performance with a pyrolysis temperature of 1023K is close to that of anthracite. The pyrolysis process is accompanied by the destruction of carbonaceous and the formation of mesopores, which affects the combustion performance. As the temperature increases, the flammability of the semi-coke is lowered, and the chemical structure of the semi-coke is a major factor affecting the flammability. The method of Coast-Redfern integration was used to calculate the kinetic parameters of the semi-coke. As the pyrolysis temperature increases, the activation energy of the combustion reaction increases, which is consistent with the trend of combustion performance change.     

Investigation into the flow behavior of high-temperature ash and low-temperature ash of high calcium coal

The flow behavior of high-temperature ash (HTA) and low-temperature ash (LTA) of high calcium coal in the heating process was investigated systematically. By means of the heating stage microscope, the behavioral changes of samples were studied visually. The composition and mineral matters transformations of HTA and LTA samples were analyzed by X-ray fluorescence and X-ray diffraction. The results show that the original composition of HTA sample is different from that of LTA sample. In addition, the HTA and LTA samples experience the shrinkage, fusion and spreading processes in succession. However, the volume change of HTA sample is different from that of LTA sample. The volume of LTA sample shows a slow change at the temperature lower than 800 °C, while the volume of HTA sample is unchanged. In the temperature range of 800°C–1100 °C, the remarkable shrinkage of HTA and LTA samples are demonstrated. The formation of srebrodolskite and gehlenite attributes to this volume change. Moreover, the sharp shrinkage of HTA and LTA samples is indicated at 1100°C–1300 °C. This is caused by the formation of eutectics. Because of the diverse content and species of mineral matters in LTA sample, the volume change of LTA sample is more remarkable than that of HTA sample. The maximal shrinkages of LTA and HTA sample are 57% and 53%, respectively.     

Mechanism of hydrogen generation from low melting point elements (Ga,In, Sn) on aluminum alloy hydrolysis

The reaction of aluminum water to produce hydrogen is prevented by an alumina film. To prepare a kind of aluminum alloy with instant hydrogen production and high hydrogen yield, this paper investigates the effect of different Ga content and In–Sn ratio on the hydrogen production performance of aluminum alloy, and also observes the effect of hydrogen production at different temperatures. The composition, structure, and thermal properties are observed by Scanning Electron Microscope, X-ray diffraction, and differential scanning calorimetry. With different ratios of In and Sn, they appear as two intermetallic compounds, In₃Sn and InSn₄. When Ga, In, and Sn were added to aluminum together, the hydrolytic properties of the Al-Ga-In-Sn alloys are greatly improved. The paper finally prepared an aluminum alloy with a hydrogen conversion rate of more than 98% and activation energy of 39.2 kJ/mol. Further the development and utilization of hydrogen energy are promoted.     

Investigation on ash deposition characteristics during Zhundong coal combustion

The reserves of Zhundong (ZD) coal in China are huge. However, the high content of Na and Ca induces serious slagging and fouling problems. In this study, the ZD coal was burned in a DTF (drop tube furnace), and the ashes collected at different gas temperature with non-cooling probe were analyzed to obtain the ash particle properties and their combination mode. The results showed that Na, Ca and Fe are the main elements leading to slagging when the gas temperature is about 1000 °C during ZD coal combustion, but their mechanisms are quite different. Some sodium silicates and aluminosilicates and calcium sulfate keep molten state in the ashes collected at 1000 °C. These molten ash particles may impact and adhere on the bare tube surface, and then solidified quickly. With the growth of slag thickness, the depositing surface temperature is increased. The molten ash particles might form a layer of molten film, which could capture the other high fusion temperature particles. The Fe₂O₃ sphere were captured by the formed molten slag and then they blended together to form a new molten slag with lower melting temperature.     

Experimental investigation on melting characteristics of ethanolamine–water binary mixture used as PCM

An experimental investigation of the melting process of ethanolamine–water binary mixture used as PCM (phase change material) in a rectangular enclosure with a heated vertical wall is reported in this work. The liquid–solid interfaces were captured and the instantaneous liquid fraction was presented. The effect of natural convection was studied in terms of the molten fraction and the shape of the solid–liquid interface. The correlations of molten fraction and time-averaged Nusselt number are obtained so that the time of the melting process can be predicted. The results indicate that natural convection enhances the rate of melting compared with the pure conduction model and that pure conduction mechanism only occurs at the initial stage of melting. Conduction–convection coupled model is necessary for predicting melting process exactly.     

A three-dimensional numerical model for a convection-diffusion phase change process during laser melting of ceramic materials

Using a fixed-grid source-based method, a three-dimensional numerical model for a convection-diffusion phase change process during laser melting of ceramic materials has been studied. The model was applied to a realistic binary phase diagram containing a eutectic composition, including both an isothermal phase change occurring at a distinct temperature and a phase change taking place over a temperature range (the “mushy” region phase change). The effects of latent heat of fusion and fluid flow in the melt pool on the temperature, velocity fields and shape of the melt pool were analysed and compared. Results indicated that the effects of latent heat of fusion were more significant than those of fluid flow for two simulation cases, considered in the model. The best prediction accuracy for the profiles of the melt/solid interfaces was achieved from the developed model by considering both the latent heat of fusion and fluid flow in the melt pool.     

Study on the efficiency of effective thermal conductivities on melting characteristics of latent heat storage capsules

Improvement of the thermal conductivity of a phase change materials (PCM) is one effective technique to reduce phase change time in latent heat storage technology. Thermal conductivity is improved by saturating porous metals with phase change materials. The influence of effective thermal conductivity on melting time is studied by analyzing melting characteristics of a heat storage circular capsule in which porous metal saturated with PCM is inserted. Numerical and approximate analyses were made under conditions where there are uniform or non-uniform heat transfer coefficients around the cylindrical surface. Four PCMs (H₂O, octadecane, Li₂CO₃, NaCl) and three metals (copper, aluminum and carbon steel) were selected as specific materials. Porosities of the metals were restricted to be larger than 0.9 in order to keep high capacity of latent heat storage. Results show that considerable reduction in melting time was obtained, especially for low conductivity PCMs and for high heat transfer coefficient. Melting time obtained by approximate analysis agrees well with numerical analysis. A trial estimation of optimum porosity is made balancing the desirable conditions of high latent heat capacity and reduction of melting time. Optimum porosity decreases with increase in heat transfer coefficient.     

温度对纳米氧化镁颗粒污垢特性的影响

为了探讨温度对纳米氧化镁颗粒污垢结垢特性的影响,通过改变循环工质入口温度和水浴温度实验研究了温度对纳米颗粒污垢在交叉缩放椭圆管中的结垢特性,并通过静置沉降实验验证了入口温度对循环工质聚沉情况的影响。结果表明,循环工质入口温度和水浴温度对纳米颗粒污垢特性都有显著的影响。随着循环工质入口温度的升高,污垢热阻渐近值明显减小,并且污垢热阻达到渐近值的时间缩短。随着水浴温度的升高,污垢热阻渐近值也随之减小,但是达到渐近值的时间略有增加。     

Effects on enrichment characteristics of trace elements in fly ash by adding halide salts into the coal during CFB combustion

The effects on enrichment characteristics of trace elements (TEs) in fly ash by adding halide salts into the coal during coal combustion were conducted on a 6 kW_th circulating fluidized bed (CFB) experimental device. Results show that unburn carbon content in fly ash has little relationship with the concentration of TEs namely Hg, As, Pb, Cr and Mn. All the TEs are enriched in fly ash for the raw coal CFB combustion. Concentration of Hg and Mn increases with increasing the addition amount of CaCl₂, NH₄Cl and NH₄Br. As, Pb and Cr enrich in fly ash more strongly when adding more CaCl₂ into the coal while more addition of NH₄Cl and NH₄Br leads to the decrease of their enrichment compared to addition amount of 0.1 wt%. On the whole, putting halide salts into the coal results in the TEs enriched in fly ash, which benefits for TEs removal during the coal combustion. Combining this method with the chemical sequential extraction or thermal treatment of the fly ash will be a promising way to realize the TEs removal and their recovery.     

Experimental study on gasification and kinetic characteristics of inferior coal with high ash content under CO2 atmosphere

The effect of heating rate and particle size on gasification of one inferior coal was experimentally studied. A homogeneous reaction model was used to calculate kinetic parameters with the Freeman–Carroll method. The results show that gasification reactivity can be enhanced by reduction of coal particle size and increase of heating rate. Additionally, coal ash plays a catalytic role to a certain extent on gasification. It was also found that the reaction rate can be enhanced significantly, when increasing the ash-coal weight ratio from 1:2 to 2:1. The gasification order under CO₂ atmosphere is close to 1. There is a kinetic compensation effect between activation energy and frequency factor for the gasification of the inferior coal investigated.     

Experimental investigation of ice and snow melting process on pavement utilizing geothermal tail water

Road ice and snow melting based on low temperature geothermal tail water is of significance to realize energy cascading utilization. A small scale ice and snow melting system is built in this work. Experiments of dynamic melting processes of crushed ice, solid ice, artificial snow and natural snow are conducted on concrete pavement. The results show that the melting process of ice and snow includes three phases: a starting period, a linear period and an accelerated period. The critical value of the snow free area ratio between the linear period and the accelerated period is about 0.6. The physical properties of ice and snow, linked with ambient conditions, have an obvious effect on the melting process. The difference of melting velocity and melting time between ice and snow is compared. To reduce energy consumption, the formation of ice on roads should be avoided if possible. The idling process is an effective pathway to improve the performance of melting systems. It is feasible to utilize geothermal tail water of about 40 °C for melting ice and snow on winter roads, and it is unnecessary to keep too high fluid temperatures during the practical design and applications. Besides, with the exception of solid ice, the density and porosity of snow and ice tend to be decreasing and increasing, respectively, as the ambient temperature decreases.     

成灰温度对污泥灰矿物质演变及熔融特性的影响研究

采用STA、SEM、XRD等谱学表征技术对不同成灰温度下的污泥灰样进行理化特性分析。研究表明,低温灰样仍含有残余未燃尽物而呈黑棕色,矿物质成分变以方解石、石英以及焦磷酸盐为主,随着成灰温度升高,灰样中的未燃尽物逐渐燃烧分解而逐渐变为铁红色,并形成较多晶枝结构,直至熔融,同时矿物质成分变化显著,主要以中长石类、硬石膏、赤铁矿以及磷酸正盐为主。同步热分析实验表明,随着受热温度升高,不同成灰温度下的灰样均出现了吸附水、结晶水析出,污泥灰残余有机物燃烧分解,白云石、方解石和白云母分解,以及随后的硬石膏分解等失重阶段,而且成灰温度越低,终止失重质量越大。由于低温灰样保留了较多的污泥原有特征,因此吸热量大于高温灰样。     

A combined experimental and computational study on the melting behavior of a medium temperature phase change storage material inside shell and tube heat exchanger

A combined experimental and numerical study is performed aiming to understand the role of buoyancy-driven convection during constrained melting of phase change materials (PCMs) inside a shell and tube heat exchanger. A series of experiments is conducted to investigate the effect of increasing the inlet temperature of the heat transfer fluid (HTF) on the charging process (melting) of the PCM. The computations are based on an iterative, finite-volume numerical procedure that incorporates a single-domain enthalpy formulation for simulation of the phase change phenomenon. It was observed from experimental results that the melting front appeared at different times at positions close to the HTF tube and progressing at different rates outwards towards the shell. The computational results show that by increasing the inlet water temperature to 80 °C, the total melting time is decreased to 37%.     

Variations in surface fractal characteristics of coal subjected to liquid CO2 phase change fracturing

Enhancement of coal permeability plays the key role in methane extraction underground coalmine. As the physical blasting method, liquid CO₂ phase change fracturing (LCPCF) technique can effectively stimulate the coal reservoirs, further enhance the coal permeability. In this work, the combination of scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) was adopted to quantitatively evaluate the variations in the pore/fracture structure and fractal characteristics of coal subjected to LCPCF. Fracture fractal dimension (D_F) and pore fractal dimensions (D_P1, D_P2) are calculated based on the SEM images and MIP data, respectively. After conducting LCPCF, a large number of microfracture and macropore clusters are generated and observed in SEM images. The maximum fracture ratio in treated coal is enhanced by approximately 200% compared with that in raw coal. MIP results show that pore distribution within coal exhibits a nonlinear alteration with four stages and the pore connectivity of coal is improved after LCPCF. The impact of LCPCF on pore/microfracture characteristics of coal is closely correlated with the distance from the fracturing borehole. The maximum values of D_F and D_P1 are found at the distance of around 2.0 m, indicating the best fracturing effect at such distance. It has been found that the effective influence scope of LCPCF on coal is within 7.0 m. The evolution of coal pore/fracture structure during LCPCF is attributed to the new pore/fracture generation and the conversion of original micropores into larger ones. Knowledge of these properties is essential for the application LCPCF in methane drainage.     

Numerical study on the melting thermal characteristics of a microencapsulated phase change plate

ABSTRACT

The melting thermal characteristics of a microencapsulated phase change material (MEPCM) plate under constant heat flux are numerically investigated. The effective property relations of the MEPCM plate related to the parameters of base materials are first established and verified by the measured thermal properties of 10 samples. A one-dimensional phase change thermal model based on the enthalpy method is built, and the predicted results are also verified with test data. The temperature profile and phase interface movement in the MEPCM plate are discussed, and the effects of Stefan number, phase change temperature range, particle and core fraction, and additive fraction are also analyzed. Three states of solid, mushy, and fluid phases of phase change material (PCM) core divide the melting process of the MEPCM plate into five stages as follows: Fo ≤ 0.1, 0.1 < Fo ≤ 0.2, 0.2 < Fo ≤ 0.9, 0.9 < Fo ≤ 1.2, and Fo ≥ 1.2. The time point of regular regime for heat transfer in the MEPCM plate is Fo = 0.2. The addition of conductivity additive homogenizes the temperature profile in the MEPCM plate. Under the combined effects of thermal diffusivity and Ste number, an optimum additive fraction exists for the MEPCM plate to achieve the minimum melting completion time or the maximum latent storage efficiency.