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。     

准东煤灰熔融特性试验研究

将神华准东煤（神华煤）和天池能源准东煤（天池煤）与碱沟煤按照不同质量掺混比进行混合并制得灰样,将NaCl、CaO、Al2O3和SiO2按不同添加比例加入神华煤和天池煤并制成灰样,对上述混合灰样的熔融特性进行研究.结果表明：碱沟煤掺混2种准东煤后,随着准东煤质量掺混比的增大,混合灰各个灰熔点特征温度先降低后升高;随着灰样中Na含量增加,准东煤灰样的变形温度显著降低,软化温度、半球温度和流动温度先降低后趋于不变;当灰样中Na含量达到一定比例后,NaCl对准东煤灰熔融特性的影响明显减弱;CaO对准东煤灰熔点的影响较复杂,可以降低也可以提高灰熔点;随着Al2O3添加比例的增加,准东煤灰熔点先升高后急剧降低;随着SiO2添加比例的增加,神华煤灰样的变形温度先升高后降低,而天池煤灰样的变形温度逐步升高,其他3个特征温度均逐渐降低.     

煤灰熔融行为及其矿物质作用机制的量化研究

选取典型高灰熔点和低灰熔点煤种,利用X射线衍射仪(XRD)和扫描电镜能谱仪(SEMEDX)对高温气化条件下煤灰熔融行为及其矿物质演变规律进行了实验研究与量子化学计算.结果表明:高温下大量莫来石的生成是导致煤灰试样A具有高灰熔融温度的主要原因;煤灰试样B中由于存在较多的硬石膏、钠长石等低熔融矿物质,且CaO与莫来石反应生成钙长石与钙黄长石的化学反应在煤灰试样B熔融过程中起到了关键作用,从而使其具有低的熔融温度.经量子化学计算分析表明,由于莫来石易与电子接受体结合而难与电子给予体结合,在煤灰熔融过程中,莫来石易与煤灰中常见的碱性阳离子(Ca2+、Mg2+、Fe2+、Na+、K+)电子接受体反应生成其他物质,通过添加不同的阳离子可促使莫来石向不同矿物质转变,可以进一步控制煤灰的熔融变化过程及其熔融温度.     

基于不同输入参数的煤灰熔点预测模型及改进方法

为提高煤灰熔点预测精度,采用支持向量机算法,分别建立了以8种煤灰主要成分为输入量的8输入参数模型以及以8种灰成分加5种煤灰熔融性参数为输入的13输入参数模型,用于预测煤灰软化温度,并利用误差补偿方法对13输入参数模型进行了改进.结果显示,13输入参数模型相比8输入参数模型可以缩小灰熔点预测误差区间,尤其使负误差减小;相...     

添加剂对煤灰熔融特性的影响

在8种煤灰中添加不同矿物质作助熔剂,对煤灰熔融特性进行研究;并用灰色系统方法对8种煤灰的矿物质成分和综合成分与煤灰熔融特性的相关度进行研究,然后对实验方法与灰色系统关联度方法进行比较研究.结果表明:添加剂可以降低煤灰熔融温度,也可以升高煤灰熔融温度,添加剂CaCO3为30%时,F煤和D煤得到最低熔点分别为1 250℃和1 350℃;添加剂硼砂(Na2B4O7·10H2O)为15%时,F煤到最低灰熔点1 150℃,硼砂为20%时,D煤可到熔点1 300℃以下.根据关联度方法可得到:酸性矿物质是影响煤灰熔融温度的主要因素,钠系物质对灰熔融性的关联度比钙系物质影响大,数学方法计算结果与实验结果相吻合.     

添加剂对垃圾焚烧炉飞灰熔融特性的影响

将SiO2、CaO和Al2O3按不同比例与垃圾焚烧炉飞灰均匀混合,对混合后试样的熔融特性进行实验研究。结果表明:当添加剂加入量在15%左右时,试样的灼烧减量基本趋于稳定,添加量过高或过低试样灼烧减量波动均很大。适量(15%左右)的加入3种添加剂时,SiO2可使试样达到更好的熔融效果,CaO不利于试样的熔融,Al2O3可提高试样的硬度和致密性。添加剂对熔融试样的重金属分布有显著影响,添加SiO2、CaO均能促使Cr、Ni固溶在熔融体中,且SiO2含量增加有助于As的挥发;而CaO可抑制As挥发。Al2O3除对Ni固溶有正面影响外,对Cr、As、Cu的固溶有负面影响。     

煤灰对石油焦水蒸气气化的影响

通过热天平实验，研究了煤灰存在时石油焦的水蒸气气化反应行为．实验研究发现，煤灰对石油焦水蒸气气化反应活性具有较好的催化作用，而且催化作用的好坏受煤灰添加均匀性的影响．煤灰含量增加，石油焦气化反应速率增加；在煤灰含量较小时，煤灰含量的变化对反应速率的影响较大．但随着煤灰含量增加，煤灰含量的变化对反应速率的影响逐渐不明显．煤灰的存在降低了石油焦气化反应的反应活化能．     

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.     

循环流化床锅炉飞灰特性研究

CFB锅炉飞灰的化学成分以及物理特性和煤粉炉有所不同.研究讨论了CFB锅炉飞灰和煤粉炉飞灰的区别.在实验中发现CFB锅炉飞灰中SiO2、Al2O3、TFeO、CaO、MgO的含量随着粒度的变化而有规律地变化.随着粒度的减小,飞灰中SiO2的含量逐渐降低,而Al2O3、TFeO、CaO、MgO含量则逐渐升高.在实验的基础上对铁元素存在形式进行了理论上的分析,得出在CFB锅炉和煤粉炉的燃煤飞灰中,铁元素因为运行工况的不同其存在形式不同,进而呈现出颜色上的差异.CFB锅炉飞灰含碳量高,比电阻低.     

神华煤配煤的试验研究

介绍了选用榆林D矿区神华煤和平朔煤进行配煤试验,通过工业分析、灰熔点和灰成分测试分析研究混煤的灰熔融特性。掺入平朔煤能有效地改变神华煤高钙高铁的灰成分特点,提高神华煤的灰熔点。不同混配比例混煤的沉降炉燃烧结渣试验结果表明,平朔煤能降低神华煤的粘结性、熔融性和结渣趋势,且灰渣易吹落。     

中国南方典型农业生物质结渣特性实验研究

实验研究了广东省典型农业生物质稻杆、甘蔗渣/叶的燃烧结渣特性。采用GB/T212-2001和ASTM E1755标准进行灰化实验,采用角锥法和一步法检测生物质的熔融特性。实验结果证实ASTM的低温灰化标准更适合稻杆类高无机盐含量的生物质原料。稻杆中碱金属氧化物含量达20%以上,是导致灰渣粘结和熔融的主要因素。由于角锥法灰熔点检测法提前将部分碱金属和Cl元素转化和析出,导致检测结果远高于实际燃烧的熔融温度;相比而言,一步法更具有直观性和指导作用。通过一步法实验获得稻杆临界结渣温度为700℃ ~ 750℃,甘蔗渣为850℃ ~ 900℃,甘蔗叶为900℃ ~ 950℃。CaO和Al₂O₃添加剂对于生物质燃烧过程具有一定的抗结渣功能,CaO通过与SiO₂ (s) 反应生成高熔点的固态Ca₃Si₂O₇ (s) 和MgOCa₃O₃Si₂O₄ (s),因此能消耗物料周围的SiO₂ (s),抑制低温共融;Al₂O₃则通过生成高熔点温度的固态KAlSiO₄和固态KAlSi₂O₆,减少低温共熔现象的发生。     

Computer-controlled scanning electron microscopy of minerals in coal-Implications for ash deposition

The nature of mineral matter in coal determines its transformation into ash during combustion and the nature of resulting ash (e.g. chemical composition and particle size distribution), and subsequently influences the ash deposition behaviour. The behaviour of mineral matter is primarily influenced by two parameters: the mineral grain size, and whether the mineral grains are within the coal matrix or not. Computer-controlled scanning electron microscopy (CCSEM) of coal provides such information on mineral matter in coal. CCSEM data are, therefore, processed to predict the fouling and slagging characteristics of several coals. The fraction of basic oxides in each mineral grain may be considered as an indicator of stickiness of the corresponding ash particle due to formation of low melting compounds. The cumulative mass fraction of mineral grains with certain basic oxides or viscosity of resulting ash particles from included and excluded minerals are proposed as alternative indices for ash deposition.

The excluded mineral matter is in equilibrium with the combustion flue gases at the gas temperatures, whereas the included minerals are in equilibrium with the atmosphere within char at the burning char particle temperature. It is predicted from thermodynamic calculations based on this understanding that almost all the evaporation is either from the included mineral matter or from the atomically dispersed minerals in coal. This is due to the high temperature and reducing atmosphere inside the char particle. The release of the evaporated species is controlled by diffusion through the burning char particle and, therefore, may be estimated theoretically. The amount of mineral matter that is vaporized may then be related to fouling, whereas the melt phase present on the surface of large ash particles may be related to slagging. The theoretical speculations on the physical character of ash derived from these indices are compared with the experimental data obtained from combustion of coals in a drop-tube furnace.     

含盐有机废液焚烧煤灰熔融特性试验研究

研究3种不同灰熔融性的煤(元宝山褐煤、崔家沟烟煤、徐州烟煤,分别简称为Y煤、C煤和X煤)与不同含盐率(碱金属钠盐Na2SO4、NaNO3、Na2CO3等在红水中的含量,通称含盐率)化工废液红水混合焚烧的灰熔融特性。研究结果表明,在不添加石灰石时,随着红水含盐率的增加,X煤、C煤的灰熔融温度均呈下降趋势,其中在相同的含盐率下X煤的灰熔融温度下降较多,Y煤的灰熔融温度则呈先下降后增加再下降的趋势;添加石灰石(Ca/S=2.0)后,随着红水含盐率的增加,X煤的灰熔融温度呈先下降后增加的趋势,且在红水含盐率为10%处其4个特征温度均存在一个最小值,而C煤和Y煤的灰熔融温度变化情况与不加石灰石时类似,但变化幅度相对较小;在一定的含盐率(15%)下,X煤和C煤的灰熔融温度均随着石灰石量的增加,先下降后增加,但X煤的变化明显,Y煤的变形温度、软化温度增加,而半球温度和流动温度则先下降后增加。研究结果为含盐有机废液在流化床中焚烧时防止床料结焦提供理论依据。     

Effect of temperature on Lu’an bituminous char structure evolution in pyrolysis and combustion

In the process of pyrolysis and combustion of coal particles, coal structure evolution will be affected by the ash behavior, which will further affect the char reactivity, especially in the ash melting temperature zone. Lu’an bituminous char and ash samples were prepared at the N₂ and air atmospheres respectively across ash melting temperature. A scanning electron microscope (SEM) was used to observe the morphology of char and ash. The specific surface area (SSA) analyzer and thermogravimetric analyzer were respectively adopted to obtain the pore structure characteristics of the coal chars and combustion parameters. Besides, an X-ray diffractometer (XRD) was applied to investigate the graphitization degree of coal chars prepared at different pyrolysis temperatures. The SEM results indicated that the number density and physical dimension of ash spheres exuded from the char particles both gradually increased with the increasing temperature, thus the coalescence of ash spheres could be observed obviously above 1100°C. Some flocculent materials appeared on the surface of the char particles at 1300°C, and it could be speculated that β-Si₃N₄ was generated in the pyrolysis process under N₂. The SSA of the chars decreased with the increasing pyrolysis temperature. Inside the char particles, the micropore area and its proportion in the SSA also declined as the pyrolysis temperature increased. Furthermore, the constantly increasing pyrolysis temperature also caused the reactivity of char decrease, which is consistent with the results obtained by XRD. The higher combustion temperature resulted in the lower porosity and more fragments of the ash.     

煤粉锅炉掺烧高炉煤气对煤粉燃尽影响的研究

针对某钢铁企业实际燃用的燃料，计算得到了高炉煤气掺烧率变化引起的烟气生产量变化和燃料理论燃烧温度变化曲线，在此基础上分析了高炉煤气掺烧对煤粉燃尽影响的各种因素，其中煤粉在炉膛内停留时间缩短、炉膛温度水平下降是最主要的因素。通过在一维炉和滴管炉上进行的温度对该种煤粉燃尽影响的试验研究，分析了高炉煤气掺烧率超过20%时飞灰可燃物含量急剧上升的原因，从而提出基于燃尽的煤粉锅炉掺烧高炉煤气的最佳热量掺烧率应该在25％左右。图5表3参6     

垃圾焚烧灰渣的成分分析及其熔融特性

在垃圾焚烧余热锅炉中,垃圾灰熔融特性是决定灰沉积危害程度的最重要特性之一。本研究通过测定垃圾灰的成分、灰熔点,系统分析垃圾灰熔融特性与其成分的关系,以及垃圾灰与低熔点煤灰在熔融特性与成分之间的区别,并以此对垃圾燃烧提出一些建议。     

影响烧结过程最初液相形成的因素分析

试验考察添加SiO2、Al2O3和MgO对铁酸盐黏结相(20%CaO-80%Fe2O3)最初液相熔化行为的影响,同时考察对于最初液相形成矿石中脉石含量与CaO的关系。试验结果表明:矿石中的SiO2和Al2O3脉石成分对烧结过程中最初熔体的形成都有抑制作用,但从熔化温度区间考察,2%~6%SiO2的添加可以显著减小熔体的熔化时间,而不同含量Al2O3和MgO的添加都会增加熔体的熔化时间;同时随着矿石中脉石含量的增加,形成最低液相的CaO含量也在增加。     

不同添加剂对生物质灰分及床料的熔融性影响

使用灰熔点法,分析Al2O3、高岭土、CaO对稻草、麦秸秆与河砂及煤灰混合物的熔融性质的影响,研究结果表明灰熔点法在预测添加剂对生物质灰分与床料熔融粘结改善方面具有较强的适用性。煤灰与两种生物质混合物的灰熔点要高于河砂与两种生物质灰分混合物的灰熔点,麦秸秆与床料混合后的灰熔点要高于相同奈件下稻草与床料混合后的灰熔点,三种添加剂对提高生物质灰与煤灰、河砂混合物的灰熔点结果从高到低依次是Al2O3,高岭土,CaO。     

煤灰对流化床氮氧化物排放影响的试验研究

在流化床试验台上分别燃烧典型烟煤和褐煤,测量加入煤灰和煤灰中无机矿物质（CaO、MgO、Fe2O3、Al2O3、CaSO4、MgSO4）前后N2O和NO排放质量浓度的变化,研究煤灰对流化床氮氧化物排放的影响及其主要活性成分.结果表明：煤灰能降低N2O排放质量浓度,提高NO排放质量浓度;燃料氮向NOx的总转化率随着灰分质量分数的增加而提高;煤灰中影响氮氧化物排放的主要活性成分为CaO、Fe2O3和MgO.     

焦炭体系下添加剂对CO2重整CH4特性的影响

利用固定床试验装置,以SiO2、MgO和CaO为添加剂,在焦炭体系下进行了CO2重整CH4活性的试验研究,并分析了反应温度和CaO含量对重整反应的影响.利用热重分析仪和扫描电镜分别对重整过程中焦炭失重和反应后焦炭微观形貌进行研究,探讨了反应机理.结果表明:加入SiO2后,制得的焦炭催化活性降低,加入CaO和MgO后,制得的焦炭催化活性提高,且CaO优于MgO;温度对重整反应影响显著,随着温度升高,反应气转化率增加;CaO添加剂含量控制在15%~20%之间对反应速率的提高较合适,且CaO的添加使焦炭失重速率也有所提高.