新型双流化床炉内NOx生成特性数值模拟

运用煤燃烧及NO_x生成的详细化学反应机理,通过搭建一维化学反应器网络（1D-CRN）,对一个新型双流化床（DCFB）内燃料型N转化为NO_x的基元化学反应进行了敏感性分析并讨论了反应温度、过量空气系数以及一、二次风配比对燃料型NO_x生成的影响。研究发现,在相同条件下,循环流化床炉膛出口的NO_x排放值为224.48 mg·m^-3,而双流化床炉膛出口的NO_x排放值为97.29 mg·m^-3,双流化床对于燃料型NO_x的减排幅度达到了56.66%。此外,促进NO_x生成的基元反应主要有R398（NH₂+O?HNO+H）、R1-N-1（N-Vol?NH₃+HCN）、R569（NCO+O₂?NO+CO₂）、R17（H+O₂?O+OH）等反应,而抑制NO_x生成的反应包括R411（NH₂+NO?N₂+H₂O）、R412（NH₂+NO?NNH+OH）、R570（NCO+NO?N₂O+CO）、R571（NCO+NO?N₂+CO₂）以及R5（Char+NO?Char+N₂+O₂）和R6（Soot+NO?n Soot+N₂+CO）等反应。这说明反应区域氧气浓度是影响NO_x生成的关键,低氧浓度可抑制燃料N向NO_x转化。另外,NO_x生成值随着反应温度的升高而降低,但随着过量空气系数和一次风所占比例的增大而增加。     

高海拔地区大型循环流化床锅炉特性研究

结合青海盐湖工业股份有限公司供热中心4×480 t/h循环流化床(CFB)锅炉的启动调试,通过理论论证及实际应用,对高海拔地区大型循环流化床锅炉特性进行研究,解决了低气压地区流化床锅炉高负荷工况下频繁结焦问题。给出了流化床锅炉正常运行所要维持的流化风速范围,明确了高海拔地区循环流化床锅炉流化风速计算应选用标态风量,与低海拔地区一致,使得此类技术具备实际可参考性及可操作性,对解决同类型问题有一定的参考价值。     

Model for drying during fluidized-bed combustion of wet low-rank coals

An unsteady state heat conduction model with a convective boundary condition is proposed for the drying of low-rank, high-porosity coals, such as lignites, during fluidized-bed combustion. The drying front is assumed to be the receding surface of a wet core. The solution technique for this moving boundary problem is based on the heat balance integral approach with immobilization of the moving boundary by a change in space variable. The governing cubic equation describing the drying curve in dimensionless form may be solved easily by the Newton—Raphson method. The model predictions are compared with experimental data for Mississippi lignite with excellent agreement. A correlation for estimation of total drying time is proposed. The temperature profiles obtained may be used for the study of the coupled drying and devolatilization in fluidized-bed combustors. The profiles could also be of importance in the study of formation of fissures/cracks in lignites subjected to intense heating conditions encountered during fluidized-bed combustion.     

Regulating characteristics of loop seal in a 65 t/h oil shale-fired circulating fluidized bed boiler

In this paper, an industrial cold experiment was conducted for studying regulating characteristics of a loop seal in a 65 t/h oil shale-fired circulating fluidized bed (CFB) boiler. The starting characteristic of the loop seal, and the effect of the supplying air and the fluidizing air in the loop seal were investigated. Compared with other regulating modes, the combined regulating mode of keeping the fluidizing air rate constant and regulating the supplying air rate can make the loop seal obtain better regulating quality, and offer more reliable guarantee for steady operation of the CFB boiler as well. In order to prevent circulating material depositing and slagging at the bottom of the loop seal, it was suggested that the fluidizing air rate and the supplying air rate is 2-3 and 1.2-1.5 times of the minimum fluidizing velocity of circulating material, respectively. These experimental results may be used as a reference for regulating the loop seal of the 65 t/h CFB boiler in hot condition and designing a new loop seal.     

循环流化床锅炉SNCR脱硝系统的模型优化及应用

介绍了选择性非催化还原法(SNCR)脱硝系统的特点,针对传统SNCR系统存在的自动化投入率低、NO_x浓度波动大、取样系统简单、样气不具代表性、控制效果欠佳等问题,提出了网格法混合取样改造、基于预测控制的SNCR优化控制方法和炉内氧含量优化控制模型,克服了传统PID控制大滞后、抗延迟能力差、控制精度不高等问题。实际应用效果表明,优化改造后净烟气NO_x浓度波动显著下降,系统喷氨量整体减少,有效降低了氨逃逸。     

小颗粒油页岩及半焦CFB锅炉燃烧适应性研究

油页岩经低温干馏可以得到页岩油,因生产工艺限制,干馏炉无法使用粒径12 mm以下的油页岩,同时会产生大量副产品(页岩半焦)。为提高副产品的利用能力,实现资源利用最大化。通过在1 MW_(th)CFB燃烧试验台对小颗粒页岩及页岩半焦进行试烧试验,研究小颗粒页岩及页岩半焦的理化特性、着火特性、燃尽特性、结焦特性。试验结果表明,控制床温在720~850℃内,由油页岩小颗粒和半焦掺混而成的设计燃料在试验台采用CFB方式能够稳定燃烧,试验各工况灰渣含碳量均低于1.81%,试验燃料较易燃尽。CFB锅炉适合油页岩小颗粒与半焦掺烧利用,且燃烧效率高,燃烧稳定性较好。     

Characterisation of some Australian oil shale using thermal, X-ray and IR techniques

Thermogravimetric analysis (TGA), Diffuse Reflectance Infrared Fourier Transforms Spectroscopy (DRIFTS) and X-ray diffraction (XRD) were used in conjunction to characterise oil shale samples from an Australian Tertiary oil shale deposit. Results from these techniques were compared with conventional Modified Fisher Assay (MFA) data. DRIFTS and TGA results showed clear correlations with each other as well as with the MFA values. DRIFTS results indicated that most of the kerogen is in aliphatic hydrocarbon form. It was evident from TGA analysis that the weight loss in the 450-550 °C temperature region has a strong and direct correlation with the amount of oil in the samples, as determined by the MFA method. Calibration curves were generated in which oil content can be predicted from TGA and DRIFTS data. The combination of TGA and DRIFTS is mostly useful in examining organic matter in oil shale while DRIFTS and XRD combination is useful in examining the minerals phases. XRD and DRIFTS showed good agreement in identifying the presence of minerals such as quartz, clay and carbonates. Combination of these three techniques can provide an alternative and inexpensive method to the MFA analysis in determining the kerogen content, while overcoming the limitations of each other.     

The chemistry and mineralogy of the Negev oil shale ashes

The characteristic feature of the oil shale ashes produced by fluidized bed combustion (700-800 °C) in PAMA's demonstration power plant is the large amount of amorphous phases, Ca-Al-silicates and Al-silicates, together with anhydrite and lime. Practically all the S and heavy metals in the oil shales are retained in the ash, which, from an ecological point of view, is important. Two kinds of ashes were examined: industrial ashes produced at PAMA's demonstration plant and ashes produced in laboratory experiments. Three different types of ash are produced at the demonstration plant. Ash Cooler (AC), which is comparable to bottom ash in coal power plants. This ash is produced from oil shale subjected to the lowest temperatures and is the most coarse-grained. It contains relatively larger quantities of unaltered minerals (calcite, clays, apatite, etc.) than the other two. The two other ashes Boiler Bank (BB) and Fly Ash (FAS) are not much different from each other and both may be compared to fly ash in coal power plants. Both BB and FAS ashes contain more authigenic (formed in the boiler) phases than AC. The results of the laboratory experiments show that the main factor in the raw material controlling the mineralogy and chemistry of the oil shale ashes is the Al₂O₃ concentration (clay content), and not the organic matter concentration.     

煤粉炉和循环流化床锅炉飞灰吸附汞动力学及其吸附机制

在固定床吸附反应器内对两台300MW等级燃煤发电机组循环流化床锅炉和煤粉锅炉飞灰样品进行气相零价汞吸附实验,通过改变实验工况研究温度、入口汞浓度和入口气体流量对飞灰汞吸附能力的影响。采用颗粒内扩散模型、准一阶和准二阶动力学模型、耶洛维奇（Elovich）模型对实验数据分别进行拟合,从动力学的角度探讨两种锅炉飞灰对气相零价汞吸附的影响机制以及两种锅炉飞灰与气相零价汞之间吸附动力学行为差异。结果表明：相同工况下循环流化床锅炉飞灰汞吸附过程的穿透时间和平衡吸附量远大于煤粉锅炉飞灰。吸附温度为150℃时,两种锅炉飞灰对气相零价汞的平衡吸附量最大。由于外扩散阻力随气体入口流量的增加而减小,入口汞浓度的增加可提高传质推动力,飞灰对汞的吸附得以增强。动力学分析表明飞灰的零价汞吸附由外扩散、内扩散和表面化学吸附共同控制,其中表面化学吸附是该吸附过程中的控制步骤;准二阶动力学模型和Elovich动力学模型更适合于描述该吸附过程。相同实验条件下,循环流化床锅炉飞灰吸附过程拟合所得的颗粒内扩散系数、准一阶动力学常数和初始吸附速率均大于煤粉锅炉飞灰。     

Co-current combustion of oil shale - Part 2: Structure of the combustion front

Timahdit oil shale was used as a porous medium to characterize the structure of a combustion front propagating with co-current downward air supply. A new 1D experimental device was first calibrated using a model porous medium. With the model porous medium, the front propagates as a plane and horizontal surface while using oil shale the front propagates as an inclined curved surface. The peak temperature was 1100 °C; despite the relatively large diameter of the cell (91 mm) and the good thermal insulation, the heat losses were estimated at 42% of the heat released by the combustion. The thickness of the front was characterized using a new gas micro-sampling system: the char oxidation and the carbonate decarbonation zones are approximately 10 and 15 mm thick, respectively. The oil formed during the pyrolysis is adsorbed in the porous medium in the course of the experiment, and expulsed from the cell by the end.     

Flow structure and combustion characteristic of 65 t/h oil shale-fired circulating fluidized bed riser—2: Dilute phase

In this paper, a 65 t/h oil shale-fired circulating fluidized bed (CFB) boiler was put into commercial operation in Huadian of China in 1996 and industrial hot experiment was done for studying the flow structure and combustion characteristic of CFB dilute phase regime. Flow structure and solid flux of dilute phase regime were investigated along both vertical direction and horizontal direction under different boiler loads. Particle-size distribution and carbon content of oil shale combustion residues were obtained. Experimental investigation shows that SO₂ concentration decreases with increasing the furnace height, and NO_X emission can be reduced by adopting staged combustion technology, low-temperature combustion and circulating combustion. Experimental results are valuable for adjusting the 65 t/h boiler and designing large-scale oil shale-fired CFB boiler. At the same time, the experiment lays a foundation for modeling the flow structure, combustion, heat transfer and abrasion of oil shale-fired CFB dilute phase regime.     

Co-current combustion of oil shale - Part 1: Characterization of the solid and gaseous products

Co-current combustion front propagation in a bed of crushed oil shale (OS) leads to the production of liquid oil, of a flue gas and of a solid residue. The objective of this paper was to provide a detailed chemical characterization of Timahdit oil shale and of its smoldering combustion products. The amount of fixed carbon (FC) formed during devolatilization is measured at 4.7% of the initial mass of oil shale whatever the heating rate in the range 50-900 K min⁻¹. The combustion of oil shale was operated using a mix of 75/25 wt. of OS/sand with an air supply of 1460 l min⁻¹ m⁻². In these conditions, not all the FC is oxidized at the passage of the front, but 88% only, with a partitioning of 56.5% into CO and the rest into CO₂. A calorific gas with a lower calorific value of 54 kJ mol⁻¹ is produced. Approximately 52% of the organic matter from OS is recovered as liquid oil. The front decarbonates 83% of carbonates.     

Calculation of qualitative and quantitative composition of Estonian oil shale and its combustion products. Part 1. Calculation on the basis of heating value

A method for calculation of the composition of Estonian oil shale and its combustion products is based on the various correlations governing the composition of this oil shale, and relations between its components. To understand better the properties of oil shale and the influence of mining conditions on oil shale quality, a general characterisation of Estonian oil shale is first presented. This unique fuel is utilized for power production, by direct firing in boilers. This paper presents calculations useful for the boiler design engineer for estimating the average characteristics of received oil shale as well as the possible deviations from these mean values.

The calculations in this part allow finding the composition of oil shale and the composition of combustion products of oil shale based only upon its heating value. Various considerations in performing oil shale combustion calculation are presented. A calculational example is presented in the appendix of this part. Part 2 of this study extends the method, given the availability of additional fuel analysis data.     

黄磷尾气在循环流化床锅炉中的掺烧使用

国内大部分中小型黄磷企业受制于矿、电因素无法连续稳定生产,给黄磷尾气的净化和规模化综合利用造成很大困难。为适应这一工况,提高黄磷尾气的利用率,分析黄磷尾气对热工设备的腐蚀机制,在降低投资和净化成本的基础上,探索出在循环流化床锅炉中掺烧黄磷尾气的方法,并辅以脱硫固磷、超音速喷涂等防腐蚀措施,并对防腐机理进行分析。锅炉近十年运行安全平稳,达到了节能减排的目的。     

Countermeasures against alkali-related problems during combustion of biomass in a circulating fluidized bed boiler

The purpose of this work was to study different ways to mitigate alkali-related problems during combustion of biomass in circulating fluidized beds. Wood chips and wood pellets were fired together with straw pellets, while the tendency to agglomerate and form deposits was monitored. In addition to a reference case, a number of countermeasures were applied in related tests. Those were addition of elemental sulphur, ammonium sulphate and kaolin to a bed of silica sand, as well as use of olivine sand and blast-furnace slag as alternative bed materials. The agglomeration temperature, composition and structure of bed-ash samples were examined. The flue-gas composition, including gaseous alkali chlorides, was measured in the hot flue gases and in the stack. Particles in the flue gas were collected and analysed for size distribution and composition. Deposits were collected on a probe in hot flue gases and their amount and composition were analysed. Addition of kaolin was found to be the best method to counteract the agglomeration problem. The deposition problem is effectively counteracted with addition of ammonium sulphate, while kaolin is too expensive to be used commercially against deposits, and sulphur is less effective than ammonium sulphate.     

Kinetics of pyrolysis and combustion of oil shale sample from thermogravimetric data

Thermogravimetric (TG) data of oil shale obtained at MI (Waste to Energy laboratory) were studied to evaluate the kinetic parameters for El-Lujjun oil shale samples. Different heating rates were employed simulating pyrolysis reaction using Nitrogen as purging gas up to ∼800 °C. The extent of char combustion was found out by relating TG data for pyrolysis and combustion with the ultimate analysis. Due to distinct behavior of oil shale during pyrolysis, TG curves were divided into three separate events: moisture release; devolatization; and evolution of fixed carbon/char, where for each event, kinetic parameters, based on Arrhenius theory, were calculated. Three methods were used and compared: integral method; direct Arrhenius plot method; and temperature integral approximation method. Results showed that integral method is closer to the experiment, while no relationship was observed between activation energy and the heating rate.     

An advanced ash fusion study on the melting behaviour of coal,oil shale and blends under gasification conditions using picture analysis andgraphing method

This study investigates the potential of solid fuel blending as an effective approach to manipulate ash melting behaviour to alleviate ash-related problems during gasification, thus improving design, operabil-ity and safety. The ash fusion characteristics of Qinghai bituminous coal together with Fushun, Xinghua and Laoheishan oil shales (and their respective blends) were quantified using a novel picture analysis and graphing method, which incorporates conventional ash fusion study, dilatometry and sintering strength test, in a CO/CO2 atmosphere. This image-based characterisation method was used to monitor and quan-tify the complete melting behaviour of ash samples from room temperature to 1520 ℃. The impacts of blending on compositional changes during heating were determined experimentally via X-ray diffraction and validated computationally using FactSage. Results showed that the melting point of Qinghai coal ash to be the lowest at 1116 ℃, but would increase up to 1208 ℃, 1161 ℃ and 1160 ℃ with the addition of 30％–50％ of Laoheishan, Fushun, and Xinghua oil shales, respectively. The formation of high-melting anorthite and mullite structures inhibits the formation of low-melting hercynite. However, the sintering point of Qinghai coal ash was seen to decrease from 1005 ℃ to 855 ℃, 834 ℃, and 819 ℃ in the same blends due to the formation of low-melting aluminosilicate. Results also showed that blending directly influences the sintering strength during the various stages of melting. The key finding from this study is that it is possible to mitigate against the severe ash slagging and fouling issue arising from high calcium and iron coals by co-gasification with a high silica-alumina oil shale. Moreover, blending coals with oil shales can also modify the ash melting behaviour of fuels to create the optimal ash chemistry that meets the design specification of the gasifier, without adversely affecting thermal performance.     

神华煤锅炉低氮燃烧特性研究

神华煤极易着火、燃尽,燃烧性能优良,且煤中氮、硫含量低,使神华煤在低氧和低氮结合的燃烧条件下,保持了较高的燃尽性能和较一般烟煤偏低的NOx生成量。神华煤的低硫特性保证了在贫氧(没有足够的氧气保证充分燃烧)条件下,炉内H2S含量不是太高,没有明显的高温腐蚀倾向。采用低氮燃烧后,燃烧器区燃烧强度降低,缓解了炉内结渣,部分锅炉屏区的结渣也有所缓解,提高了具有严重结渣倾向的神华煤的掺烧比例。神华煤采用低氧燃烧和低氮燃烧相结合的技术,保证了锅炉的燃烧经济性、安全性和低NOx生成特性,指标明显优于国内其他典型烟煤。     

An investigation into physicochemical characteristics of ash produced from combustion of oil palm biomass wastein a boiler

Ash derived from combustion of Malaysian oil palm biomass (empty fruit bunches consisting of fibers) was physically and chemically characterized in order to provide a comprehensive understanding of its specific properties in terms of toxicity, compositions and reusability. Principal analyses conducted include particle size distribution, scanning electron microscopy, elemental dispersive X-ray, elemental analysis, toxicity characteristic leaching procedure (TCLP) as well as thermogravimetric, X-ray diffractometry and Fourier-transform infrared analyses. TCLP result indicated that the oil palm ash (OPA) should not be classified as toxic wastes in terms of heavy metal leachability since leachable copper, cadmium, lead and nickel concentrations were detected below the stipulated leachability limits. It was determined that the OPA contained high amount of potassium as well as presence of silica which implied its suitability to be reused as crude fertilizer or cement replacement material.