纤维素催化热解定向调控制取不含氧烃类液体燃料

为了将生物质能高效转化为高品位不含氧的液体燃料,以纤维素为例,研究了以催化热解方式将热解产物转化为芳香烃类液体燃料的过程.实验发现,纤维素热解产生的含氧有机小分子,可以通过催化热解的形式高效转化为不含氧的芳香烃类液体.催化剂采用HZSM-5(23)、催化剂原料质量比例为5∶1、热解温度为650℃、升温速率为10000 K/s的工况为纤维素催化热解的最佳工况,单环芳烃、多环芳烃产率分别为9.90%和12.91%,总芳香烃类产率为22.81%.热解温度提升至650℃前,更高的热解温度能获得更高的芳香烃产率.继续提高热解温度,单环芳烃、多环芳烃分子间还可能进一步发生聚合反应,最终产生积碳.同时本文也提出了一种可行的纤维素催化热解中的反应途径,与本文实验结果较为匹配.     

基于EPR检测技术的木质素模型化合物催化热解反应机理

针对生物质三大组分中最难分解的木质素,选取了愈创木酚及香兰素作为其模化物,为明晰其催化热解机理以实现对催化热解定向调控进行指导,采用电子顺磁共振(EPR)检测技术,结合Py-GC/MS的分析,研究了愈创木酚及香兰素催化热解的反应机理及反应路径.结果表明:以HZSM-5为催化剂,催化剂与反应物质量比为2∶1时,催化热解对于反应物的热解效果均优于非催化热解,愈创木酚催化热解主要液相产物有呋喃类、酚类、单环芳烃和多环芳烃.对于香兰素的催化热解产物主要为芳烃类、酚类和醛类.在催化热解过程中通过EPR技术可检测到甲基自由基的存在.依据自由基反应,分别梳理了愈创木酚及香兰素的催化热解机理及反应路径.     

生物质焦油的特性及其净化研究现状

通过分析生物质热解气化过程中焦油的特性和生成机制,以及净化方法研究现状,了解焦油的主要组成和基本特性参数,发现焦油随着反应温度的升高,逐步经过裂解、聚合、缩合反应生成多环芳香烃。而焦油的脱除应当根据不同的生物质气化反应特性,多种方法结合,以减少催化剂损失、提高焦油脱除率和转化率。     

乙醇/正庚烷燃烧过程PAH形成的数值模拟

应用CHEMKIN化学动力学软件,构建乙醇/正庚烷的芳香烃(PAH)形成机理(包含241种组分,1,703个基元反应).在激波管和预混火焰条件下,研究乙醇/正庚烷燃烧过程中前驱体单环芳香烃(苯)和多环芳香烃(萘、菲、芘)的形成,探讨乙醇掺混比对PAH形成的影响.对生成速率的分析结果表明,丙炔基的聚合与环化、苯基的加氢反应是形成苯的主要反应;多个苯环的形成主要通过脱氢加乙炔反应;具有氧化性的H和OH自由基减少了PAH的生成.敏感性分析结果表明,乙醇/正庚烷燃烧过程中,促进苯生成的主要反应是戊基、戊烯、烯丙基和丙基的分解.随着乙醇掺混比的增加,燃烧过程中分解形成的活性羟基(—OH)摩尔分数增加,PAH的生成速率下降,表明乙醇具有抑制PAH形成的作用.     

煤的理化性质对生物质和煤共热解焦油性质的影响

将木屑分别与黑山煤、神木煤以不同比例掺混,利用自制热解干馏炉进行共热解实验。比较木屑的添加对共热解焦油、水和轻质焦油产率的不同影响,结合煤和生物质的热重分析结果与煤的13C核磁共振分析表征,探讨煤的结构、煤和生物质的热化学反应特性,对共热解焦油产率和品质的作用机理。结果表明:在一定配比范围内,木屑和煤之间的交互作用明显提高了共热解焦油中轻质组分的产率,同时热解水产率低于计算值;轻质焦油中的脂肪烃组分主要由木屑和煤热解产生的烷基自由基相互化合生成;煤热解产生的芳烃类自由基由于与生物质热解产生的羟基自由基生成杂酚化合物,从而抑制了热解水的生成。     

裂解温度对生物质热解焦油成分的影响

以锯末粉体为生物质热解焦油研究对象,研究了热解温度对焦油产量和焦油化学成分的影响规律,结果表明,热解温度为500℃时,生物质热解产生的焦油量最大,温度过高或过低都有利于焦油的减少。不同热解温度下,焦油中碳氢化合物的成分主要是芳香烃和少量的脂肪烃,含氧化合物主要是苯酚及其烷基衍生物,含氮化合物主要是吡啶、吡咯及其烷基衍生物等杂环化合物。     

生物质气化过程中焦油的生成

总结了生物质气化过程中焦油的生成和分类,以及气化炉炉型、温度与氧量对焦油生成量和组成的影响规律。初级、二级和三级焦油是应用最为广泛的一种分类方法;不同炉型气化炉产气中焦油质量浓度从大到小依次为:上吸式流化床下吸式,分别在100,10,1g/m~3的量级,两段式等改进炉型在焦油控制上更有优势;上吸式气化炉焦油多为初级组分,下吸式则以无取代基的多环芳香烃等三级焦油为主,而流化床的焦油涵盖了二、三级焦油组分;温度的升高使得焦油量下降,且趋向于转化为化学结构更稳定的三级组分;氧量的增多对焦油的生成具有抑制作用。     

生物质废弃物在回转窑内热解研究--Ⅱ.热解终温对产物性质的影响

考察了不同热解终温下木块和稻壳在回转窑内热解产物－燃气、焦油和炭的成分和性质的变化。在试验温度范围内,热解气体热值约10．0－15．9MJ／Nm^3,密度1.21-1.52Nm^3/kg,且随热解终温变化呈规律性变化,木块炭的热值为29.0-33.9MJ／kg,稻壳炭则为17.6-20.8MJ/kg,热解终温的提高使炭中挥发份的降低,灰分增多,从而导致热值的降低;炭的C含量高于原始物料的C含量,而H、O则相反;元素残留率的计算表明,热解过程中H和O元素的脱除易于C元素。热解终温对焦油中饱和烃、芳香烃成分含量的影响不大,饱和链烃成分主要集中为C14－C34正构烷烃和含末端双链烯烃的碳分子链,芳香烃主要为蒽（菲）、芘、萤蒽及各自衍生物的稠环芳烃。     

气体停留时间对流化床褐煤热解产物的影响

在小型流化床热解反应器上,以小龙潭褐煤为热解原料,通过控制二次热解段尺寸和加热条件,研究不同热解温度(500~800℃)和热解气停留时间(5.5~18.7 s)对煤热解挥发产物产率及组分的影响。通过增加管径和增加长度控制气体停留时间,在各个温度下,均会出现焦油产率的下降,气体产率的上升,焦油气相二次反应更为明显。焦油中轻质组分的含量增加,其中苯、二甲苯及多环芳烃含量在较长停留时间下的增加明显,酚类及脂肪烃含量有所下降。焦油发生裂解、缩聚、加氢等二次反应,CO_2、CO等主要煤气组分均有所上升,并随温度的升高更为明显。     

正庚烷HCCI燃烧下芳香烃及多环芳烃形成的数值模拟

通过修改化学动力学软件CHEMKINⅢ,建立了正庚烷HCCI燃烧下排放特性数值模拟的多区模型.利用此模型对正庚烷HCCI燃烧下芳香烃(苯)与多环芳烃(萘、菲及芘)的生成及演变规律进行了详细分析.计算中采用了正庚烷的燃烧与分解、多环芳烃生成的详细反应机理(共包括107种组分、542个基元反应).结果表明,缸内压力变化趋势的计算结果与实验值基本吻合;核心区由于温度较高,其中的正庚烷已充分燃烧,多环芳烃的质量分数极小;边界层区和缝隙区温度较低,尤其是缝隙区,其温度与壁面温度保持一致,正庚烷在其中不能充分燃烧和分解,同时这两个区域成为多环芳烃的主要来源.     

Ash-forming elements in four Scandinavian wood species. Part 1: Summer harvest

Woody biomass in Finland and Sweden comprises mainly four wood species: spruce, pine, birch and aspen. To study the ash, which may cause problems for the combustion device, one tree of each species were cut down and prepared for comparisons with fuel samples. Well-defined samples of wood, bark and foliage were analyzed on 11 ash-forming elements: Si, Al, Fe, Ca, Mg, Mn, Na, K, P, S and Cl. The ash content in the wood tissues (0.2–0.7%) was low compared to the ash content in the bark tissues (1.9–6.4%) and the foliage (2.4–7.7%). The woods’ content of ash-forming elements was consequently low; the highest contents were of Ca (410–1340 ppm) and K (200–1310), followed by Mg (70–290), Mn (15–240) and P (0–350). Present in the wood was also Si (50–190), S (50–200) and Cl (30–110). The bark tissues showed much higher element contents; Ca (4800–19,100 ppm) and K (1600–6400) were the dominating elements, followed by Mg (210–2400), P (210–1200), Mn (110–1100) and S (310–750), but the Cl contents (40–330) were only moderately higher in the bark than in the wood. The young foliage (shoots and deciduous leaves) had the highest K (7100–25,000 ppm), P (1600–5300) and S (1100–2600) contents of all tissues, while the shoots of spruce had the highest Cl contents (820–1360) and its needles the highest Si content (5000–11,300). This paper presented a new approach in fuel characterization: the method excludes the presence of impurities, and focus on different categories of plant tissues. This made it possible to discuss the contents of ash element in a wide spectrum of fuel-types, which are of large importance for the energy production in Finland and Sweden.     

NEXT GENERATION ENGINEERED MATERIALS FOR ULTRA SUPERCRITICAL STEAM TURBINES

正1 ABSTRACT To reduce the effect of global warming on our climate,the levels of CO2emissions should be reduced.One way to do this is to increase the efficiency of electricity production from fossil fuels.This will in turn reduce the amount of CO2emissions for a given power output.Using US practice for efficiency calculations,then a move from a typical US plant running at 37%efficiency to a 760℃/38.5 MPa(1 400/5 580 psi)plant running at 48%efficiency would reduce CO2emissions by 170kg/MW.hr or 25%.     

Performance assessment of some ice TES systems

In this paper, a performance assessment of four main types of ice storage techniques for space cooling purposes, namely ice slurry systems, ice-on-coil systems (both internal and external melt), and encapsulated ice systems is conducted. A detailed analysis, coupled with a case study based on the literature data, follows. The ice making techniques are compared on the basis of energy and exergy performance criteria including charging, discharging and storage efficiencies, which make up the ice storage and retrieval process. Losses due to heat leakage and irreversibilities from entropy generation are included. A vapor-compression refrigeration cycle with R134a as the working fluid provides the cooling load, while the analysis is performed in both a full storage and partial storage process, with comparisons between these two. In the case of full storage, the energy efficiencies associated with the charging and discharging processes are well over 98% in all cases, while the exergy efficiencies ranged from 46% to 76% for the charging cycle and 18% to 24% for the discharging cycle. For the partial storage systems, all energy and exergy efficiencies were slightly less than that for full storage, due to the increasing effect wall heat leakage has on the decreased storage volume and load. The results show that energy analyses alone do not provide much useful insight into system behavior, since the vast majority of losses in all processes are a result of entropy generation which results from system irreversibilities.     

Aerodynamic performance effects of leading-edge geometry in gas-turbine blades

The purpose of this paper is to illustrate the advantages of the direct surface-curvature distribution blade-design method, originally proposed by Korakianitis, for the leading-edge design of turbine blades, and by extension for other types of airfoil shapes. The leading edge shape is critical in the blade design process, and it is quite difficult to completely control with inverse, semi-inverse or other direct-design methods. The blade-design method is briefly reviewed, and then the effort is concentrated on smoothly blending the leading edge shape (circle or ellipse, etc.) with the main part of the blade surface, in a manner that avoids leading-edge flow-disturbance and flow-separation regions. Specifically in the leading edge region we return to the second-order (parabolic) construction line coupled with a revised smoothing equation between the leading-edge shape and the main part of the blade. The Hodson–Dominy blade has been used as an example to show the ability of this blade-design method to remove leading-edge separation bubbles in gas turbine blades and other airfoil shapes that have very sharp changes in curvature near the leading edge. An additional gas turbine blade example has been used to illustrate the ability of this method to design leading edge shapes that avoid leading-edge separation bubbles at off-design conditions. This gas turbine blade example has inlet flow angle 0°, outlet flow angle −64.3°, and tangential lift coefficient 1.045, in a region of parameters where the leading edge shape is critical for the overall blade performance. Computed results at incidences of −10°,   −5°,   +5°,   +10° are used to illustrate the complete removal of leading edge flow-disturbance regions, thus minimizing the possibility of leading-edge separation bubbles, while concurrently minimizing the stagnation pressure drop from inlet to outlet. These results using two difficult example cases of leading edge geometries illustrate the superiority and utility of this blade-design method when compared with other direct or inverse blade-design methods.     

Effect of co-cultivation of Chlamydomonas reinhardtii with Azotobacter chroococcum on hydrogen production

Chlamydomonas reinhardtii cc124 and Azotobacter chroococcum bacteria were co-cultured with a series of volume ratios and under a variety of light densities to determine the optimal culture conditions and to investigate the mechanism by which co-cultivation improves H₂ yield. The results demonstrated that the optimal culture conditions for the highest H₂ production of the combined system were a 1:40 vol ratio of bacterial cultures to algal cultures under 200 μE m^?2 s^?1. Under these conditions, the maximal H₂ yield was 255 μmol mg^?1 Chl, which was approximately 15.9-fold of the control. The reasons for the improvement in H₂ yield included decreased O₂ content, enhanced algal growth, and increased H₂ase activity and starch content of the combined system.     

Natural-gas fueled spark-ignition (SI) and compression-ignition (CI) engine performance and emissions

Natural gas is a fossil fuel that has been used and investigated extensively for use in spark-ignition (SI) and compression-ignition (CI) engines. Compared with conventional gasoline engines, SI engines using natural gas can run at higher compression ratios, thus producing higher thermal efficiencies but also increased nitrogen oxide (NO_x) emissions, while producing lower emissions of carbon dioxide (CO₂), unburned hydrocarbons (HC) and carbon monoxide (CO). These engines also produce relatively less power than gasoline-fueled engines because of the convergence of one or more of three factors: a reduction in volumetric efficiency due to natural-gas injection in the intake manifold; the lower stoichiometric fuel/air ratio of natural gas compared to gasoline; and the lower equivalence ratio at which these engines may be run in order to reduce NO_x emissions. High NO_x emissions, especially at high loads, reduce with exhaust gas recirculation (EGR). However, EGR rates above a maximum value result in misfire and erratic engine operation. Hydrogen gas addition increases this EGR threshold significantly. In addition, hydrogen increases the flame speed of the natural gas-hydrogen mixture. Power levels can be increased with supercharging or turbocharging and intercooling. Natural gas is used to power CI engines via the dual-fuel mode, where a high-cetane fuel is injected along with the natural gas in order to provide a source of ignition for the charge. Thermal efficiency levels compared with normal diesel-fueled CI-engine operation are generally maintained with dual-fuel operation, and smoke levels are reduced significantly. At the same time, lower NO_x and CO₂ emissions, as well as higher HC and CO emissions compared with normal CI-engine operation at low and intermediate loads are recorded. These trends are caused by the low charge temperature and increased ignition delay, resulting in low combustion temperatures. Another factor is insufficient penetration and distribution of the pilot fuel in the charge, resulting in a lack of ignition centers. EGR admission at low and intermediate loads increases combustion temperatures, lowering unburned HC and CO emissions. Larger pilot fuel quantities at these load levels and hydrogen gas addition can also help increase combustion efficiency. Power output is lower at certain conditions than diesel-fueled engines, for reasons similar to those affecting power output of SI engines. In both cases the power output can be maintained with direct injection. Overall, natural gas can be used in both engine types; however further refinement and optimization of engines and fuel-injection systems is needed.     

Hydrogen production by steam-gasification of carbonaceous materials using concentrated solar energy – V. Reactor modeling,optimization, and scale-up

A chemical reactor for the steam-gasification of carbonaceous particles (e.g. coal, coke) is considered for using concentrated solar radiation as the energy source of high-temperature process heat. A two-phase reactor model that couples radiative, convective, and conductive heat transfer to the chemical kinetics is applied to optimize the reactor geometrical configuration and operational parameters (feedstock's initial particle size, feeding rates, and solar power input) for maximum reaction extent and solar-to-chemical energy conversion efficiency of a 5 kW prototype reactor and its scale-up to 300 kW. For the 300 kW reactor, complete reaction extent is predicted for an initial feedstock particle size up to 35 μm at residence times of less than 10 s and peak temperatures of 1818 K, yielding high-quality syngas with a calorific content that has been solar-upgraded by 19% over that of the petcoke gasified.     

Assessment methods of material ageing using Sdobyrev''s creep rupture model

The physical aspects of the activation energy, in higher and high temperatures, of the metal creep process were examined. The research results of creep-rupture in a uniaxial stress state and the criterion of creep-rupture in biaxial stress states, at two temperatures, are then presented. For these studies creep-rupture, taking case iron as an example the energy and pseudoenergy activation was determined. For complex stress states the criterion of creep-rupture was taken to be Sdobyrev's, i.e. σ_red = σ₁ β + (1 − β)σ_i, where: σ₁-maximal principal stress, σ_i-stress intensity, β-material constant (at variable temperature β = β(T)). The methods of assessment of the material ageing grade are given in percentages of ageing of new material in the following mechanical properties: 1) creep strength in uniaxial stress state, 2) activation energy in uniaxial stress state, 3) criterion creep strength in complex stress states, 4) activation pseudoenergy in complex stress states. The methods 1) and 3) are the relatively simplest because they result from experimental investigations only at nominal temperature of the structure work, however, for methods 2) and 4) it is necessary to perform the experimental investigations at least at two temperatures.     

Production of hydrogen from sewage biosolids in a continuously fed bioreactor: Effect of hydraulic retention time and sparging

Hydrogen was produced from primary sewage biosolids via mesophilic anaerobic fermentation in a continuously fed bioreactor. Prior to fermentation the sewage biosolids were heated to 70 °C for 1 h to inactivate methanogens and during fermentation a cellulose degrading enzyme was added to improve substrate availability. Hydraulic retention times (HRT) of 18, 24, 36 and 48 h were evaluated for the duration of hydrogen production. Without sparging a hydraulic retention time of 24 h resulted in the longest period of hydrogen production (3 days), during which a hydrogen yield of 21.9 L H₂ kg⁻¹ VS added to the bioreactor was achieved. Methods of preventing the decline of hydrogen production during continuous fermentation were evaluated. Of the techniques evaluated using nitrogen gas to sparge the bioreactor contents proved to be more effective than flushing just the headspace of the bioreactor. Sparging at 0.06 L L min⁻¹ successfully prevented a decline in hydrogen production and resulted in a yield of 27.0  L H₂ kg⁻¹ VS added, over a period of greater than 12 days or 12 HRT. The use of sparging also delayed the build up of acetic acid in the bioreactor, suggesting that it serves to inhibit homoacetogenesis and thus maintain hydrogen production.     

汽轮机数字电液调节系统挂闸异常的技术完善

分析了200MW汽轮机数字电液调节系统在运行中存在的挂闸异常问题,采取了相应的技术处理措施,且运行实践效果良好。