褶皱式玻璃纤维基底的钒基催化剂性能研究

基于NH₃选择性催化还原（selective catalytic reduction, SCR）反应机理,对采用褶皱式玻璃纤维基底的钒基催化剂在重型柴油机中的应用性能进行模拟研究,并与传统堇青石基底钒基催化剂进行对比。利用国六发动机台架测试结果对模拟程序进行了验证,然后研究了氨氮比、NO₂/NO_x比及空速对褶皱式玻璃纤维基底的钒基催化剂在低温下NO_x转化及NH₃泄漏特性的影响。结果表明：低温下褶皱式玻璃纤维基底钒基催化剂的NO_x转化性能明显优于相同条件下的堇青石基底钒基催化剂。氨氮比的增加对褶皱式玻璃纤维基底的钒基催化剂的NO_x转化性能无明显影响;当氨氮比从0.8增加到1.2时,在200 ℃~500 ℃的区间内NH₃的泄漏量由1×10^-6提高到100×10^-6。NO₂/NO_x比增加可有效提高钒基催化剂的低温性能。当温度为150 ℃时,NO₂/NO_x比由0提高为0.5,钒基催化剂的NO_x的转化效率从14.0%上升到76.0%,而NH₃泄漏量由428×10^-6下降为9×10^-6。当温度为200 ℃时,30 000 h^-1空速下钒基催化剂的NO_x转化效率为98.5%,比90 000 h^-1下提升近30.0%;NH₃泄漏量为7×10^-6,比90 000 h^-1下降低150×10^-6。     

水热老化温度和时长对Cu-SSZ-13分子筛催化剂性能和理化特性影响的研究

通过离子交换法合成具有优异催化活性的Cu-SSZ-13分子筛催化剂,分别在不同的温度和时长条件下对其进行水热老化处理。比较了数个不同老化条件下的催化剂的NO_x催化性能、NH₃吸附性能,同时通过Brunauer–Emmett–Teller（BET）方法、X射线衍射（X-ray diffraction, XRD）和H₂程序升温还原（temperature programmed reduction, TPR）方法对这些催化剂的孔特性、晶体结构和铜位点的数量分布等进行探究。测试结果发现水热老化会引起催化剂催化活性、催化温度窗口范围的全面下降,并导致气体吸附性能的下降和氧化还原性能的大幅改变。进一步研究发现水热老化引起晶体结构和孔结构的破坏,并导致大量活性位点的转变和流失。制备的Cu-SSZ-13分子筛催化剂总体上具有良好的耐久性,对老化温度的敏感性比老化时间更高。     

氢发动机SCR催化器的NOx转化效率模拟

建立一维选择性催化还原（selective catalytic reduction,SCR）催化器模型,采用稳态、瞬态小样试验标定SCR化学反应动力学机理,并分析SCR催化器对氢发动机排气中NO_x的催化还原过程。结果表明：入口O₂体积分数对NO_x催化还原有抑制作用,但入口H₂O体积分数对NO_x转化效率没有明显影响;当温度为250~400 ℃时,线性温升工况NO_x转化效率高于稳态工况且超过98%;氢发动机排气温度和原排NO_x体积分数随功率增大而增大,当功率大于60 kW且氨氮比等于1时,SCR催化器转化效率小于95%;增加氨氮比对NO_x转化效率的提高作用较小,这是由于在高温条件下增加的NH₃倾向与O₂反应。     

铜分子筛涂覆颗粒捕集催化剂的实验研究

针对柴油催化氧化系统（diesel oxidation catalyst，DOC）、颗粒捕集器（diesel particulate filter，DPF）、选择性催化还原（selective catalytic reduction，SCR）系统应用于轻型车时面临的催化剂布置困难和SCR催化剂温度低等问题，将SCR催化剂涂覆到DPF载体（简称SDPF），实现NO_x减排和PM捕集功能，同时可显著减小后处理催化剂的体积。分别考察SDPF在200、300和400 ℃时不同碳烟加载量下的台架测试背压，测试结果表明SDPF催化剂加载碳烟在0~4.0 g/L范围内背压增长显著，在4.0~6.0 g/L范围内背压增长不明显。选取体积类似的SDPF和SCR催化剂进行新鲜态NO_x转化性能对比测试，测试结果表明：SDPF催化剂仅需相同体积SCR催化剂约2/3的涂覆量即可达到相当的NO_x转化能力，碳烟加载主要影响230 ℃以下的低温段NO_x转化。SDPF载体积炭量达到6.0 g/L后进行快速升温，以测试催化剂的积炭再生性能。测试结果表明：SDPF积炭再生时高温区域集中在出气端中心区域，可探测最高温度低于650 ℃，较充分的碳烟再生时间应大于15 min。     

低负荷工况下城市类重型柴油车的实际道路排放特性研究

应用便携式排放测试系统（portable emission measurement system, PEMS）,对3辆不同类型的城市类重型柴油车分别进行实际道路行驶排放测试。试验车辆包括：邮政车、垃圾自卸车、小学专用校车。对于处在不同负荷段的数据进行分类整理,分析车辆在低负荷工况下不同负荷段的CO、NO_x、颗粒物数量（particulate number, PN）的排放占比和比排放结果,并结合功基窗口法分析NO_x的排放特性。试验结果表明：在低负荷工况时,尤其是负荷率处于0~20%的阶段,CO、NO_x、PN的排放量占比分别达到72%~86%、60%~87%、52%~88%,且CO、NO_x、PN在低负荷阶段的比排放高于或接近国六排放限值。     

工作环境对自然吸气柴油机性能影响仿真

基于CY4102BG四冲程自然吸气柴油机,利用GT-POWER一维仿真计算软件建立柴油机工作过程仿真模型,研究高原和水下工作环境对柴油机性能的影响。仿真结果表明：随着海拔的增高,柴油机有效功率有所下降,NO_x排放上升,排气温度增加;随着水下排气背压的增高,柴油机有效功率下降,NO_x排放显著上升。针对柴油机在非标况环境下NO_x排放性能的恶化,通过调节喷油参数来优化柴油机综合性能。经优化,在不同工作环境下柴油机NO_x排放降低7.3%~21.4%,优化效果较为明显。     

650MW电厂SCR脱硝系统喷氨装置协调优化

山东某电厂650MW燃煤机组SCR（selective catalytic reduction）脱硝系统氨气逃逸率较大,导致催化剂的堵塞、失活及中毒。通过FLUENT数值模拟建立三维脱硝系统模型,模拟了在反应器顶部不同导流板数量及喷氨速度下SCR系统流场分布,通过对结果的分析比较,得出适当增加导流板组数和合理差异化的调整各喷口喷氨速度能够使第一层催化剂入口的NH₃浓度、NO_X浓度及NH₃/NO_X分布更加均匀化合理化,很好的满足了设计和运行的双重检测,为SCR脱硝系统的协调优化和机组运行的稳定性提供了实际参考价值。     

船用低速柴油机低压SCR系统台架试验研究

结合船用低速柴油机的技术特点设计了低压SCR系统并开展了台架试验研究。试验结果表明:所设计的SCR系统NO_x减排效果明显,NH₃逃逸量较小,满足相关法规要求;柴油机在加装SCR系统后排气压力损失满足设计要求,且对燃油消耗率影响较小。     

柴油甲醇组合燃烧对机车柴油机排放性能的影响

对一台应用于机车的中速大型柴油机,按照柴油/甲醇组合燃烧(DMCC)的要求,进行了相应的改造,以探究DMCC燃烧模式对其排放性能的影响。结果表明:在800 r/min@9 600 N·m工况下,掺烧甲醇后,NO_x比排放大幅降低,但过分提高甲醇替代率,则NO_x比排放会有所升高;CO₂比排放、燃料费用随甲醇替代率的升高而降低;当量油耗则先随甲醇的替代率提高而升高,随后降低;HC比排放随甲醇替代率提高有所升高。相比于原机,在800 r/min、9 600 N·m、-4° ATDC、35.9%替代率工况, NO_x比排放仅为3.15 g/(kW·h),最大降幅达到56.5%;DMCC模式,640 r/min@6 850 N·m工况下,随着供油提前角的推迟,NO_x、HC比排放降低,排气温度逐渐升高;中等替代率下最低油耗对应的供油提前角推迟,高替代率下供油提前角提前。     

国六重型柴油–液化天然气车实际道路排放特性研究

利用便携式排放测试系统（portable emission testing system, PEMS）分别对4辆典型重型柴油车和4辆典型重型液化天然气（liquefied natural gas, LNG）车开展实际道路排放测试,并利用功基窗口法与行程平均法分析其实际道路NO_x、CO、CO₂和颗粒数量（particulate number, PN）排放特性。结果表明：排放后处理技术路线能够有效控制国六重型柴油车在实际道路工况下的NO_x、CO和PN排放;但LNG车的CO排放存在超排放限值的风险,部分LNG车存在NO_x排放超过限值的现象,而PN排放则存在较大不确定性,部分LNG车的PN排放较高。在碳排放方面,LNG车实际道路CO₂比排放较柴油车降低6%~18%,有较为明显的减碳优势。     

Optical properties and thermal stability of pulsed-sputter-deposited AlxOy/Al/AlxOy multilayer absorber coatings

Spectrally selective Al_xO_y/Al/Al_xO_y multilayer absorber coatings were deposited on copper (Cu) and molybdenum (Mo) substrates using a pulsed sputtering system. The Al targets were sputtered using asymmetric bipolar-pulsed DC generators in Ar+O₂ and Ar plasmas to deposit an Al_xO_y/Al/Al_xO_y coating. The compositions and thicknesses of the individual component layers were optimized to achieve high solar absorptance (α=0.950-0.970) and low thermal emittance (ε=0.05-0.08). The X-ray diffraction data in thin film mode showed an amorphous structure of the Al_xO_y/Al/Al_xO_y coating. The X-ray photoelectron spectroscopy data of the Al_xO_y/Al/Al_xO_y multilayer absorber indicated that the Al_xO_y layers present in the coating were non-stoichiometric. The optical constants (n and k) of the multilayer absorber were determined from the spectroscopic ellipsometric data. Drude's free-electron model was used for generating the theoretical dispersion of optical constants for Al films, while the Tauc-Lorentz model was used for modeling optical properties of the dielectric Al_xO_y layers. In order to study the thermal stability of the Al_xO_y/Al/Al_xO_y coatings, they were subjected to heat treatment (in air and vacuum) at different temperatures and durations. The multilayer absorber deposited on Cu substrates exhibited high solar selectivity (α/ε) of 0.901/0.06 even after heat-treatment in air up to 400 °C for 2 h. At 450 °C, the solar selectivity decreased significantly on Cu substrates (e.g., α/ε=0.790/0.07). The coatings deposited on Mo substrates were thermally stable up to 800 °C in vacuum with a solar selectivity of 0.934/0.05. The structural stability of the absorber coatings heat treated in air (up to 400 °C) and vacuum (up to 800 °C) was confirmed by micro-Raman spectroscopy measurements. Studies on the accelerated aging tests suggested that the absorber coatings on Cu were stable in air up to 75 h at 300 °C and the service lifetime of the multilayer absorber was predicted to be more than 25 years. Further, the activation energy for the degradation of the multilayer absorber heat treated for longer durations in air is of the order of 64 kJ/mol.     

Hydrogen storage properties of multi-principal-component CoFeMnTixVyZrz alloys

This study presents an innovative multi-principal-element CoFeMnTiVZr alloy system for the absorption and desorption of hydrogen. Pressure-composition-isotherms (PCIs) demonstrate that CoFeMnTi_xVZr, CoFeMnTiV_yZr, and CoFeMnTiVZr_z can absorb and desorb hydrogen for x, y, and z that satisfy 0.5 ≤ x ≤ 2.5, 0.4 ≤ y ≤ 3.0, and 0.4 ≤ z ≤ 3.0, respectively. X-ray diffraction (XRD) reveals that CoFeMnTi_xV_yZr_z alloys have a simple C14 Laves phase with a single set of lattice parameters before and after PCI tests. The distributions of each element in CoFeMnTi_xV_yZr_z alloys are roughly equal, as revealed by SEM/EDS mapping. The effects of values x, y, and z on the hydrogen storage properties are elucidated in terms of lattice constant, element segregation, hydride formation enthalpies of the alloy components and hydrogen, and the averaged formation enthalpy. The high-entropy effect promotes the formation of a single C14 Laves phase, and the maximum hydrogen storage capacity is strongly related to the hydride formation enthalpy of the alloy and hydrogen.     

Optimization of buffer layers for lattice-mismatched epitaxy of GaxIn1−xAs/InAsyP1−y double-heterostructures on InP

We optimize InAs_yP_1−y buffer layers and compositional grades for lattice-mismatched heteroepitaxy of Ga_xIn_1−xAs/InAs_yP_1−y double-heterostructures on InP. The strains of the active and buffer layers depend on the bulk misfit difference between these layers. The misfit difference is adjusted to eliminate strain in the active layer, thus avoiding misfit dislocations and surface topography that would otherwise form to relieve strain. The optimized structure uses an “overshoot” with respect to the conventional design in the misfit and As composition of the InAs_yP_1−y buffer. Nearly optimized heterostructures typically show excellent structural quality and extended minority-carrier lifetimes.     

Electrochromic properties of NiOxHy thin films

NiO_xH_y films were prepared by DC magnetron sputtering in H₂/O₂ atmosphere. NiO_xH_y coatings with transparency and high electrochromic efficiency were obtained by changing H₂ content. A 60 nm thick NiO_xH_y film with transmittance of 0.57 (as-deposited state), 0.78 (bleached state) and 0.24 (coloured state) at wavelength of 550 nm was deposited in an atmosphere of H₂(60%)+O₂(40%). Analysis of infrared spectra (60002400 cm⁻¹) showed that the absorption peaks for bleached and colored states are associated with free ‘OH’ and OH stretching vibrations, respectively. XPS Ni2p core level spectra of colored NiO_xH_y film exhibited a peak at 856.2±0.2 eV which is attributed to Ni³⁺. Ni2p core level spectra of the bleached and as-deposited films exhibited two peaks at 856.4±0.2 and 854.6±0.2 eV which are attributed to Ni³⁺ and Ni²⁺.     

Structural and transport properties of LixNi1−y−zCoyMnzO2 cathode materials

In this work structural and transport properties of layered LiNi_1−y−zCo_yMn_zO₂ (y = 0.25, 0.35, 0.5 and z = 0.1) cathode materials are presented. In the considered group of oxides, LiNi_1−y−zCo_yMn_zO₂, there is no clear correlation between electrical conductivity and the a parameter (M-M distance in the octahedra layers). A non-monotonic modification of electrical properties of Li_xNi_0.65Co_0.25Mn_0.1O₂ cathode materials is observed upon lithium deintercalation.     

Explosion behavior of CH4/O2/N2/CO2 and H2/O2/N2/CO2 mixtures

In this work, the explosion behavior of stoichiometric CH₄/O₂/N₂/CO₂ and H₂/O₂/N₂/CO₂ mixtures has been studied both experimentally and theoretically at different CO₂ contents and oxygen air enrichment factors. Peak pressure, maximum rate of pressure rise and laminar burning velocity were measured from pressure time records of explosions occurring in a closed cylindrical vessel. The laminar burning velocity was also computed through CHEMKIN–PREMIX simulations.     

C/H/O/N/S/Cl/K/Na元素的详细化学反应机理的简化与验证

基于Senkin模型,应用自编化学反应机理简化程序,结合Kinalc和Mechmod开源程序,发展了详细化学反应机理的简化与验证方法.以电站锅炉燃烧的计算流体力学(CFD)数值模拟为应用背景,建立了考虑C/H/O/N/S/Cl/K/Na元素的详细化学反应机理(115组分,1,342基元反应),并运用此方法得到简化反应机理(28组分,20反应).验证结果表明,该简化机理在锅炉运行的主要参数变化范围内(温度T=1,100～1,500,℃,过量空气系数λ=0.8～1.2)具有较好的准确性和较高的计算效率,可应用于锅炉燃烧的CFD计算.     

Characterization and voltammetric behavior of PtyMozOx/C electrodes prepared by the thermal decomposition of polymeric precursors

Carbon-supported catalysts containing platinum and molybdenum oxide are prepared by thermal decomposition of polymeric precursors. The Pt_yMo_zO_x/C materials are characterized by energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The catalysts present a well-controlled stoichiometry and nanometric particles. Molybdenum is present mainly as the MoO₃ orthorhombic structure, and no Pt alloys are detected. The voltammetric behavior of the electrodes is investigated; a correlation with literature results for PtMo/C catalysts prepared by other methods is established. The formation of soluble species and the aging effect are discussed.     

Experimental and modeling studies of C2H4/O2/Ar, C2H4/methylal/O2/Ar and C2H4/ethylal/O2/Ar rich flames and the effect of oxygenated additives

The addition of dimethoxymethane (DMM or methylal) and diethoxymethane (DEM or ethylal) to a rich ethylene/oxygen/argon flame has been investigated by measuring the depletion of soot precursors. Three rich premixed ethylene/oxygen/argon (with and without added methylal or ethylal) flat flames have been stabilized at low-pressure (50 mbar) on a Spalding–Botha type burner with the same equivalence ratio of 2.50. Identification and monitoring of signal intensity profiles of species within the flames have been carried out by using molecular beam mass spectrometry (M.B.M.S.). The replacement of some C₂H₄ by C₃H₈O₂ or C₅H₁₂O₂ is responsible for a decrease of the maximum mole fractions of the detected intermediate species. This phenomenon is noticeable for C₂–C₄ intermediates and becomes more effective for C₅–C₁₀ species, mainly when C₃H₈O₂ added.A new kinetic model has been elaborated and contains 546 reactions and 107 chemical species in order to simulate the three investigated flames: C₂H₄/O₂/Ar, C₂H₄/DMM/O₂/Ar and C₂H₄/DEM/O₂/Ar. The reaction mechanism well reproduces experimental mole fraction profiles of major and intermediate species, and underlines the effect of methylal and ethylal addition on species concentration profiles for these flames.     

Preparation and electrochemical properties of layer-structured LiNi1/3Co1/3Mn1/3−yAlyO2

Layer-structured LiNi_1/3Co_1/3Mn_1/3−yAl_yO₂ has been synthesized via a sol–gel method. The lattice constants of LiNi_1/3Co_1/3Mn_1/3−yAl_yO₂ decrease with the concentration of aluminum ions. XANES analysis further confirms that the valence of cobalt ion is 3+, and that of Ni is between 2+ and 3+ in LiNi_1/3Co_1/3Mn_1/3−yAl_yO₂. With doping aluminum ions, the redox centers for the electrochemical reaction change from nickel ions alone to both nickel and cobalt ions. The amounts of de-intercalatable lithium ions are affected by the concentration of aluminum ions; however, the extracting efficiency of lithium ions is improved by doping aluminum ions. Among all the samples, LiNi_1/3Co_1/3Mn_0.23Al_0.1O₂ exhibits the best capacity retention and the least irreversible capacity.