煤粉再燃过程对煤焦异相还原NO的影响

利用高温携带流反应装置,研究了煤种(包括褐煤、烟煤和贫煤)、再燃区内反应温度、煤粉粒径、一次燃烧区空气过量系数SR1和再燃区空气过量系数SR2对煤焦异相还原NO作用的影响,探讨了煤焦异相还原NO的机理.结果表明:随着SR2和煤粉粒径的减小以及再燃区反应温度的提高,煤粉NO还原效率增加;在相同的SR2下,随着煤中挥发分含量的提高,煤粉粒径的增加和再燃区反应温度的降低,煤焦异相还原NO贡献上升;对于相同再燃燃料份额:SR1=1.0和SR1=1.2时煤焦异相还原NO的贡献均大于SR1=1.1时的异相还原NO的贡献.     

煤粉再燃过程中NO异相还原机理的重要性

用两种褐煤的一种烟煤及其煤焦作为再燃燃料，实验研究了再燃环境下NO的还原。通过比较煤粉和煤焦对NO还原过程的不同，分析了异相机理对NO还原的重要性。结果表明，褐煤及其煤焦是有效的再燃燃料。褐煤作为再燃燃料时，煤焦的异相还原机理对NO还原起重要作用。煤中的金属氧化物对NO还原具有催化作用。     

煤粉MILD燃烧NOx生成和还原机理的数值分析

采用计算流体动力学(CFD)软件分析了国际火焰研究基金会(IFRF)试验系统上煤粉低氧稀释(MILD)燃烧特性和NO_x排放特性。比较了不同的湍流与化学反应相互作用模型、挥发分气相反应机理和焦炭燃烧模型对煤粉MILD燃烧特性预测的影响,通过对比烟气速度场、温度场、组分浓度场的模型预报结果与试验结果,得到了能够准确预测煤粉MILD燃烧特性的模型组合,即EDC-WD-MSR模型。采用此模型对煤粉MILD燃烧NO_x生成和还原路径进行分析,结果表明：煤粉MILD燃烧中燃料型NO占主导地位,热力型NO、N₂O中间体路径和快速型NO之和对NO总排放的贡献小于10%。煤粉MILD燃烧存在强烈的NO均相和异相还原反应,其中NO异相还原反应使燃料型NO的排放量占单独计算的焦炭NO和挥发分NO排放量之和的71.1%。     

再燃烧条件下煤焦结构其对NO还原的影响

在携带流反应装置中测量了再燃条件下煤粉在高温烟气环境中迅速热解时的质量损失,通过扫描电镜观察和分析了煤焦的显微结构;分析了煤种、热解温度、热解气氛和煤粉粒径等因素对煤粉热解特性的影响;探讨了煤焦形成条件对NO还原的影响.结果表明,随着煤的挥发分含量增加,煤的质量损失份额和煤焦还原NO的能力增加;热解温度升高,将导致煤焦还原NO能力下降;在一次燃烧区空气过量系数SR1＝1.0～1.2范围内,煤粉质量损失变化不大.     

停留时间对微细煤粉再燃还原NO效率的影响

以 4种细度的混煤 (烟煤与褐煤 )微细煤粉作为再燃燃料 ,用N2 、O2 、CO2 和NO配制模拟烟气 ,在 13 0 0℃立式管式携带炉中 ,对停留时间与再燃还原NO效率的关系进行了实验研究 ,分析了停留时间对再燃还原NO效率的影响机制 .在前 0 .8s内随停留时间的增加 ,NO还原率增加幅度较大 ,当停留时间继续增加时 ,NO还原效率增加幅度较小 .使用较细的煤粉可以适当缩短煤粉在再燃区的停留时间 .但是 ,如果低于 0 .6s ,NO的还原效率会大幅度下降 ,煤粉燃尽率也会降低 .这是因为煤粉的热解、挥发分的释放、NO的还原以及煤粉的燃烧需要一定的反应时间 .为使这些反应得以充分进行 ,0 .8s的停留时间是必需的     

不同煤种再燃过程中脱硝煤耗的试验研究

定义还原1 gNO 消耗的煤量为脱硝煤耗.在煤粉携带炉上进行了再燃试验,对不同煤种、不同工况下的脱硝煤耗进行了研究,分析了挥发分含量、再燃区温度、氧浓度、再燃燃料比等因素对脱硝煤耗的影响.结果表明:脱硝煤耗不仅能直观反映出不同煤种在还原 NO 方面的特性差异,而且还能有效反映再燃过程投入与收益之比;脱硝煤耗随着挥发分含量增加呈线性降低;再燃区氧浓度越低,脱硝煤耗也就越低;在49/6和6%氧浓度条件下,提高再燃燃料比,脱硝煤耗显著下降;在2%氧浓度条件下,提高再燃燃料比,脱硝煤耗增加;再燃区温度升高时,脱硝煤耗下降,并且挥发分越高的煤,脱硝煤耗随温度的变化越显著.     

采用微细煤焦再燃还原NO的反应机理

以3种细度的混煤煤焦作为再燃燃料,用N2、O2、CO2和NO配制模拟烟气,在1200℃、1300℃和1400℃立管式携带炉中进行了再燃还原NO的实验研究,对其化学反应机理进行了分析.结果表明:微细化煤焦再燃还原NO的反应速率受扩散-反应动力学的联合控制.因此,提高再燃区温度水平、使用反应活性高的煤焦或提高再燃煤焦的细度,均能明显提高再燃还原NO的化学反应速率.     

煤焦催化CO还原N2O的反应机理

为了研究燃烧过程中氮氧化物的转化特性,采用M06-2X/6-311G(d)密度泛函理论研究了CO还原N_2O的均相和异相反应过程,并通过计算热力学与动力学参数分析其反应机理。结果表明:CO均相还原N_2O的活化能为216.93 kJ/mol,煤焦异相催化CO还原N_2O反应的活化能为133.06 kJ/mol;CO还原N_2O的均相和异相反应过程差异较大,CO与N_2O的均相还原反应速率决定反应步是R→TS1,而异相还原反应速率决定反应步是IM→TS,在298.15～1 800 K内,异相还原的反应速率始终大于均相反应速率;煤焦表面可以为N_2O的还原提供反应位点,对气体之间的反应具有催化作用。     

煤粉再燃过程中最佳停留时间的实验研究

采用实验研究了煤粉再燃过程中停留时间与氧浓度影响脱硝效率的依赖关系,发现最佳停留时间与煤粉着火状态有直接关联。在再燃温度及氧浓度较低时,煤粉尚未着火,同相脱硝作用在整个脱硝反应中占优,最佳停留时间与烟气中碳氢化合物的消耗速率有关。随着再燃区氧浓度进一步上升,挥发分着火,大量挥发分被燃烧反应消耗掉,最佳停留时间与挥发分着火时间基本吻合,过多延长停留时间对脱硝没有实际意义。氧浓度更高时煤焦被挥发分的燃烧热引燃,颗粒大幅升温,煤焦的异相脱硝作用在总体脱硝作用中开始占优,并随停留时间延长持续上升,此时最佳停留时间的确定应与煤粉燃尽一起来考虑。     

煤焦再燃过程中催化剂对NO还原的影响

以小龙潭褐煤、富拉尔基褐煤和大同烟煤等制成的三种煤焦为再燃燃料 ,研究了它们在再燃区内对NO的还原过程 ,分析了煤灰中金属氧化物对NO还原的影响。为了研究碱金属氧化物对NO还原的催化作用 ,本文特别研究了烟煤焦经过浸泡催化剂处理后对NO的再燃过程及对NO还原率的影响。实验是在NO初始浓度为 10 0 0× 10 -6,反应温度分别为 90 0℃和 110 0℃条件下完成的。实验结果表明 ,煤灰中金属氧化物在再燃区中对NO还原有很强的催化作用 ,原来对NO还原效果很差的烟煤焦 ,添加廉价催化剂后对NO的异相还原有很大的影响 ,在合适的反应温度和化学当量比(SR)条件下 ,煤焦中的催化剂能降低NO还原反应的活化能 ,加快NO还原反应进行的速度 ,从而提高NO的还原率。     

Synthesis of FeCo2O4@Co3O4 nanocomposites and their electrochemical catalytical performaces for energy-saving H2 prodcution

In this study, FeCo₂O₄@Co₃O₄ bifunctional catalysts with a unique structure combining nanosheets and nanowires were prepared on nickel foam by a simple hydrothermal + annealing method. The catalysts exhibited excellent catalytic activity for hydrogen production during urea electrooxidation reaction (UOR) and ethanol oxidation reaction (EOR). For UOR, the potential at 10 mA/cm² current density is 1.387 V and the tafel slope is 67 mV/dec. In the configured two-electrode electrolytic cell, the FeCo₂O₄@Co₃O₄ catalysts in the UOR and EOR processes required only 1.425 and 1.471 V, respectively, to produce a current density of 10 mA/cm², which is much less than that of the (oxygen evolution reaction) OER (1.640 V). In addition, the current density remained stable at a fixed potential during a long time (20 h) i-t test in the urea solution.     

The electropositive environment of Rh in Rh1Sn2/SWNTs for boosting trifunctional electrocatalysis

Designof the high-efficiency multifunctional electrocatalysts is highly demanded for many electrochemical energy devices, such as water electrolyzers, metal-air batteries and fuel cells. Here, Rh–Sn bimetallic nanocrystal catalysts supported on single-walled carbon nanotubes (Rh_xSn_y/SWNTs) are reported, and the Rh₁Sn₂/SWNTs electrocatalyst show best multifunctional electrocatalytic performance. Strong electron synergy between Rh and Sn is the source of high catalytic activity.Sn transfers electrons from Rh to Sn, forming a unique positive environment around Rh, which effectively optimizes the binding energy of the reaction intermediate and further improves the catalytic activity. An alkaline electrolyzer using Rh₁Sn₂/SWNTs catalyst demands an ultra-low cell voltage of 1.56 V at the current density of 10 mA cm⁻² for overall water splitting. In addition, Rh₁Sn₂/SWNTs demonstrates good oxygen reduction reaction (ORR) performance, making it an excellent catalyst for long-life Zn-air batteries. This work provides a facile strategy for the development of multifunctional electrocatalysts for the highly demanded electrochemical energy technologies.     

Benzimidazole Schiff base copper(II) complexes as catalysts for environmental and energy applications: VOC oxidation,oxygen reduction and water splitting reactions

The new copper(II) complexes [Cu(μ-1κO:2κONN′-HL1)(μ-1κO:2κO′-NO₃)]₂.[Cu(μ-1κO:2κONN′-HL1)(CH₃OH)]₂(NO₃)₂ (1) and [Cu(κONN′-HL2)(μ-1κOO’:2κO′-NO₃)]_n (2), derived from the new pro-ligands H₂L1 = 2-(5,6-dihydroindolo[1,2-c]quinazolin-6-yl)-5-methylphenol and H₂L2 = 2-(5,6-dihydroindolo[1,2-c]quinazolin-6-yl)-4-nitrophenol, were synthesized and characterized by elemental analysis, FT-IR, ESI-MS, and their structural features were unveiled by single-crystal X-ray diffraction analysis. This discloses a dimeric structure for 1 and a polymeric infinite 1D metal-organic chain for 2. The complexes were evaluated as catalysts for the oxidation of toluene, a volatile organic compound (VOC), and for oxygen reduction and water splitting reactions. 1 exhibits a higher activity for the peroxidative conversion of toluene to oxygenated products (total yields up to 38%), whereas 2 demonstrates a superior performance for electrochemical energy conversion applications, i.e., for oxygen reduction (ORR), oxygen evolution (OER) and hydrogen evolution (HER) reactions in an alkaline medium in terms of higher ORR current densities, lower Tafel slope (73 mV dec^?1) and higher number of electrons exchanged (3.9), comparable to that of commercial Pt/C. Complex 2 also shows a better performance with lower onset potential and higher current densities for both OER and HER when studied as electrocatalyst for water splitting.     

Monometallic,bimetallic, and trimetallic chalcogenide-based electrodes for electrocatalytic hydrogen evolution reaction

Cu₂CoSnS₄, Cu₂SnS₃, Cu₂CoS₄, Co₂SnS₃, Cu₂S, CoS₂, and SnS₂ were synthesized using a one-step solvent-free solid-phase approach. The surface structure, morphology, and composition were characterized using an X-ray diffractometer (XRD), Fourier-Transform Infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and X-ray Photoelectron Spectroscopy (XPS). The characterizations reveal pure phase formation and porous morphology. Further, the Hydrogen evolution reaction was performed using Cu₂CoSnS₄, Cu₂SnS₃, Cu₂CoS₄, Co₂SnS₃, Cu₂S, CoS₂, and SnS₂-based electrodes. Amid all electrocatalysts, Cu₂CoSnS₄ shows an excellent hydrogen evolution reaction with a low overpotential of ?192.1 mV at ?10 mA/cm² in 0.5 M H₂SO₄. And higher current density. Cu₂CoSnS₄ also shows a lower Tafel slope of 98.6 mV/dec and charge transfer resistance than mono and bimetallic chalcogenide-based electrodes. The Cu₂CoSnS₄ exhibit very good stability for ～22 h at ?10 mA/cm² current density in 0.5 M H₂SO₄.     

Highly efficient methanol oxidation reaction on durable Co9S8 @N,S-doped CNT catalyst for methanol fuel cell applications

The implementation of direct methanol fuel cells is seen as a reliable factor in the future energy mix. Efficient energy conversion from methanol requires an active and durable catalyst to drive the anodic methanol oxidation reaction (MOR) in direct methanol fuel cells. As an alternative to high cost noble metals, cobalt-based electrocatalysts are considered potential replacements that meet the high activity and long-term stability for MOR. Herein, we report the preparation of hierarchical Co₉S₈ nanowires trapped in N-doped carbon nanotubes (N,S–Co@CNT) derived from melamine showing high activity for MOR in alkaline medium. In order to identify the main active sites, we synthesized cobalt particles embedded in carbon structures in absence of a sulphur source (Co@CNT) and evaluated its performance for MOR. The material characterization shows that adding sulphur during pyrolysis enhances the surface area, pore size and lattice defect. In addition, the morphology changes from hemi-spherical particles to nanowires, that significantly improves the electrochemical properties. The current density of N,S–Co@CNT is exceptionally higher (5.5 times) and the onset potential of MOR is shifted to lower potential when compared to Co@CNT. The enhanced activity, durability and stability of N,S–Co@CNT is ascribed to the unique hierarchical structure and surface properties.     

Nanofiber-based Sm0.5Sr0.5Co0.2Fe0.8O3-δ/N-MWCNT composites as an efficient bifunctional electrocatalyst towards OER/ORR

It is of significance to search non-noble metal OER/ORR catalysts with perfect performance. The introduction of carbon into perovskite can significantly enhance oxygen electrocatalytic activity. Herein, nanofiber-based Sm_0.5Sr_0.5Co_0.2Fe_0.8O_3-δ/rGO (SSCF28/rGO) and Sm_0.5Sr_0.5Co_0.2Fe_0.8O_3-δ/N-MWCNT (SSCF28/N-MWCNT) hybrids with various mass ratios were synthesized successfully by a facile ultrasonic mixing method and their oxygen evolution reaction (OER)/oxygen reduction reaction (ORR) properties were compared and studied. In 0.1 M KOH, SSCF28/N-MWCNT = 1.3 with optimal mass ratio shows better OER/OER bifuntional catalytic activity than SSCF28/rGO = 2:1. After 1000 CV cycles, SSCF28/N-MWCNT = 1.3 remains stable. Compared to SSCF28/rGO = 2:1, SSCF28/N-MWCNT = 1:3 shows promising practical applicability in metal-air batteries. The excellent OER/ORR activity of SSCF28/N-MWCNT = 1:3 can be attributed to the component optimization of perovskite and carbon and the synergistic effect between nanofiber-structured SSCF28 and N-functionalized MWCNT (N-MWCNT).     

Heterostructure PtNi supported by Pd nanosheets high-performance catalysts for multifunctional fuel cell

Platinum (Pt) based catalysts have multiphase structure, such as two-dimensional (2D) nanosheets structure, with a large specific surface area and high atomic utilization ratio, and a large contact area with carbon support, which promotes the combination of catalyst and support, and improves the activity of catalyst. However, there are still many difficulties in the synthesis of 2D polymetallic alloy nanosheet catalysts. Herein, we synthesized palladium nanosheets (Pd NSs) catalyst with smooth surface structure via solvothermal method, smooth surface structure palladium platinum nanosheets (PdPt NSs) and palladium platinum nickel island particle nanosheets (PdPtNi IPNSs) catalyst. Compared with commercial TKK-Pt/C, the prepared PdPtNi IPNSs catalyst has better catalytic performance for oxygen reduction reaction (ORR), ethanol oxidation reaction (EOR) and methanol oxidation reaction (MOR). This work provides a simple and feasible strategy for the synthesis of stable and efficient polymetallic 2D alloy nanostructured catalysts.     

Electrodeposition of Ni–Fe–Mn ternary nanosheets as affordable and efficient electrocatalyst for both hydrogen and oxygen evolution reactions

The synthesis of high performance and economical electrocatalysts in the process of overall water splitting is very important for the production of hydrogen energy and has become one of the most important challenges. Here, various Ni, Ni–Fe, Ni–Mn nanosheets and Ni–Fe–Mn ternary nanosheets were created using cost-effective, versatile and binder-free electrochemical deposition methods, and the electrocatalytic activity of various electrodes for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were investigated in an alkaline environment. Due to the high electrochemical active surface area due to the fabrication of nanosheets, the synergistic effect between different elements on the electronic structure, the high wettability due to the formation of nanosheets and the quick detachment of formed gasses from the electrode, the Ni–Fe–Mn nanosheets electrode showed excellent electrocatalytic activity. In order to deliver the 10 mA cm⁻² current density in HER and OER processes, this electrode required values of 64 mV and 230 mV overpotential, respectively. Also, the stability test showed that after 10 h of electrolysis at a current density of 100 mA cm⁻², the overpotential changes was very small (less than 4%), indicating that the electrode was excellent electrostatic stability. Also, when using as a bi-functional electrode in the full water splitting system, it only needed a cell voltage of 1528 V to deliver a current of 10 mA cm⁻². The results of this study indicate a new strategy for the synthesis of active and stable electrocatalysts.     

One-pot wet-chemical synthesis of uniform AuPtPd nanodendrites as efficient electrocatalyst for boosting hydrogen evolution and oxygen reduction reactions

Uniform trimetallic AuPtPd nanodendrites (NDs) were synthesized by a simple and quick method, using l-proline and ascorbic acid (AA) as eco-friendly structure-guiding agent and reducing agent, respectively. The obtained AuPtPd NDs displayed greatly enlarged electrochemically active surface area (27.65 m² g^?1_metal) relative to home-made AuPt nanocrystals (NCs, 21.76 m² g^?1_metal), AuPd NCs (3.91 m² g^?1_metal), Pt black (20.88 m² g^?1_metal) and Pd black (8.30 m² g^?1_metal). For hydrogen evolution and oxygen reduction reactions, AuPtPd NDs showed excellent catalytic performances relative to the referenced catalysts. These results reveal the practical applications of the as-obtained catalyst in energy storage and conversion.     

Detailed chemical kinetic mechanisms of ethyl methyl, methyl tert-butyl and ethyl tert-butyl ethers: The importance of uni-molecular elimination reactions

A reaction mechanism of ethyl methyl ether (EME), methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE) for pyrolysis and oxidation have been constructed using the same method applied to di-ethyl ether (DEE) in our recent work [1]. The mechanism, comprising of 1051 reactions involving 215 species, was tested against the experimental data obtained using shock tubes with good agreement. It was found that the uni-molecular elimination reaction has a larger influence on the pyrolysis and oxidation of MTBE and ETBE compared to EME and DEE at high temperatures. The energy barrier height between reactants and transition states of molecular elimination reactions calculated by high level ab initio MO methods has revealed the difference in reactivity among the four ethers. It is also shown that ETBE or MTBE inhibit the reactivity of an equi-molar 2% mixture of hydrogen and oxygen, whereas EME and DEE do not inhibit reactivity.