V6O15团簇钾、钠、钙中毒机理研究

为分析碱金属及碱土金属对催化剂主要活性组分V_6O_(15)分子团簇的影响,应用Gaussian软件结合密度泛函理论的B3LYP方法对V_6O_(15)分子团簇模型进行结构优化,并计算加入金属原子K、Na、Ca后钒基的分子结构参数、吸附能、LUMO轨道能量和加氢反应放热量,得出金属原子对钒基催化剂的作用机理和影响规律。结果表明:催化剂在吸附K、Na、Ca金属原子后催化活性下降;吸附碱金属后,V_6O_(15)团簇氧化性强弱顺序为:未中毒Ca中毒Na中毒K中毒;V_6O_(15)团簇中毒程度的影响顺序为:K中毒Na中毒Ca中毒未中毒。     

Oxy-Steam燃烧方式下的NO生成特性

以甲烷掺混氨气为燃料对oxy-steam气氛下NO生成特性进行实验和模拟研究.在常压柱塞流反应器中开展了一系列O_2/N_2和O_2/H_2O气氛的对比实验,当量比从富燃至贫燃(1.6、1.0、0.2),温度范围为973~1,773,K.实验结果表明,O2/H_2O气氛下高浓度的水蒸气在当量和贫燃工况下抑制NO的生成,而在富燃工况下促进NO生成.更新并构建的详细化学机理能够很好地重现并解释实验中NO的生成特性.当量和贫燃工况下,极少的O基团抑制了反应NH_2+O H+HNO从而抑制了NH_2→HNO→NO反应路径,最终降低了NO的生成.富燃工况下,充足的OH基团显著促进了反应NH_2+OH=NH+H_2O从而促进了NH_2→NH→HNO→NO反应路径,最终增加了NO的生成.     

CuO与负载间相互作用的密度泛函理论

通过密度泛函理论(DFT)模拟了不同负载对Cu基氧载体反应性能和抗烧结性能的影响.首先通过DFT模拟计算得出了CuO纳米团簇在4种不同负载(TiO_2、ZrO_2、CuAl_2O_4和MgAl_2O_4)上的吸附能分别为-2.96eV、-5.14eV、-4.25eV和-5.42eV,其中TiO_2的吸附能最低,不利于氧载体颗粒的抗烧结性,但CuO在ZrO_2、CuAl_2O_4和Mg Al2O4上的高吸附能有助于抑制氧载体的烧结.通过计算不同负载下团簇释氧过程的能量势垒来比较负载对氧载体释氧性能的影响.结果表明,氧气分子从表面的脱附过程是整个释氧过程的速控步骤.不同负载(TiO_2、ZrO_2、CuAl_2O_4和MgAl_2O_4)下CuO纳米团簇总的释氧能量势垒分别为3.45eV、3.33eV、3.28eV和3.41eV,其中负载于CuAl_2O_4的CuO释氧能量势垒最低,反应活性最高.     

SCR催化剂表面NH3和NO吸附实验与机理研究

选择性催化还原(SCR)技术被广泛应用于大型燃煤机组烟气氮氧化物脱除中,脱硝效率达到90%以上。烟气温度下降会导致SCR系统的催化剂受损,在停机之前会停止向SCR系统喷氨,导致此期间的NO_x排放超标。采集并计算了某电厂停炉过程中排放NO的数据,实验发现NO排放量在此过程中仍会有不同幅度的降低。运用密度泛函理论(DFT)基于V_2O_5团簇模型研究了NO和NH_3在催化剂不同吸附位上的吸附机理。研究结果表明:NO不会稳定吸附在催化剂的表面;NH_3既能吸附在钒基表面的Lewis酸性位,又可吸附在Br?nsted酸性位,而且更稳定。由此可知,停机后由于吸附在催化剂表面的NH_3与烟气中的NO反应,使得出口处的NO量降低。     

常温空气MILD燃烧过程中CO形成特性

采用实验和数值计算的方法,研究了甲烷在常温空气下的MILD燃烧.计算结果表明耦合机理GRI-Mech2.11的数值计算模型能很好地预测炉内CO、O_2和温度等参数.通过模拟发现,可以将整个炉膛划分成3个区域(Ⅰ:中心区,Ⅱ:高浓度区,Ⅲ:回流区),在不同区域内,CO的生成与消耗是不同的,其中CO的生成反应主要为(R166)(HCO+H_2O■H+CO+H_2O)、(R167)(HCO+M■H+CO+M)、(R168)(HCO+O_2■HO_2+CO),CO的消耗反应主要为(R99)(OH+CO■H+CO_2).     

等离子体辅助甲烷燃烧的主要反应路径/通道

通过实验和模拟的方法,对等离子体辅助甲烷燃烧主要基元反应进行了研究.实验测量了等离子体辅助甲烷燃烧火焰不同位置的发射光谱图,得到了参与该过程的重要组分;模拟过程中,基于密度泛函理论,研究了甲烷燃烧反应中O_2+H→OH+O、CH_4+OH/O/H→CH_3+H_2O/OH/H_2、CH_3+O→CH_2O+H、CH_2O+OH/O/H→CO+H_2O/(H+H_2O)/(H+H_2)等几个重要基元反应,在B3LYP/6-311++G**水平找到了各反应可能的反应路径/通道,并进行分析.在此基础上,对比分析了放电等离子体作用下各反应路径/通道的变化,结果表明,在研究等离子体辅助甲烷燃烧机理时,应基于甲烷燃烧机理进行完善,通过加入*2HO(v)、O(1D)、CH_4(v)等激发态组分,并对一些基元反应进行拆分或合并,重新计算各反应活化能;生成的激发态组分会提升反应势能面,降低活化能,加速反应进程;在CH_2O与O/OH/H的反应中,放电等离子体可将生成的HCO直接分解,降低了HCO对H原子的消耗,同时还会释放一个H原子,有利于燃烧反应的进行.     

MoO3催化剂上苯酚加氢脱氧制取芳烃研究

以(NH_4)_6Mo_7O_(24)·4H_2O为前驱体通过简单的焙烧方法制备非负载型MoO_3催化剂,通过低温N_2吸附、X射线衍射(XRD)、X射线光电子能谱(XPS)和H_2程序升温还原(H_2-TPR)技术对催化剂特性进行表征,以苯酚为模型化合物进行加氢脱氧实验制备以苯为主要产物的芳烃化学品。重点考察反应温度、反应时间、反应气组成等参数对苯酚转化率、目标产物苯选择性的影响,并就氧化钼催化加氢脱氧反应机制及催化剂的可重复使用性能进行讨论与考察。实验结果表明,在340℃、0.5 MPa H_2与3.0 MPa N_2混合气氛的优化工况下,苯酚的转化率达到98.1%,产物苯选择性达到99.5%。MoO_3催化材料中的氧缺陷位是催化苯酚分子中C_(AR)—OH键直接氢解生成芳烃苯的主要活性位。此外,MoO_3重复使用3次后催化活性仍无明显下降,表明该催化剂的加氢脱氧催化活性具有良好的稳定性。     

水蒸气浓度对层流甲烷扩散火焰中碳烟生成的影响

对甲烷在氧—汽燃烧过程中碳烟生成状况进行了数值模拟研究。通过对比O_2/N_2和O_2/H_2O氛围下四种工况(21%O_2、30%O_2、40%O_2、50%O_2)的火焰形态和碳烟体积分数,发现相同O_2浓度下,前者火焰温度、火焰高度、碳烟体积分数均低于后者,表明H_2O能够明显抑制碳烟生成。通过对比O_2/N_2、O_2/H_2O和O_2/FH_2O氛围下四种工况的最大碳烟体积分数和最大颗粒数量密度,表明不仅H_2O的化学效应抑制碳烟生成,而且其他三大效应也共同抑制碳烟生成。通过进一步分析化学效应随H_2O浓度的变化规律,确定了H_2O浓度为60%时,化学效应的抑制效果最佳。     

飞灰未燃尽碳吸附(HgS)n及(HgO)n的量化分析

为研究飞灰中未燃尽碳对(HgS)_n及(HgO)_n(n=1~4)的吸附机理,构建了三碳环石墨烯结构作为未燃尽碳分子表面模型,应用密度泛函理论在B3LYP/6-31G(d)水平上进行结构优化,在PWPB95/def 2-Tzvp水平上计算了体系的单点能。研究表明:HgS及HgO团簇在未燃尽碳表面的吸附形式为化学吸附,吸附能为-646.546~-105.116 k J/mol;HgS及HgO团簇以解离和非解离形式吸附于未燃尽碳表面,更倾向于稳定的解离吸附;相同情况下HgO团簇的吸附稳定性高于Hg S团簇;团簇数量的增加对吸附能几乎无影响,当吸附位点增多时,吸附能绝对值显著增加,吸附稳定性提高。     

烟气中各成分含量的测算方法

<正> 调试锅炉、焦炭装置及其他热工设备,必须了解成分及其含量。但多数情况下,传统计算方法不能真实的反映出各燃烧产物的含量,因为烟气的含量都是根据查表来计算的(其中有V_(A·m)和H_2O)或是用规定的试验方法确定。建议根据气体分析结果计算各烟气成分含量,水蒸汽的含量(％)用下式计算: H_2O=100(RO_2+O_2+N_2) 燃烧产物中氮的含量(％)用下式计算: N_=(3.76α×O_2)/(α-1)     

Evaluation of in-situ formed La2O3–TiO2–La2O2CO3 nanocomposite photocatalyst for H2 production

The photocatalytic evolution of H₂ over La₂O₃ decorated TiO₂ catalyst was examined under solar light. It was observed that during the course of the reaction, the transformation of La₂O₃/TiO₂ into La₂O₃–TiO₂–La₂O₂CO₃ occurred and these species effectively suppressed electron-hole pair recombination by forming electron trapping centres on the surface, resulting in an increased visible light absorption and improved H₂ yield. The 2 wt%La₂O₃/TiO₂ nanocomposite demonstrated better H₂ yield (～8.76 mmol (g_cat)^?1) than the bare TiO₂ (～1.1 mmol (g_cat)^?1). The catalyst was stable even after several consecutive recycles with no substantial loss of hydrogen production rate. The H₂ rates were correlated with the physicochemical characteristics of the catalysts examined by BET–SA, H₂-TPR, XRD, UV-DRS, Raman spectroscopy, FTIR, HRTEM, EPR and PL spectroscopy.     

Photocatalytic H2 production over RuO2@ZnS and RuO2@CuS nanostructures

Photocatalytic hydrogen production is a promising approach of sustainable economy, because a use of sunlight and water to produce a fuel will solve a problem of fossil fuels depletion. Metal sulfides are well known photocatalysts in water splitting process, but in absence of sacrificial electron donor they undergo a photocorrosion. In this paper we studied a possible strategy to protect the sulfide photocatalysts and to improve its photostability by a deposition of small amount of ruthenium oxide at surface of sulfides. Nanocrystalline zinc sulfide and copper sulfide were prepared in a hydrothermal way and have been functionalized by RuO₂. As prepared photocatalysts showed good activity towards hydrogen formation. Modification of sulfides with ruthenium oxide had a few positive effects: it expanded a light absorption range by photocatalysts, enhanced the photocatalytic activity towards H₂ formation, improved a photostability in comparison with neat ZnS and CuS as well as protected from the electronic and structural changes within semiconductors due to irradiation.     

Numerical study of the O2/CO2, O2/CO2/N2, and O2/N2-syngas MILD combustion: Effects of oxidant temperature,O2 mole fraction,and fuel blends

Moderate or Intense Low-oxygen Dilution (MILD) combustion of a syngas fuel under air-fuel, oxygen-enhanced, and oxy-fuel condition are numerically studied with using counterflow diffusion flame. Fuel composition, temperature of oxidant (T_ox), and oxygen mole fraction (X_O2) are selected as the main parameters. Fake species (FCO₂) with the same CO₂ physical properties is used for separation the physical and chemical effects of replacing CO₂ with N₂. According to the results, under the high preheating temperatures, the chemical effect of changing the oxidant composition from N₂ to CO₂ is the main reason of the changes in flame structure, ignition delay time (IDT) and heat release rate (HRR) while physical differences play a more prominent role in the low preheating temperature MILD combustion. In all X_O2, the physical and chemical effects of replacing CO₂ with N₂ have almost the same role on the maximum flame temperature. The results of IDT expressed that chemical discrepancies of CO₂ and N₂ play a key role on IDT enhancement by increasing CO₂ in the oxidant composition. The sensitivity analysis of CH₂O for variations of T_ox and X_O2 shows that reactions R54, R56, R58, and R101 are the main responsible of lower HRR and higher IDT by moving from air-syngas to oxy-fuel MILD combustion.     

Photocatalytic reduction of CO2 using TiO2 powders in supercritical fluid CO2

The photocatalytic reduction of CO₂ was investigated using TiO₂ powders in supercritical fluid CO₂. These were irradiated in a stainless steel vessel at 9.0 MPa and 35°C. After reducing the CO₂ pressure to the ordinary state, pure water was added to the vessel while avoiding air contamination. No gaseous reduction products were observed. Formic acid was obtained only in aqueous solution. The optimal irradiation time for the production of formic acid was 5 h. Addition of acidic solutions rather than pure water was preferable for formic acid formation. Formic acid seems to be produced through the protonation of reaction intermediates on TiO₂ powders in solutions. The CO₂-reduction system described here may be of practical value for efficient CO₂-conversion and fixation, storage of solar energy, and production of raw materials for the photochemical industry.     

保护气氛烧结炉

介绍了HIC封装管壳中玻璃绝缘子网带烧结炉的特殊机械结构、氮氢保护气氛系统和电气保护措施。确立了网带炉低速爬行力学模型及炉内合理的气氛流向。     

New gas chromatographic packing ZIF-67@NH2–SiO2 for separation of hydrogen isotope H2/D2

ZIF-67@NH₂–SiO₂ composites were prepared by loading the metal-organic frameworks ZIF-67 on amino modified SiO₂ gel particles (NH₂–SiO₂, 80–100 mesh) through layer-by-layer self-assembly method. Systematic investigation on the effects of ZIF-67 loading amounts on NH₂–SiO₂ packed stainless steel chromatographic column (specification 1.0 m×2.0 mm I.D.), the flow rate of He as carrier gas and the injection amount of mixed gas (H₂/D₂) on the hydrogen isotope H₂/D₂ separation performance at liquid nitrogen temperature, unraveled the optimal conditions for H₂/D₂ isotope separation. The results showed that the optimal stationary phase materials under the optimized conditions can effectively separate H₂ and D₂ with separation resolution R = 1.52 and the separation time t = 10.15 min. The superior performance of the ZIF-67 is tentatively thought to be due to kinetic quantum sieving (pore size 3.3 Å) effect and chemical affinity sieving effect of Co ion in ZIF-67.