碳纳米管负载金属氮化物催化剂的制备及其性能研究

采用等体积浸渍法结合程序升温还原技术制备出一系列负载型过渡金属氮化物催化剂。利用XRD、BET、TPR等表征手段,结合氨分解制氢反应,研究了它们的表面性质和反应性能。发现改性碳纳米管负载的氮化钴催化剂具有较大的比表面积,对氨分解制氢反应的催化活性最高。新鲜态CoNx/CNTs催化剂的比表面积可达151.85m2/g,在650℃时氨转化率为80.3%,850℃达到完全转化。     

乙二醇还原Ru／CNTs的制备及催化氨分解性能研究

为获得高分散的Ru负载催化剂,采用乙二醇液相化学还原沉积法制备Ru／CNTs,TEM、XRD、H2-TPD表征,结果表明,乙二醇液相还原法可以制备金属粒径小（2—4nm）而均匀的高分散度的钌修饰CNTs,其表面存在较高稳态浓度吸附氢。以氨分解制氢作探针反应,实验结果表明,在相同反应条件下,经乙二醇油浴液相还原沉积制备的Ru／CNTs催化剂上氨转化率约为浸渍法制得相应催化剂上的1．6倍,同时发现钌微晶粒径在3—4nm范围的Ru／CNTs对氨分解制氢的催化性能最佳,钌微晶粒径≤2nm时氨分解转化率明显下降。     

微乳液法制备CNTs/PbO、CNTs/CuO复合材料

采用W/O型微乳液法制备出了CNTs/PbO和CNTs/CuO,利用电导率仪测量体系的溶水量,通过绘制三元相图研究了微乳液组成的表面活性剂和助表面活性剂的配比、温度以及盐的浓度等因素对W/O型微乳液相区的影响。分析得出最佳微乳液体系环己烷和活性剂的比为4 6,表面活性剂和助表面活性剂的比为2 3,反应温度为25℃。根据推进剂的成分,将一定量的燃烧催化剂和黑索今混合,通过热分析表征CNTs/PbO、CNTs/CuO对黑索今的催化热分解。结果表明,新的催化剂明显加快黑索今的热分解,分解峰位降低16.07℃。     

Li的掺杂对Ni/CNTs催化苯加氢反应性能的影响

采用浸渍的方法制得不同含Li量的NiLi/CNTs催化剂,以苯加氢反应为探针反应考察了催化剂的催化活性,利用H2化学吸附、H2-TPR、XRD、抗硫性能测试等手段,研究了Li的添加对Ni/CNTs催化性能的影响.结果表明,Li的添加对Ni/CNTs的催化性能有较大的影响.适量Li的添加有助于增加金属Ni在催化剂表面的裸露度,增加了苯加氢反应活性和耐硫性能.当Ni和Li的原子比为10:1时,Ni/CNTs催化剂的催化性能最好,在较低的反应温度(413K)苯的摩尔转化率和选择性达到100%,催化剂的极限耐流量为545.5μLCS2/gNi.     

负载型催化剂对风化煤制备腐植酸的影响

以自制碳纳米管(CNTs)为载体,制备了负载型催化剂CeO2/CNTs、TiO2/CNTs和Ce-Ti-Ox/CNTs,并进行了TEM及XRD表征。以所得样品为催化剂用于东都风化煤降解制备腐植酸的研究,探讨了催化剂用量、反应温度及不同负载型催化剂对风化煤降解制备腐植酸的产率、分子结构及吸光度的影响。结果表明,所用负载型催化剂催化性能明显高于未负载的催化剂,能显著提高腐植酸的产率,而且所得腐植酸分子量较小,吸光度较高,其中Ce-Ti-Ox/CNTs催化效果最为显著,可使腐植酸的产率提高到65.43%,表明铈钛活性组分表现出了协同催化效应。     

聚合物热解法制备碳纳米管/铝复合粉末及其反应动力学研究

采用聚合物热解化学气相沉积(PP-CVD)法, 通过聚乙二醇(PEG)的原位热解提供碳源、柠檬酸(CA)和硝酸钴反应产生催化剂纳米粒子, 在微纳米级的片状铝粉基底上原位生长碳纳米管(CNTs)。通过实验和反应动力学建模研究了PP-CVD反应机理, 揭示了PEG热解气相成分和催化剂纳米粒子表面气-固反应对CNTs生长速率的影响规律。CO初始分压和反应温度提高, CNTs生长速率提高; H₂初始分压和催化剂密度提高, CNTs生长速率降低。模型预测的CNTs平均长度随反应温度和反应时间的变化趋势符合实验结果。因此, 本研究为进一步优化CNTs/铝复合粉末制备工艺提供了新的理论依据。     

CoMoN_x/CNTs催化剂氯代硝基苯选择性催化加氢反应性能

采用等体积浸渍法结合程序升温还原技术制备出一系列负载型过渡金属氮化物催化剂,并利用XRD、BET、TG-DSC等手段对催化剂进行表征。将此催化剂用于邻氯硝基苯液相催化加氢。结果表明,单组分MoN/CNTs催化剂的活性较低,氯代硝基苯转化率为57.5%,双组份CoMoN_x/CNTs的活性较高,氯代硝基苯转化率为89.8%,添加了稀土La后CoMoN_x/CNTs催化剂活性改善不明显,但对o-CAN选择性达到了99.3%。     

铜/碳纳米管复合粒子的制备及其对高氯酸铵热分解性能研究

以碳纳米管为载体, 用化学沉积法制备了Cu/CNTs复合粒子, 并用TEM、SEM、FT-IR、XRD、XPS和DTA对其表观形貌、结构及催化性能进行了表征. 结果表明, CNTs和Cu之间无论是简单混合还是复合, 对高氯酸铵(AP)的热分解均有催化作用. 与纯AP相比, Cu/CNTs复合粒子中的AP高温分解峰温降低126.3℃, 低温分解峰几乎消失, 表观分解热由309.92J/g提高到711.13J/g; 与简单混合物相比, 复合粒子中的AP高温分解峰温降低11.4℃, 表观分解热由494.06J/g提高到711.13J/g. 表明CNTs与Cu的复合处理可显著提高其对AP热分解反应的催化作用.     

碳纳米管/羟基磷灰石复合材料的制备及表征

以含钴介孔分子筛为催化剂、乙醇为碳源, 采用CVD法制备碳纳米管(CNTs)。通过原位合成法制备一系列不同碳纳米管含量的碳纳米管/羟基磷灰石(CNTs/HA)复合材料。分别采用XRD、FTIR、TEM、N₂吸附-脱附和Raman光谱等分析手段, 对所合成CNTs/HA复合材料的晶相、结构、形貌和比表面积等进行了表征。同时研究了碳纳米管的添加量对所合成CNTs/HA复合材料形貌的影响。XRD与Raman结果表明, 所得CNTs/HA复合粉体中仅有CNTs与HA两种物相, 纯度较高, 结晶度较好; TEM结果显示, CNTs/HA复合材料中CNTs表面均匀包裹着一层纳米级的针状HA晶粒, 两者形成了较强的界面结合, 且当CNTs与HA的质量比为3:17时, CNTs与HA形成最佳结合状态; N₂吸附-脱附表征结果表明, 与HA的比表面积相比, CNTs/HA复合材料具有较高比表面积。     

SO_2促进的碳纳米管负载V_2O_5催化剂用于NH_3选择性还原NO

采用透射电镜(TEM)、X射线光电子能谱(XPS)、红外光谱(FT-IR)、SCR反应和程序升温脱附(TPD)等手段研究了碳纳米管(CNTs)担载的五氧化二钒(V2O5/CNTs)催化剂的形貌、表面形态以及SO2对选择催化NO还原活性的影响.结果表明,SO2对V2O5/CNTs催化剂的催化活性具有明显的促进作用,其促进作用源于SO2在催化剂表面的吸附.吸附的SO2主要位于碳表面而非钒表面,而且这种促进作用与V2O5和碳表面之间协同作用有关.     

Modeling and simulation of ammonia removal from purge gases of ammonia plants using a catalytic Pd-Ag membrane reactor

In this work, the removal of ammonia from synthesis purge gas of an ammonia plant has been investigated. Since the ammonia decomposition is thermodynamically limited, a membrane reactor is used for complete decomposition. A double pipe catalytic membrane reactor is used to remove ammonia from purge gas. The purge gas is flowing in the reaction side and is converted to hydrogen and nitrogen over nickel-alumina catalyst. The hydrogen is transferred through the Pd-Ag membrane of tube side to the shell side. A mathematical model including conservation of mass in the tube and shell side of reactor is proposed. The proposed model was solved numerically and the effects of different parameters on the rector performance were investigated. The effects of pressure, temperature, flow rate (sweep ratio), membrane thickness and reactor diameter have been investigated in the present study. Increasing ammonia conversion was observed by raising the temperature, sweep ratio and reducing membrane thickness. When the pressure increases, the decomposition is gone toward completion but, at low pressure the ammonia conversion in the outset of reactor is higher than other pressures, but complete destruction of the ammonia cannot be achieved. The proposed model can be used for design of an industrial catalytic membrane reactor for removal of ammonia from ammonia plant and reducing NO(x) emissions.     

热分解露点法测量超纯氨中的痕量水分

介绍了运用热分解露点法测量超纯氨气中微量水分的方法与设备。主要包括SH-7000冷镜式露点仪与热分解露点检测装置(TDDP)两部分。SH-7000露点仪基于冷镜式露点仪原理,采用微型专用制冷机,可准确地测量高纯气体的露点。TDDP系统基于氨气在高温环境下通过催化剂会发生不可逆的分解反应,而氨气中微量水分不会变化的原理,配合微量氧含量的测量,可准确得到氨气中的微水分含量。     

pH值调节剂对MnZn铁氧体纳米晶形成及磁性能影响

用硝酸盐-柠檬酸溶胶凝胶自燃法获得锰锌铁氧体（MZF）纳米晶。采用TG-DTA,XRD、VSM等方法对不同种类pH调节剂和不同pH值处理的凝胶热分解过程及产物的性能进行了表征结果表明：溶胶pH值和溶胶pH值调节剂对锰锌铁氧体纳米晶的形成有很大的关系。氨水调节凝胶的自燃点温度会随着溶胶的pH值从3．4增加到10而从196℃变到207℃。用乙二胺调节pH值,可以控制锰锌铁氧体纳米晶颗粒在19nm和57nm间变化。乙二胺调节pH值的系统热分解反应速度比氨水调节的系统反应速度慢,其反应生成粉体的饱和磁化强度为60emu／g,而氨水调节的系统生成粉体的饱和磁化强度为70emu／g。乙二胺调节系统生成粉体的矫顽力在pH值大于7后会有所增大。     

Synthesis, characterization and properties of nitrogen-rich salts of trinitrophloroglucinol

Five different nitrogen-rich salts of trinitrophloroglucinol (H(3)TNPG) have been prepared by the reaction of ammonia, aminoguanidine (AG), carbohydrazide (CHZ), semicarbazide (SCZ) and 5-aminotetrazo (ATZ) with trinitrophloroglucinol in aqueous solution through the heating method of water bath, with the yield up to 80%. These salts were characterized by elemental analysis, FT-IR, DSC and TG-DTG techniques. Their melting temperature is consistent with the thermal decomposition temperature. Their thermal decomposition process and kinetic parameters from 323 to 673K were investigated under a linear heating rate by DSC. The thermal decomposition of these salts undergoes an intensive exothermic decomposition stage to evolve abundant gas products and the enthalpies of exothermic decomposition reaction are high. The tests of sensitivity properties show these salts are insensitivity. All the properties of five nitrogen-rich salts appeared to depend on molecule structures and interconnection. It can be concluded that the five compounds are worthy of further in-depth studies as the gas-generating composition, emission reagents and propellants.     

Decomposition of acetamide and formamide in pressurized hot water

Acetamide and formamide were individually decomposed in a pressurized hot water in a tubular flow reactor at temperatures from 573 to 693 K, and pressure of 23 MPa, residence times up to 500 s, and the initial concentrations of both amides from 0.005 to 0.5 mol/L. The major products were ammonia and acetic acid from decomposition of acetamide, and ammonia and formic acid from that of formamide. Formic acid was further decomposed readily into carbon dioxide. Although the decomposition reactions for both amides were represented acceptably by the first order reaction kinetics, the rate constants increased with increasing the initial sample concentrations due to the autocatalytic effect. Apparently the second order reaction kinetics with respect to the concentration of each amide remained more represented the global decomposition rates, and the rate constants decreased with increasing the initial concentrations. The effects of hydrogen peroxide added on the global decomposition rates and the product yields were not evident: the addition slightly lowered the rates, but the major products were almost the same as those in the absence of hydrogen peroxide at temperatures lower than 653 K. Above 653 K more CO₂ was produced.     

Hydrogenation of the intermetallic compound Zr2Ni

We have determined conditions for the preparation of hydride phases with the composition Zr₂NiH_～5 by reacting the intermetallic compound Zr₂Ni with hydrogen or ammonia and identified the products of the reaction between the intermetallic compound and ammonia in the temperature range 150–500°C in the presence of NH₄Cl as an activator. The results demonstrate that the use of ammonia at 500°C leads to decomposition of the intermetallic compound and formation of zirconium hydride, zirconium nitride, and metallic nickel.     

氨硼烷同分异构体H_2B(NH_3)_2BH_4的制备

本文以NaBH_4为硼源、氨基络合物为氨源制备出了能缩短氨硼烷热分解放氢诱导期的氨硼烷同分异构体H_2B(NH_3)_2BH_4。研究了反应温度、时间和溶剂等因素对H_2B(NH_3)_2BH_4产率的影响。实验结果表明:在温度为25℃,物质的量Cu(NH_3)_6Cl_2∶NaBH_4=1∶2,反应时间为10h的条件下,制得的H_2B(NH_3)_2BH_4产率高达74%。XRD检测到反应产物中有金属Cu,经超景深显微镜观测,其粒径大小约为20μm。     

Nitridation characteristics of floating aluminium powder

Experimental parameters for floating nitridation process were examined to study the effect on moving behaviour and direct nitridation characteristics of aluminium powder, which was carried over from a fluidized bed. The conversion increased with increasing reactor temperature and mole ratio of ammonia to aluminium. It was also strongly dependent on the thermal decomposition of ammonia participated in the reaction. Aluminium powder was converted to aluminium nitride as high as 0.90 when the reactor temperature was 1300 °C and the mole ratio was 19.5 The particle size and specific surface area of the powder increased with increasing conversion, which was due to the volumetric and structural change of aluminium particles when nitrided to form fine crystallites with higher porosity.     

溶胶-凝胶自蔓延法制备球形纳米铜粉

以硝酸铜、柠檬酸为原料,利用氨水调节pH制备溶胶,将溶胶蒸发干燥得到的干凝胶通过自蔓延法制得金属铜纳米粉体,研究pH在制备溶胶-凝胶过程中对成胶时间的影响,以及pH、自蔓延温度对产物组成的影响;通过差热分析、X射线衍射和扫描电镜分别对凝胶的热分解机制、产物的物相组成以及形貌和粒度进行分析。结果表明,当pH=6～7时,形成的凝胶均一,凝胶时间最短(4 h);当自蔓延反应温度为250℃时,可以制得粒径为50～70 nm的球形纳米铜颗粒。