氢氧直接合成法制备过氧化氢过程中的催化剂探究

通过氢氧直接合成过氧化氢法常见应用于印染纺织、污水处理以及化学合成等方面。作为一种简单高效且环保的绿色氧化剂,过氧化氢的合成成为了社会研究热点。通过对过氧化氢氢氧直接合成的路径进行研究,并对这一过程中的催化剂金属进行分析,包括单金属以及双金属。随后对催化剂的载体进行研究分析,分析载体酸性、表面物质以及掺杂物等对催化剂性能所产生的影响,发现今后过氧化氢直接合成过程中催化剂的发展方向将定位为高选择性与高产率。     

碳纳米管、碳化钨在直接法合成过氧化氢中的应用

选用新型纳米材料——碳纳米管（CNTs）作为催化剂载体,用沉积沉淀法制备负载型钯-铂合金催化剂。同时选用过渡金属碳化物材料（碳化钨）为催化剂,其具有类似于Pt的表面电子结构,有望替代贵金属催化剂。探讨了Pd-Pt/CNTs及碳化钨在氢氧直接合成过氧化氢反应中的催化性能。     

氢氧直接合成过氧化氢催化剂研究进展

从性组分和载体两方面,总结了近年来氢氧直接合成过氧化氢催化剂的研究进展,重点介绍了Au-Pd、Pt-Pd双金属催化剂在氢氧直接合成过氧化氢中的应用研究。指出负载型纳米双金属催化剂将是氢氧直接合成过氧化氢催化剂研究的发展方向。摘要：从活性组分和载体两方面，总结了近年来氢氧直接合成过氧化氢催化剂的研究进展，重点介绍了Au—Pd、Pt—Pd双金属催化剂在氢氧直接合成过氧化氢中的应用研究。指出负载型纳米双金属催化剂将是氢氧直接合成过氧化氢催化剂研究的发展方向。     

由氢与氧直接合成过氧化氢研发新进展

综述了2016年以来国内外由氢与氧直接合成过氧化氢的研发进展,其中主要包括所用催化剂性能提高、合成装置和方法改进以及合成反应机理。介绍了多种不同催化金属(仍以Pd为主)、不同载体的催化剂和催化金属纳米颗粒(簇)形态及粒径、载体多种选择等对提高催化性能尤其是生成过氧化氢选择性的影响,以期获得更理想的催化剂。简要介绍了不同形式反应器和不同反应条件对反应结果尤其是反应选择性的影响。最后介绍了一些学者对直接合成过氧化氢过程中化学反应途径和机理所进行的较为详细和深入的研究以及所取得的结果和新发现。     

由氢、氧直接合成过氧化氢研究新进展

介绍了由氢、氧直接合成过氧化氢研究新进展,研究重点是催化剂的组成和制备,其中包括催化金属的组成和载体的选择以及它们的预处理等。研究结果普遍表明,双金属催化物质(Pd-Au或Pd-Pt)的催化性能优于单金属催化物质(Pd);载体对催化剂性能也有显著影响,大多优选活性炭。在一些研究中,进行了对比实验,得出上述结论。实验中主要考察了催化剂生成H2O2的活性和选择性等。此外,还介绍了一些学者对催化金属颗粒在载体表面的形态结构、分布、粒径(纳米级)等对催化剂催化性能影响的研究。     

氢氧直接合成过氧化氢用PdO/γ-Al2O3催化剂过渡金属改性研究

采用等体积浸渍法制得过渡金属改性的系列催化剂MOx-PdO/γ-Al2O3 (M=La、Mn、Ni、Ce).在10℃、常压下考察了过渡金属种类及氧化镧负载量对催化剂MOx-PdO/γ-Al2O3催化氢氧直接合成过氧化氢性能的影响.采用能谱(EDS)、X射线衍射(XRD)、程序升温还原(H2-TPR)等手段对催化剂进行表征分析.结果表明,经过渡金属改性后的MOx-PdO/γ-Al2O3催化剂活性高于未改性的催化剂PdO/γ-Al2O3;以镧为助剂制得的La2O3-PdO/γ-Al2O3(氧化镧质量分数为1％、氧化钯质量分数为2.5％)催化剂性能优于其他过渡金属改性的催化剂,与PdO/γ-AhO3相比,所得过氧化氢的浓度、收率、选择性分别提高了76.54％、76.61％、44.21％.     

Pd-SiO2催化剂制备、结构及其用于氢氧直接合成过氧化氢的反应性能

利用水热法原位合成制备了一种活性组分Pd颗粒尺寸可控且表面具有一定酸性位的大孔容Pd-SiO2催化剂.通过调节前驱液的pH值控制SiO2层的结构性质,利用TEM、XRD、N2吸附-脱附和NH3-TPD等手段对催化剂的结构和表面性质进行了表征分析,并考察了Pd-SiO2催化剂催化氢氧直接合成过氧化氢的反应性能.结果表明:水热法原位合成制备的Pd-SiO2催化剂,Pd颗粒分散较好,其尺寸范围为10～ 20 nm;对直接法催化合成过氧化氢反应,水热法原位合成制备的Pd-SiO2催化剂的催化性能明显优于传统浸渍法制备的Pd/SiO2催化剂,这是由于调节前驱液的pH值可减少催化剂的表面强酸量,有利于提高过氧化氢的稳定性.     

不同金属改性剂对Rh/FePO4催化剂氢甲酰化性能的影响

采用等体积浸渍法制备了不同金属（La、Co、Ce、Cr）改性的M-Rh/FePO₄催化剂,考察不同催化剂在1-辛烯氢甲酰化中的反应性能;利用XRD、H₂-TPR、XPS等对催化剂进行表征。结果表明,不同改性剂对Rh/FePO₄催化剂中金属Rh与载体FePO₄改性效果不同,其中金属Cr的加入对Rh/FePO₄催化性能的提高明显优于其他3种改性剂,同时,过多金属Cr的加入降低了催化性能。当金属Cr质量分数为0.1%时,可显著增强金属Rh与载体FePO₄之间的相互作用,在1-辛烯氢甲酰化反应中表现出较好的催化性能,可获得99.4%的转化率和92.8%的醛收率。催化剂经5次循环反应后仍保持较好的活性和选择性,具有良好的循环稳定性。     

国外由氢氧直接催化合成过氧化氢研究概况

概述了国外由氢氧直接催化合成过氧化氢的研究近况;详述了以溴化物为促进剂由氢氧直接催化合成过氧化氢的工艺过程与试验结果。此外,还对合成所用某些催化剂的制备方法作了介绍。     

过氧化氢绿色合成工艺研究进展

过氧化氢是一种重要的绿色化工产品。由氢气和氧气直接催化合成过氧化氢是一种理想的原子经济性反应,但是该方法的工业化应用面临严峻的技术挑战。本文介绍了近年来氢氧直接合成过氧化氢反应过程相关的活性催化组分Pd、双金属Pd-Au、固体酸类载体、膜反应器和微通道等新型反应器的研究与应用性能;基于过程集成与强化的角度,提出将氢氧直接合成过氧化氢过程与其它特定生产工艺相集成,减少不必要的提浓、运输和稀释等环节,以实现安全、环保的过氧化氢绿色生产和应用。     

Direct synthesis of hydrogen peroxide over Pd nanoparticles embedded between HZSM-5 nanosheets layers

Direct synthesis of hydrogen peroxide (DSHP) was studied over Pd loaded on HZSM-5 nanosheets (Pd/ZN). Pd nanoparticles with average size of ca. 4.3 nm were introduced into the adjacent nanosheet layers (thickness of ca. 2.9 nm) by impregnation method. Pd/ZN with theoretical Si/Al molar ratio of 25 showed the highest selectivity for H₂O₂ among the prepared catalysts, together with highest formation rate of H₂O₂ (38.0 mmol·(g cat)^-1·h^-1), 1.9 times than that of Pd supported on conventional HZSM-5 zeolite (Pd/CZ-50). Better catalytic performance of nanosheet catalysts was attributed to the promoted Pd dispersion which promoted H₂ dissociation, more Brønsted acid sites and stronger metal-support interaction which inhibited the dissociation of O-O bond in H₂O₂. The embedded structure sufficiently protected the Pd nanoparticles by space confinement which restrained the Pd leaching, leading to a better catalytic stability with 90% activity retained after 3 cycles, which was almost 3 times than that of Pd/CZ-50 (30.4% activity retained).     

Renewable hydrogen production from steam reforming of glycerol (SRG) over ceria-modified γ-alumina supported Ni catalyst

Excess crude glycerol derived as a by-product from biodiesel industry prompts the need to valorise glycerol to value-added chemicals. In this context, catalytic steam reforming of glycerol (SRG) was proposed as a promising and sustainable alternative for producing renewable hydrogen (H₂). Herein, the development of nickel (Ni) supported on ceria-modified mesoporous γ-alumina (γ-Al₂O₃) catalysts and their applications in catalytic SRG (at 550-750 °C, atmospheric pressure and weight hourly space velocity, WHSV, of 44,122 ml·g^-1·h^-1 (STP)) is presented. Properties of the developed catalysts were characterised using many techniques. The findings show that ceria modification improved Ni dispersion on γ-Al₂O₃ catalyst support with highly active small Ni particles, which led to a remarkable catalytic performance with the total glycerol conversion (ca. 99%), glycerol conversion into gaseous products (ca. 77%) and H₂ yield (ca. 62%). The formation rate for H₂ production (14.4 × 10^-5 mol·s^-1·g^-1, TOF (H₂) = 3412 s^-1) was significantly improved with the Ni@12Ce-Al₂O₃ catalyst, representing nearly a 2-fold increase compared with that of the conventional Ni@Al₂O₃ catalyst. In addition, the developed catalyst also exhibited comparatively high stability (for 12 h) and coke resistance ability.     

Ni-Mn/Al2O3催化剂在浆态床中CO甲烷化催化性能

采用共浸渍法制备了Ni-Mn/Al₂O₃催化剂,考察了助剂Mn的含量对催化剂结构及浆态床CO甲烷化性能的影响。采用XRD、H₂-TPR、BET、TEM、H₂-化学吸附等表征对催化剂进行了测试分析,结果表明,Mn助剂的引入能够促进Ni物种在载体表面的分散,减弱Ni物种与载体的相互作用,降低催化剂的还原温度,提高催化剂的比表面积,减小活性金属Ni的晶粒尺寸。随着Mn含量的增加,Ni-Mn/Al₂O₃催化剂的甲烷化性能先升后降,其中以Mn含量为4%（质量分数）时的催化甲烷化性能最佳,添加过量的Mn导致活性组分Ni被部分覆盖,催化甲烷化性能下降。通过对16Ni4Mn/Al₂O₃催化剂样品的浆态床反应温度及反应压力的研究发现,当反应温度为280℃、反应压力为1.5 MPa时,催化剂样品16Ni4Mn/Al₂O₃的CO转化率及CH₄选择性分别达到96.2%和88.8%。     

溶胶-凝胶原位合成宽活性温度V2O5/TiO2脱硝催化剂

利用溶胶-凝胶技术原位合成一系列不同V₂O₅担载量的V₂O₅/TiO₂催化剂,通过BET、XRD、NH₃-TPD及紫外-可见光等手段对催化剂进行表征。结果表明：制备的催化剂均具有介孔结构,V₂O₅在TiO₂表面高度分散,且存在3种典型的酸性位。通过选择性催化还原反应对V₂O₅/TiO₂催化剂进行活性评价,结果显示随着V₂O₅含量的增加,NO转化率大于75%的温度窗口向低温方向偏移,含10% （质量分数）V₂O₅的催化剂的NO转化率为80%的温度窗口最宽为200～450℃,240℃时20 h连续实验表现出稳定的抗硫抗水性能。结合紫外-可见光谱分析,揭示了钒掺杂所形成的单聚和低聚钒酸盐为催化剂的活性组分。     

Co/Al_2O_3催化剂制备及其合成重质烃的反应性能

以不同孔道结构Al_2O_3作载体,甲醇、乙醇和柠檬酸作分散剂,通过等体积浸渍法制备系列Co/Al_2O_3费托合成催化剂。采用XRD、TG-DSC和H2-TPR等考察制备方法对催化剂结构的影响,并在固定床反应器中对催化剂进行性能评价。结果表明,采用具有适宜孔道结构Al_2O_3作载体才能获得综合性能较好的催化剂,3种分散剂的加入,促进了钴物种在载体上的分散,增强了钴与载体间的相互作用,改善了催化剂费托合成反应活性,显著提高了重质烃时空收率。     

动物骨源羟磷灰石负载Co3O4用于N2O催化分解

通过焙烧猪骨和鸡骨获得羟磷灰石(nHAP)载体,并采用浸渍法制备Co3O4/nHAP催化剂。采用XRD、N2物理吸附-脱附、FT-IR和H2-TPR等对催化剂进行表征,在连续流动微反装置上考察催化剂催化分解N2O的性能。结果表明,相比于鸡骨源Co3O4/nHAP催化剂,以猪骨源HAP为载体的催化剂因其较大的比表面积以及较小的Co3O4粒径尺寸,提供了更多的活性位点。特别是猪骨源Co3O4/nHAP催化剂中适量的K、Na等元素促进了Co^3+到Co^2+的还原,削弱了Co-O键,使催化剂的催化活性显著提高。     

Catalytic synthesis of methanethiol from hydrogen sulfide and carbon monoxide over vanadium-based catalysts

The direct synthesis of methanethiol, CH₃SH, from CO and H₂S was investigated using sulfided vanadium catalysts based on TiO₂ and Al₂O₃. These catalysts yield high activity and selectivity to methanethiol at an optimized temperature of 615 K. Carbonyl sulfide and hydrogen are predominant products below 615 K, whereas above this temperature methane becomes the preferred product. Methanethiol is formed by hydrogenation of COS, via surface thioformic acid and methylthiolate intermediates. Water produced in this reaction step is rapidly converted into CO₂ and H₂S by COS hydrolysis.

Titania was found to be a good catalyst for methanethiol formation. The effect of vanadium addition was to increase CO and H₂S conversion at the expense of methanethiol selectivity. High activities and selectivities to methanethiol were obtained using a sulfided vanadium catalyst supported on Al₂O₃. The TiO₂, V₂O₅/TiO₂ and V₂O₅/Al₂O₃ catalysts have been characterized by temperature programmed sulfidation (TPS). TPS profiles suggest a role of V₂O₅ in the sulfur exchange reactions taking place in the reaction network of H₂S and CO.     

富氧条件下氢气选择催化还原汽车尾气氮氧化物的研究进展

汽车尾气中的氮氧化物（NO _x ）是大气主要污染物之一,严重危害了环境和人类健康。选择催化还原（SCR）消除技术是一种在富氧条件下能够高选择性消除NO _x 的技术。氢气选择催化还原氮氧化物（H₂-SCR）由于其低温高活性的优势备受关注。目前H₂-SCR研究中以Pt和Pd作活性组分催化剂使用较多,其中Pt基催化剂的研究最为广泛,本文介绍了催化剂载体类型、载体性质（如酸碱性、比表面积、孔道结构）、助剂和预处理方式等对催化活性的影响及影响机制,综述了反应条件参数（如反应气中O₂和NO₂浓度,杂质气体H₂O和SO₂）对催化剂催化活性的影响,认为反应气组分的影响在于各组分在催化剂上的竞争吸附以及对催化剂活性位的影响,最后展望了面向实际应用H₂-SCR技术未来的研究方向。     

Coke study on MgO-promoted Ni/Al2O3 catalyst in combined H2O and CO2 reforming of methane for gas to liquid (GTL) process

MgO-promoted Ni/Al₂O₃ catalysts have been investigated with respect to catalytic activity and coke formation in combined steam and carbon dioxide reforming of methane (CSCRM) to develop a highly active and stable catalyst for gas to liquid (GTL) processes. Ni/Al₂O₃ catalysts were promoted through varying the MgO content by the incipient wetness method. X-ray diffraction (XRD), BET surface area, H₂-temperature programmed reduction (TPR), H₂-chemisorption and CO₂-temperature programmed desorption (TPD) were used to observe the characteristics of the prepared catalysts. The coke formation and amount in used catalysts were examined by SEM and TGA, respectively. H₂/CO ratio of 2 was achieved in CSCRM by controlling the feed H₂O/CO₂ ratio. The catalysts prepared with 20 wt.% MgO exhibit the highest catalytic performance and have high coke resistance in CSCRM. MgO promotion forms MgAl₂O₄ spinel phase, which is stable at high temperatures and effectively prevents coke formation by increasing the CO₂ adsorption due to the increase in base strength on the surface of catalyst.     

Catalytic activity of Pt and tungstophosphoric acid supported on MCM-41 for the reduction of NOx in the presence of water vapor

The catalytic activity of tungstophosphoric acid and Pt loaded MCM-41 for the catalytic reduction of NO_x with propene in the presence of water vapor was studied. Pt/MCM-41 was found to be most active, the loading with H₃PW₁₂O₄₀ led to an improved selectivity to N₂ formation and to an enhanced activity in the presence of water vapor. Hydrated tungstophosphoric acid generated additional sorption sites for C₃H₆ and led to a higher local concentration of the reducing agent on the catalyst surface, which was found to increase the activity of the Pt and H₃PW₁₂O₄₀ loaded catalysts in the presence of water vapor.