氢氧直接合成过氧化氢用催化剂的研究进展

过氧化氢（H₂O₂）是一种高效的绿色氧化剂,广泛应用于化学品合成、印染纺织、污水处理等领域。近年来,氢氧直接合成过氧化氢作为一种简单、环保、原子效率高的合成方法,成为一大研究热点。本文系统性地介绍了近年来氢氧直接合成过氧化氢催化剂的催化反应机理,负载金属的不同结构和性质对直接合成过氧化氢的催化性能与作用机理,重点讨论了与催化剂载体相关的载体结构、载体酸性、载体添加物、载体与金属相互作用等方面对反应活性和选择性的影响。最后对比了近年来直接合成过氧化氢用催化剂的催化性能,认为合成高选择性、高产率的催化剂仍是未来直接合成过氧化氢工业化应用的发展方向。     

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。     

氢氧直接合成过氧化氢用钯基催化剂研究进展

开发高活性、高选择性的催化剂是实现氢氧直接合成过氧化氢（DSHP）工业化应用的关键。本文系统性地综述了Pd基DSHP催化剂的设计、制备与开发,从催化作用机理、活性组分优化、形貌与尺寸调控、载体选择、制备方法改进、反应添加剂选择、反应环境调节等角度,着重讨论了目前对Pd基催化剂的活性和选择性的优化策略。最后对DSHP用Pd基催化剂的研究进展进行了总结,并对其未来发展前景进行了展望。     

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。     

制备工艺对负载型Pd催化剂催化加氢性能的影响

介绍了Pd催化剂催化加氢反应的机理,以及Pd催化剂在工业加氢反应中的应用现状和研究进展。重点讨论了负载型Pd催化剂的制备方式、载体、助催化剂等因素对其催化加氢性能的影响,以期为新型负载型加氢Pd催化剂的研究和开发提供参考。     

Ni基加氢脱氧催化剂的研究进展

以Ni基加氢脱氧催化剂为线索,分别介绍了负载型和非负载型催化剂的结构及其制备方法,总结了Ni基加氢脱氧催化剂的应用进展。对负载型Ni基催化剂从单一载体、复合载体、分子筛载体以及碳载体的角度总结了其在加氢脱氧中的应用。相对负载型催化剂活性组分负载量少的缺点,非负载型催化剂能大幅度提高活性组分的含量,具有更高的催化活性。按照金属种类的不同,总结了单金属、双金属、多金属非负载Ni催化剂在加氢脱氧中的应用。     

Al2O3负载Pd基催化剂的研究进展

氧化铝的化学性质稳定，并具有丰富的孔道结构，常被用为催化剂载体来分散金属活性组分，起到提高催化剂的催化活性和稳定性的作用，已被广泛地应用于化学工业中。负载型纳米Pd基催化剂具有优异的反应活性和产品选择性，己被广泛应用于催化加氢、脱氢、碳-碳耦合等反应中。综述了近年来Al₂O₃负载Pd基催化剂的研究进展。     

钼基加氢脱硫催化剂的制备及应用研究进展

以钼在加氢脱硫(HDS)中的应用为线索,按催化剂结构不同,简介了负载型催化剂和非负载型催化剂的制备方法,总结了钼基加氢脱硫催化剂的应用进展。对于负载型钼基催化剂,按照载体不同,从单一氧化物载体、复合氧化物载体、分子筛载体和碳材料载体角度总结了催化剂在加氢脱硫中的应用。负载型催化剂虽然应用广泛,但其活性组分受载体限制。而非负载型催化剂可以有效提高活性组分含量,具有更高的催化活性。按照催化剂组成不同,总结了近年来单金属型、双金属型和多金属型非负载型催化剂在加氢脱硫中的应用。     

钼基加氢脱硫催化剂的制备及应用研究进展

以钼在加氢脱硫(HDS)中的应用为线索,按催化剂结构不同,简介了负载型催化剂和非负载型催化剂的制备方法,总结了钼基加氢脱硫催化剂的应用进展。对于负载型钼基催化剂,按照载体不同,从单一氧化物载体、复合氧化物载体、分子筛载体和碳材料载体角度总结了催化剂在加氢脱硫中的应用。负载型催化剂虽然应用广泛,但其活性组分受载体限制。而非负载型催化剂可以有效提高活性组分含量,具有更高的催化活性。按照催化剂组成不同,总结了近年来单金属型、双金属型和多金属型非负载型催化剂在加氢脱硫中的应用。     

由氢、氧直接合成过氧化氢研发新进展

介绍了氢、氧直接合成过氧化氢过程中催化剂、反应介质、反应器(微反应器、膜反应器等)、操作方式等方面近2～3年来的研发新进展。重点介绍了Au-Pd负载催化剂研究应用情况,涉及不同载体、不同Au与Pd质量比等对过氧化氢生成速率、选择性及浓度的影响。还较详细地介绍了无机酸和卤离子在不同条件下对合成反应结果(包括氢转化率、生成过氧化氢选择率及浓度等)的提高所起到的促进作用及其机理。     

Direct Synthesis of Hydrogen Peroxide from Hydrogen and Oxygen over Palladium Catalyst Supported on SO3H-Functionalized SBA-15

Palladium catalyst supported on SO₃H-functionalized SBA-15 (denoted as Pd/SO₃H-SBA-15) was applied to the direct synthesis of hydrogen peroxide from hydrogen and oxygen. For comparison, palladium catalyst supported on SBA-15 (denoted as Pd/SBA-15) was also employed for the direct synthesis of hydrogen peroxide. Selectivity for hydrogen peroxide, yield for hydrogen peroxide, and final concentration of hydrogen peroxide over Pd/SO₃H-SBA-15 catalyst were much higher than those over Pd/SBA-15 catalyst. The high catalytic performance of Pd/SO₃H-SBA-15 catalyst was attributed to the enhanced acid amount of SO₃H-SBA-15 support, which served as an alternate acid source in the direct synthesis of hydrogen peroxide from hydrogen and oxygen.     

Comparison of supports for the direct synthesis of hydrogen peroxide from H2 and O2 using Au–Pd catalysts

The direct synthesis of hydrogen peroxide from H₂ and O₂ using a range of supported Au–Pd alloy catalysts is compared for different supports using conditions previously identified as being optimal for hydrogen peroxide synthesis, i.e. low temperature (2 °C) using a water–methanol solvent mixture and short reaction time. Five supports are compared and contrasted, namely Al₂O₃, -Fe₂O₃, TiO₂, SiO₂ and carbon. For all catalysts the addition of Pd to the Au only catalyst increases the rate of hydrogen peroxide synthesis as well as the concentration of hydrogen peroxide formed. Of the materials evaluated, the carbon-supported Au–Pd alloy catalysts give the highest reactivity. The results show that the support can have an important influence on the synthesis of hydrogen peroxide from the direct reaction. The effect of the methanol–water solvent is studied in detail for the 2.5 wt% Au–2.5 wt% Pd/TiO₂ catalyst and the ratio of methanol to water is found to have a major effect on the rate of hydrogen peroxide synthesis. The optimum mixture for this solvent system is 80 vol.% methanol with 20 vol.% water. However, the use of water alone is still effective albeit at a decreased rate. The effect of catalyst mass was therefore also investigated for the water and water–methanol solvents and the observed effect on the hydrogen peroxide productivity using water as a solvent is not considered to be due to mass transfer limitations. These results are of importance with respect to the industrial application of these Au–Pd catalysts.     

Direct synthesis of H2O2 on monometallic and bimetallic catalytic membranes using methanol as reaction medium

Tubular catalytic membranes (TMCs) active in the direct synthesis of hydrogen peroxide were prepared, characterized, and tested using methanol as the reaction medium. Low hydrogen peroxide selectivity was found when only palladium was used as a catalyst, whereas palladium/platinum bimetallic samples gave higher productivity and selectivity, with an optimum molar ratio of 18. The H₂O₂ decomposition rate is influenced by the feed gases. O₂ improves H₂O₂ stability, whereas H₂ causes hydrogen peroxide to decompose at a higher rate. The most likely decomposition pathway should be the reduction of H₂O₂ to water by H₂. Bromide ion was used as a promoter and when used in excess (60 ppm) causes a decrease in overall catalytic activity.     

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。     

国外用过氧化氢环氧化丙烯制环氧丙烷研发近况

介绍了国外用过氧化氢环氧化丙烯制备环氧丙烷（PO）工艺技术近期研发概况,内容包括所用过氧化氢来源（来自蒽醌法或氢、氧直接化合法）、丙烯环氧化反应以及反应产物精制和原料回收循环利用过程,工艺涉及催化剂、溶剂、流程、反应器、操作方法和试验结果等。不少工艺是将过氧化氢合成与丙烯环氧化加以耦合,形成完整体系,提高运转效率和经济效益。此外,简略介绍了用过氧化氢制PO工艺在产业化方面的最新进展。     

Ni—Pd／C双金属催化剂羰基化反应合成丙酸的研究

考察了Ni—Pd／C双金属催化剂上催化乙醇气相羰基化合成丙酸的反应。实验结果表明,负载活性炭Ni—Pd双金属催化剂相比普通非贵金属催化剂具有很高的活性及选择性,最佳反应工艺条件为,在少量碘代乙烷存在下,压力0．15MPa,温度220℃,n（CO）：n（C2H5OH）=2．0：1,乙醇液体空速1．5h^-1此时乙醇羰基化反应产物中丙酸及丙酸酯的选择性可高达96．7％,通过GC—MS对反应产物分析,分析了反应过程的机理。     

Direct synthesis of hydrogen peroxide from hydrogen and oxygen over palladium catalyst supported on SO<Subscript>3</Subscript>H-functionalized MCF silica: Effect of calcination temperature of mesostructured cellular foam silica

Palladium catalysts supported on SO₃H-functionalized MCF silica (Pd/SO₃H-MCF-T (T=450, 550, 650, 750, 850, and 950)) were prepared with a variation of calcination temperature (T, °C) of MCF silica. They were then applied to the direct synthesis of hydrogen peroxide from hydrogen and oxygen. Conversion of hydrogen, selectivity for hydrogen peroxide, and yield for hydrogen peroxide showed volcano-shaped curves with respect to calcination temperature of MCF silica. Yield for hydrogen peroxide increased with increasing acid density of Pd/SO₃H-MCF-T catalysts. Thus, acid density of Pd/SO₃H-MCF-T catalysts played an important role in determining the catalytic performance in the direct synthesis of hydrogen peroxide. Pd/SO₃H-MCF-T catalysts efficiently served as an acid source and as an active metal catalyst in the direct synthesis of hydrogen peroxide.     

Direct synthesis of hydrogen peroxide from H2/O2 and oxidation of thiophene over supported gold catalysts

Direct synthesis of hydrogen peroxide from H₂ and O₂ was performed over supported gold catalysts. The catalysts were characterized by means of UV–vis, H₂-TPR, TEM and XPS. Based on the results we conclude that metallic Au is the active species in the direct synthesis of hydrogen peroxide from H₂ and O₂. During preparation process of catalyst by deposition–precipitation with urea, the pH value increased and the gold particle size decreased with increasing the urea concentration. The catalyst prepared with higher urea concentration showed a higher activity and its stability also was efficiently improved. Gold nanoparticles, supported on TiO₂ or Ti contained supports, gave a higher catalytic activity. Thiophene can be efficiently oxidized by hydrogen peroxide synthesized in situ from H₂ and O₂ over Au/TS-1.     

过氧化氢合成的研究进展

过氧化氢（H2O2）是一种重要的化工产品,且需求量不断增加。综述了近几年来过氧化氢的研究进展,系统地介绍了燃料电池法,O2、CO、H2O催化合成法、贵金属直接催化合成法和H2／O2介质阻挡放电等离子体法等合成过氧化氢的方法。提出了当前需要解决的问题并对今后的研究工作进行了展望。