非贵金属乙炔加氢催化剂研究获进展

正中科院金属研究所沈阳材料科学国家研究中心研究员张炳森团队等发现,在镍基八面体间隙位点引入碳原子,并与6个镍原子配位,可调控镍的原子间距离和电子结构,提高其在乙炔选择性加氢反应中的选择性和稳定性。该工作为高效非贵金属加氢催化剂的设计和制备提供了新思路。乙炔选择性加氢反应是石油化工生产过程必不可少的步骤。工业上通过催化加氢的方式去除乙烯原料气中残留的少量乙炔,以避免接下来聚合反应的催化剂中毒失活。     

加氢反应催化剂中银组分功能综述

贵金属中的廉价金属Ag以其独特的物理化学性质在催化领域发挥了重要作用.在加氢反应中,Ag自身是一种性能优异的催化剂加氢活性组分,其显著特性是对反应物分子中含有多种加氢活性位点或者从炔烃到烯烃的部分加氢反应,能够控制加氢程度,实现选择性加氢.Ag作为催化剂助剂组分,能够提高Pt、Au和Ni催化剂选择性加氢性能、催化活性或...     

乙炔选择性加氢：催化剂结构敏感性分析及调控

Pd催化乙炔选择性加氢是石脑油蒸汽裂解和煤基电石乙炔路径制备聚合级乙烯的关键。传统的Pd基催化剂使用成本较高且选择性和稳定性较差。本文综述了近年来乙炔选择性加氢催化剂结构敏感性及其调控方面的相关研究进展,重点介绍了包括活性金属粒径、纳米颗粒形貌和电子结构等对乙炔选择性加氢反应性能的重要作用,进而阐明了催化剂结构调控的目标与方向。进一步归纳总结了针对该反应特性的催化剂结构定向调控的研究进展,主要包括合金和金属间化合物催化剂、单原子及其合金催化剂的设计。通过合理地调控催化剂结构,优化关键物种的吸脱附和反应动力学行为,能够显著提高乙炔加氢催化剂的选择性及稳定性。在未来的研究中,如何针对该反应特性,构筑高效、稳定和低成本的催化剂将会是该体系催化剂研究的重点与难点。     

乙炔选择性加氢催化剂研究进展

乙烯是石化工业中最重要的工业原料之一,然而乙烯产品中少量乙炔杂质的存在会直接影响乙烯的下一步应用。乙炔选择性催化加氢被认为是脱除乙炔杂质最有效的方法之一。本文综述了乙炔选择性加氢催化剂近年来的研究进展,介绍了乙炔选择加氢的反应机理,归纳总结了活性组分、助剂、载体以及结构对乙炔加氢催化剂性能的影响。鉴于Pd基催化剂仍然是工业应用的主流催化剂,文中综述了Pd基催化剂的研究现状和目前存在的一些挑战,同时提出了催化性能优化的建议。最后,就如何进一步提高乙炔选择性加氢催化剂性能的发展趋势进行了归纳,主要从单原子合金催化剂、催化剂微观调控以及电化学炔烃加氢方面进行论述,为未来提高乙炔加氢催化剂的性能提供了指导方向。     

二硝基甲苯加氢制甲苯二胺催化剂的研究进展

综述了二硝基甲苯液相加氢合成甲苯二胺催化剂的研究进展,并介绍了(Pd+Pt)/C等贵金属催化剂、雷尼镍催化剂、负载型镍基催化剂、非晶态镍催化剂和漆原镍催化剂的最新研究成果。通过对比上述各催化剂在生产成本、制备工艺及催化二硝基甲苯加氢性能等方面的优缺点,发现非晶态镍催化剂不但价格低廉,而且在1 MPa低压二硝基甲苯液相加氢的反应中表现出与(Pd+Pt)/C工业催化剂相似的活性和选择性,是替代二硝基甲苯液相加氢贵金属和雷尼镍工业催化剂的首要选择;漆原镍催化剂制备工艺简单,价格低廉,且在众多的加氢反应中表现出与骨架镍催化剂相似的催化性能,也具有较大的工业化潜质。     

氯代硝基苯催化加氢制备氯代苯胺的研究进展

综述了近年来氯代硝基苯催化加氢制备氯代苯胺的研究进展。对铂基、钯基、钌基和镍基非均相催化剂的结构和催化性能进行了比较,讨论了催化剂助剂抑制脱氯副反应的机理。铂基催化剂活性和选择性较高,但是铂金属价格昂贵,且不能完全避免脱氯副反应;钯基和镍基催化剂活性好,但脱氯严重,通常需要引入脱氯抑制剂或使其形成非晶态合金提高产物的选择性;钌基催化剂的活性比铂基、钯基、镍基催化剂低,但选择性高,如何提高钌基催化剂的催化活性是今后的研究方向。     

高活性负载型纳米金属加氢催化剂的制备

<正>产品和技术简介:本技术是一种负载型纳米金属加氢催化剂的制备方法,该方法可获得分散度高的负载型纳米金属催化剂。此类催化剂所用金属包括钯、钌、铂、铑及镍。该制备方法简单,成本低,重复性好,绿色无污染,催化剂寿命长,活性高,分别适用于硝基,芳环,炔烃,酮,醛等选择性加氢反应。     

腐蚀金属对甲醇羰化合成醋酸反应的影响

结合工业生产催化体系中存在的腐蚀金属,研究了其对羰基合成醋酸反应的影响.在高压反应釜中,通过添加不同浓度的醋酸亚铁或醋酸镍考察腐蚀金属铁和镍对铑基催化剂和铱基催化剂反应活性和选择性的影响,并利用平行反应器在模拟闪蒸条件下考察腐蚀金属对主催化剂稳定性的影响.结果表明,少量腐蚀金属铁或镍的存在对铑催化羰基合成醋酸的反应活性...     

镍基催化剂催化加氢研究进展

镍基催化剂具有较高的热稳定性且对氢气有选择性,在催化领域有广泛的应用前景.本文首先介绍了镍基催化剂常见的制备方法,如共沉淀法、体积浸渍法、还原法、溶胶-凝胶法以及水热合成法,然后重点综述了镍基催化剂在顺酐加氢、芳香族加氢以及其他加氢领域的应用.     

镍基催化剂加氢还原氯代硝基苯时脱氯机制的研究

Ni-B/SiO2非晶态合金对一系列氯代芳烃硝基化合物进行加氢,脱氯顺序依次为:2-氯-5-硝基甲苯>邻氯硝基苯>间氯硝基苯=对氯硝基苯>2,5-二氯硝基苯。将Ni-B/SiO2非晶态合金和Raney Ni催化加氢邻氯硝基苯进行了对比,发现在—NO2转化成—NH2的反应终了之前,用非晶态镍催化剂的脱氯速度小于用Raney Ni催化剂的脱氯速度,但加氢反应终了之后,在非晶态镍催化剂上的脱氯速度大于Raney Ni催化剂上的脱氯速度。镍基催化剂的软硬度是催化剂选择性好坏的主要原因,镍基催化剂软度大有利于催化剂选择性的提高。     

Insights into the active sites of dual-zone synergistic catalysts for semi-hydrogenation under hydrogen spillover

A well-defined catalyst with platinum (Pt) and gold (Au) encapsulated in micropore and mesopore of micro-mesoporous zeolite (Pt-Au/TMSN), respectively, was designed to investigate the original active sites of semi-hydrogenation. Specifically, hydrogen molecules are dissociated on Pt nanoclusters (NCs) to form hydrogen atoms that migrate to the surfaces of TMSN zeolite and Au nanoparticles (NPs) through hydrogen spillover effect. The characterization and catalytic results demonstrate that the Au NPs and zeolite surface are both identified as the semi-hydrogenation sites. Especially, the Au active site with low adsorption ability of alkene possesses preferable selectivity in the semi-hydrogenation of phenylacetylene and 1,5-cyclooctadiene. Noteworthy, the Pt-Au/TMSN exhibits higher selectivity of phenylethylene and cyclooctene than Pt/TMSN, as well as higher turnover frequency than Au/MSN. This work creates an effective regulation strategy of active sites working with a tandem mechanism for improving the semi-hydrogenation performance.     

苯部分加氢催化剂失活原因的研究

探讨了环己醇装置苯部分加氢催化剂失活的原因，分析了失活机理，并结合实例——母液置换法解决催化剂的氮化物中毒。     

助剂对煤基合成气甲烷化反应用镍基催化剂的促进作用

助剂促进的合成气甲烷化反应用镍基催化剂具有反应活性高、使用寿命长以及甲烷选择性高等优点,被广泛应用于煤基合成气甲烷化制替代天然气反应中。本文重点介绍了贵金属、碱土金属、稀土金属以及过渡金属助剂等对活性镍基催化剂的分散度、还原度、双金属合金协同效应、镍基催化剂结构稳定性及其对合成气甲烷化反应速率和产物选择性的影响。较系统地分析了这些助剂改性镍基催化剂的作用机制。提出了非贵金属助剂以及复合助剂将是合成气甲烷化用镍基催化剂助剂研发的发展方向,旨在为煤基合成气制替代天然气甲烷化催化剂的研发提供借鉴和参考。     

The Role of Adsorbed and Subsurface Carbon Species for the Selective Alkyne Hydrogenation Over a Pd-Black Catalyst: An <Emphasis Type="Italic">Operando</Emphasis> Study of Bulk and Surface

The selective hydrogenation of propyne over a Pd-black model catalyst was investigated under operando conditions at 1 bar making use of advanced X-ray diffraction (bulk sensitive) and photo-electron spectroscopy (surface sensitive) techniques. It was found that the population of subsurface species controls the selective catalytic semi-hydrogenation of propyne to propylene due to the formation of surface and near-surface PdC_x that inhibits the participation of more reactive bulk hydrogen in the hydrogenation reaction. However, increasing the partial pressure of hydrogen reduces the population of PdC_x with the concomitant formation of a β-PdH_x phase up to the surface, which is accompanied by a lattice expansion, allowing the participation of more active bulk hydrogen which is responsible for the unselective total alkyne hydrogenation. Therefore, controlling the surface and subsurface catalyst chemistry is crucial to control the selective alkyne semi-hydrogenation.     

Acid‐Free Nickel Catalyst for Stereo‐ and Regioselective Hydrophosphorylation of Alkynes: Synthetic Procedure and Combined Experimental and Theoretical Mechanistic Study

The nickel catalyst prepared in situ from nickel bis(acetylacetonate) [Ni(acac)₂] precursor and bis(diphenylphosphino)ethane (DPPE) ligand has shown excellent performance in the hydrophosphorylation of alkynes. Markovnikov‐type regioselective addition to terminal alkynes and stereoselective addition to internal alkynes were carried out with high selectivity without an acidic co‐catalyst (in contrast to the palladium/acid catalytic system). Various H‐phosphonates and alkynes reacted smoothly in the developed catalytic system with up to 99% yield. The mechanisms of catalyst activation and C P bond formation were revealed by experimental (NMR, ESI‐MS, X‐ray) and theoretical (density functional calculations) studies. Two different pathways of the alkyne insertion in the coordination sphere of the metal are reported for the first time.     

超细镍基催化剂下甲苯加氢性能的分析

以正硅酸乙酯（TEOS）、酞酸丁酯、硝酸镍为原料,采用溶胶-凝胶法制备了超细镍基催化剂,并进行了表征,通过改变工艺条件进行单因素实验,确定了超细镍基催化剂催化甲苯加氢的最合适工艺条件为：反应温度170 ℃、压力0.6 MPa、空速4 h－1、氢烃比10︰1,甲苯加氢生成甲基环己烷的转化率为100%,在80～200 ℃的实验范围内,选择性良好,并无开环及其它副反应的发生,甲基环己烷的选择性100%,实验表明溶胶-凝胶法制备的超细镍基催化剂是优良的甲苯加氢催化剂。     

The effect of substituted alkynes on nickel catalyst morphology and carbon fiber growth

The growth of shaped carbon nanomaterials from a range of substituted alkynes over a NiO catalyst was investigated. It was found that the structure of the substituted alkyne affected both catalyst morphology and carbon fiber growth. For linear alkynes (1-pentyne to 1-octyne) the fiber morphology and yield varied with the type of alkyne used. It was also found that hetero-atoms (Cl, Br, OH and NH₂) greatly impacted carbon fiber growth and structure. An analysis of the catalyst particles associated with the carbon fibers grown from various alkynes showed that different alkynes gave differently shaped Ni catalyst particles. It was found that pre-treatment of the catalyst with an alkyne such as trimethylsilyl acetylene or ethynyl aniline (that did not give fiber growth), followed by treatment with acetylene initiated fiber growth morphologies (Y-junction, helical or straight fibers) different from that observed after direct treatment with acetylene. Further, sequential fiber growth from two alkynes that were both capable of producing fibers (e.g. methyl prop-2-ynoate followed by prop-2-yn-1-amine) resulted in ‘co-block’ fiber growth. These results highlight the dynamic relationships that exists between carbon source, catalyst morphology and carbon nanomaterial growth.     

甲烷干重整Ni基催化剂失活及抑制失活研究进展

使用甲烷和二氧化碳为原料,通过甲烷干重整反应可以将其转化为合成气。由于此反应可以利用甲烷和二氧化碳这两种温室气体,因而近年来受到了研究人员广泛的关注。其中,反应所使用的Ni基催化剂由于其较高的活性和较低的成本得到了较为深入的研究。针对甲烷干重整Ni基催化剂,本文简要介绍了几种常用的制备方法,并指出了在反应条件下存在的活性组分Ni的烧结和积炭的生成这两个问题,还详细分析了其各自的影响因素。另外,还从使用特殊载体、添加助剂以及构造特殊结构三方面阐述了甲烷干重整Ni基催化剂的失活解决方案,并指出解决催化剂的烧结和积炭问题是当前该领域的研究重点。     

Palladium supported on amine-functionalized mesoporous silica: Highly efficient phosphine-free catalyst for alkyne–alkyne cross-coupling reaction

An amine-functionalized mesoporous silica SBA-15 supported palladium catalyst was prepared and characterized. For the first time, this supported palladium has been used as an efficient phosphine-free and reusable catalyst for the cross-coupling of haloalkynes with terminal alkynes. A variety of haloalkynes and aromatic/aliphatic terminal alkynes were selectively coupled to afford unsymmetrical 1,4-disubstituted 1,3-diynes in good yields.     

Highly efficient and recyclable ruthenium nanoparticle catalyst for semihydrogenation of alkynes

Ru nanoparticles were used as catalysts for semihydrogenation of alkynes for the first time. Poly(ethylene glycol) (PEG)-stabilized Ru nanoparticles were used as catalysts for semihydrogenation of various terminal alkynes in thermoregulated PEG biphasic system, which allows for not only an efficient homogeneous catalytic reaction, but also an easy biphasic separation and reuse of catalyst. Under the optimized conditions, various terminal alkynes were hydrogenated to the corresponding alkenes with high selectivity. After reaction, the Ru nanoparticle catalyst could be separated from products by simple phase separation and recycled for ten times without evident loss in activity and selectivity.