Catalyst Development and Design in Propane Dehydrogenation

Propane dehydrogenation (PDH) is an industrial technology for direct propylene production, which has received extensive attention and realized large-scale application. At present, the commercial Pt/Cr-based catalysts suffer from fast deactivation and inferior stability resulting from active species sintering and coke depositing. To overcome the above problems, several strategies such as the modification of the support and the introduction of additives have been proposed to strengthen the catalytic performance and prolong the robust stability of Pt/Cr-based catalysts. This review firstly gives a brief description of the development of PDH and PDH catalysts. Then, the advanced research progress of supported noble metals and non-noble metals together with metal-free materials for PDH is systematically summarized along with the material design and active origin as well as the existing problems in the development of PDH catalysts. Furthermore, the review also emphasizes advanced synthetic strategies based on novel design of PDH catalysts with improved dehydrogenation activity and stability. Finally, the future challenges and directions of PDH catalysts are provided for the development of their further industrial application.

Propane dehydrogenation over Al2O3 supported Pt nanoparticles: Effect of cerium addition

Ethylene and propene by oxidative dehydrogenation of ethane and propane: ‘Performance of rare-earth oxide-based catalysts and development of redox-type catalytic materials by combinatorial methods’

Discovery of promising Cu-based catalysts for selective propane dehydrogenation to propylene assisted by high-throughput computations

In the chemical industry, an elaborated design of catalysts for propane dehydrogenation (PDH) should be capable of high propane conversion and propylene selectivity, strong resistance to sintering and coke deposition, and easy regeneration. Here, we report a unique design of fluorinated siliceous MFI zeolite-clothed PtSn for PDH, where the fluorination induces the formation of "holes" in all-silica molecular sieves and the position of ultrasmall PtSn nanoclusters as a result of high activity, selectivity, and especially remarkable resistance to sintering during PDH over 5000 h. The present catalyst displays a near-thermodynamic-limited propane conversion and 94% propylene selectivity in pure propane, respectively, under industrially relevant conditions. Impressively, the coked catalyst can be simply regenerated by H2 treatment at the same temperature for PDH, avoiding the complicated, poisonous, and corrosive oxychlorination process in the conventional method for regeneration, which will contribute to the extensive application of the industrial PDH process. Detailed investigations demonstrate that the strong synergy between F-modified PtSn nanoclusters and MFI zeolite can promote the selective PDH to propylene and stabilize PtSn nanoclusters against sintering and coke deposition. The unique design of the catalyst and the enhanced performance will provide a feasible strategy to solve the current difficulties in the industrial PDH process.

Bimetallic Ni-Zn site anchored in siliceous zeolite framework for synergistically boosting propane dehydrogenation

Pt‐based catalysts have been widely studied for propane dehydrogenation (PDH) because of their high activity and environmental sustainability. However, as a precious metal, the development of catalysts with high stability and low Pt content is of great significance. In this study, a series of silicalite‐1 (S‐1) supported PtMn (0.1PtxMn/S‐1) catalysts with low Pt loading amount (0.1 wt%) was prepared. The effects of different Mn loadings on the physicochemical properties and catalytic performance in the PDH reaction were studied. The addition of an appropriate amount of Mn regulated the dispersion of Pt particles and increased the number of active sites of the catalyst, enhancing the catalytic performance of PDH even at a low Pt loading. The initial propane conversion was 46.1% over 0.1Pt0.3Mn/S‐1 catalyst, and the deactivation rate constant was the lowest of 0.01 h−1. This may be because of an appropriate Mn loading was beneficial for enhancing the interaction between the metal and the support, forming MnOx is attached to the S‐1 surface, while the surface of MnOx stabilized the PtMn alloy, thereby improving the catalytic performance for PDH.

Light alkenes are the key building blocks in the chemical industry. As a propene on-purpose production technology, propane dehydrogenation has drawn particular attention due to the growing demand for propene and the discovery of large reserves of shale gas. The development of highly active and stable propane dehydrogenation catalysts is significant in the world-wide research field. Supported platinum-based catalysts are widely studied for propane dehydrogenation. This article reviews the developments of platinum-based catalysts in propane dehydrogenation, particularly focusing on the influence of the promoter effect and support effect on the structure and catalytic performance and especially on how promoters and supports enable Pt to form highly dispersed and stable active sites. At the end, we propose the prospective research directions of propane dehydrogenation.

Non-oxidative dehydrogenation of propane to propene is an established large-scale process that, however, faces challenges, particularly in catalyst development; these are the toxicity of chromium compounds, high cost of platinum, and catalyst durability. Herein, we describe the design of unconventional catalysts based on bulk materials with a certain defect structure, for example, ZrO2 promoted with other metal oxides. Comprehensive characterization supports the hypothesis that coordinatively unsaturated Zr cations are the active sites for propane dehydrogenation. Their concentration can be adjusted by varying the kind of ZrO2 promoter and/or supporting tiny amounts of hydrogenation-active metal. Accordingly designed Cu(0.05 wt %)/ZrO2 -La2 O3 showed industrially relevant activity and durability over ca. 240 h on stream in a series of 60 dehydrogenation and oxidative regeneration cycles between 550 and 625 °C.

Propane dehydrogenation catalyzed by single Lewis acid site in Sn-Beta zeolite

A review on the structure-performance relationship of the catalysts during propane dehydrogenation reaction

Promoting propane dehydrogenation via strain engineering on iridium single-atom catalyst

Catalyst design and tuning for oxidative dehydrogenation of propane – A review

Well-defined Ga(III) sites on SiO2 are highly active, selective, and stable catalysts in the propane dehydrogenation reaction. In this contribution, we evaluate the catalytic activity towards propane dehydrogenation of tri-coordinated and tetra-coordinated Ga(III) sites on SiO2 by means of first principles calculations using realistic amorphous periodic SiO2models. We evaluated the three reaction steps in propane dehydrogenation, namely the C-H activation of propane to form propyl, the beta-hydride elimination transfer to form propene, and a Ga-hydride, and the H-H coupling to release H2, regenerating the initial Ga-O bond and closing the catalytic cycle. Our work shows how Brønsted-Evans-Polanyi relationships are followed for these three reaction steps on Ga(III) sites on SiO2 and highlights the role of the strain of the reactive Ga-O pairs on such sites of realistic amorphous SiO2 models. While highly strained sites are very reactive sites for the initial C-H activation, they are more difficult to regenerate. The corresponding less strained sites are not reactive enough, pointing to the need of a right balance in strain to be an effective site for propane dehydrogenation. Overall, our work provides an understanding of the intrinsic activity of acidic Ga single sites towards the propane dehydrogenation reaction and paves the road towards the design and prediction of better single-site catalysts on SiO2 for the propane dehydrogenation reaction.

Propane dehydrogenation (PDH) is a key process to address the supply-demand imbalance of propylene. Commercial PtSn/Al2O3 and CrOx/Al2O3 catalysts, however, face limitations due to high cost and environmental concerns, motivating the development of sustainable, non-noble metal alternatives. Recent studies reveal that atomically tailored single-metal oxides, bimetallic oxides, and non-noble metal alloys can achieve comparable or even superior activity and selectivity through precise control over geometric structures, electronic states, and interfacial synergy. This review systematically summarizes the rational design strategies, key structure-performance relationships, and mechanistic insights underlying these catalysts. Emphasis is placed on the role of atomic-level active site engineering and synergistic dual-metal interactions in enhancing activity, selectivity, and stability. Looking forward, multi-scale collaborative design, advanced in situ/operando characterization, and machine-learning-assisted high-throughput screening are identified as promising approaches to accelerate the development and industrial deployment of high-performance non-noble metal-based PDH catalysts. This review aims to provide a comprehensive perspective to guide the design of efficient, stable and sustainable PDH catalysts.