Selective ethylene tetramerization: an overview

Hao, Biao‐Biao; Alam, Fakhre; Jiang, Yan; Wang, Libo; Fan, Hongmei; Ma, Jing; Chen, Yanhui; Wang, Yating; Jiang, Tao

doi:10.1039/d3qi00321c

Cited by 12 publications

(5 citation statements)

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“…The catalyst ligands for ethylene tetramerization can be divided into PNP, PNPO, PNPN, PCP, and other ligands. These above ligands have been discussed in detail by Hao [13] and will not be repeated here.…”

Section: Ethylene Tetramerizationmentioning

confidence: 99%

“…Compared with wax pyrolysis [3], Fischer-Tropsch synthesis [4][5][6], and alkane dehydrogenation [7][8][9], the ethylene oligomerization method has become the main process for producing LAOs due to its relatively mild operating conditions, flexible product distribution, and high linearity. According to literature reports, there are a wide variety of catalysts for ethylene oligomerization, mainly Ni, Fe, Co, and Cr as metal active centers [10][11][12][13], and some catalysts have been industrialized to produce linearity α-olefin products. For example, the Shell higher olefin process (SHOP) is an important catalytic system for ethylene oligomerization, with more than one million tons of α-olefins prepared industrially via this method [14].…”

Section: Introductionmentioning

confidence: 99%

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Ethylene Oligomerization Catalyzed by Different Homogeneous or Heterogeneous Catalysts

Peng,

Huang,

2024

Catalysts

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Linear α-olefins (LAOs) are linear alkenes with double bonds at the ends of the molecular chains. LAOs with different chain lengths can be widely applied in various fields. Ethylene oligomerization has become the main process for producing LAOs. In this review, different homogeneous or heterogeneous catalysts recently reported in ethylene oligomerization with Ni, Fe, Co, Cr, etc., as active centers will be discussed. In the homogeneous catalytic system, we mainly discuss the effects of the molecular structure and the electronic and coordination states of complexes on their catalytic activity and selectivity. The Ni, Fe, and Co homogeneous catalysts are discussed separately based on different ligand types, while the Cr-based homogeneous catalysts are discussed separately for ethylene trimerization, tetramerization, and non-selective oligomerization. In heterogeneous catalytic systems, we mainly concentrate on the influence of various supports (metal–organic frameworks, covalent organic frameworks, molecular sieves, etc.) and different ways to introduce active centers to affect the performance in ethylene oligomerization. Finally, a summary and outlook on ethylene oligomerization catalysts are provided based on the current research. The development of highly selective α-olefin formation processes remains a major challenge for academia and industry.

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Section: Ethylene Tetramerizationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ethylene Oligomerization Catalyzed by Different Homogeneous or Heterogeneous Catalysts

Peng,

Huang,

2024

Catalysts

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“…Linear alpha olefins (LAOs) are important for the petrochemical industry, particularly for synthesis polymers. 1,2 Among them, 1-hexene and 1-octene are the most important co-monomers for the linear low-density polyethylene (LLDPE) production. 3 Most LAOs are produced by ethylene oligomerization processes with low selectivity of 1-hexene and 1-octene, 4,5 but interest in producing low carbon LAOs technologies has grown in recent decades.…”

Section: Introductionmentioning

confidence: 99%

“…Linear alpha olefins (LAOs) are important for the petrochemical industry, particularly for synthesis polymers 1,2 . Among them, 1‐hexene and 1‐octene are the most important co‐monomers for the linear low‐density polyethylene (LLDPE) production 3 .…”

Section: Introductionmentioning

confidence: 99%

1H‐Perfluorohexane—An efficient modifier for ethylene tri‐/tetramerization

Yang,

Shao,

Hao

et al. 2023

Applied Organom Chemis

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Silicon‐bridged/N, P (PNSiP) ligand/Cr (III) catalyst system based on different fluorinated hydrocarbons as modifiers have been explored for ethylene selective tri‐/tetramerization. Modifiers like 1H‐Perfluorohexane (1H‐PFH), Hexafluorobenzene (HFB), and Perfluorobiphenyl (PFB) have been proven to show a significant influence on ethylene oligomerization toward 1‐hexene and 1‐octene of the catalytic system. Among them, 1H‐PFH showed the most significant promotion effect in improving activity from 0.95 × 106 g·(mol Cr·h)−1 to as much as 5.66 × 106 g·(mol Cr·h)−1 at high temperature 90°C. Through the analysis of nuclear magnetic resonance (NMR) spectroscopy and ultraviolet visible diffuse reflectance spectroscopy (UV–vis DRS) results, we concluded that 1H‐PFH can react with an amount of trimethylaluminum (TMA) contained in the cocatalyst modified methylaluminoxane (MMAO) and the solubility of Cr (III) in solvent can be increased after adding 1H‐PFH. Furthermore, the possible reaction routes of 1H‐PFH with TMA and MMAO were proposed.

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“…Linear alpha olefins (LAOs) containing 6- and 8-carbon atoms serve as immensely valuable feed stocks for the large-scale production of co-polymers, linear low-density polyethylene (LLDPE) exhibiting outstanding material properties. − Industrially, LAOs are manufactured by two main routes: oligomerization of ethylene and by Fischer–Tropsch synthesis followed by purification . Over the past decade, the catalytic approach to promote selective tri-/tetramerization to access 1-C 6 /1-C 8 olefins emerged as a topic of great academic/industrial research interest, thanks to the breakthrough report by the Sasol technology .…”

Section: Introductionmentioning

confidence: 99%

Unveiling meta-Alkyloxy/-Silyloxy-Substituted N-Aryl PNP Ligands for Efficient Cr-Catalyzed Ethylene Tetramerization

et al. 2023

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Novel N-aryl-functionalized PNP ligands (1−4) bearing m-alkyloxy/-silyloxy substituents were prepared and evaluated for chromium-catalyzed ethylene oligomerization using MMAO-3A as an activator. The selected Cr/PNP system under optimized condition exhibited high 1-octene-selective (up to 70 wt %) ethylene tetramerization at a remarkable rate (over 3000 kg gCr −1 h −1 ). More importantly, the undesirable polyethylene selectivity was restricted to a minimum level of ∼1−2 wt % for pre-catalysts derived with ligands 1 and 2. Employing chlorobenzene as a reaction medium yielded best productivity in conjunction to the total α-olefin (1-C 6 + 1-C 8 ) selectivity (∼88 wt %). N-aryl PNP ligands (3 and 4) incorporating m-silyloxy substituents in the phenyl ring exhibited relatively poorer tetramerization performance while yielding higher PE fraction as compared to their m-alkyloxy derivatives. A detailed molecular structure of the best-performing pre-catalyst 1-Cr was established by single-crystal X-ray diffraction analysis. The stability of 1/Cr-based catalyst system was investigated for a reaction time of up to 2 h under optimized condition.

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Selective ethylene tetramerization: an overview

Abstract: With greater market demand, interest in the selective production of linear α-olefins has been increasing. This Review discusses the principles underlying the evolution of the ligand design, co-catalysts, reaction mechanisms,...

Cited by 12 publications

References 304 publications

Ethylene Oligomerization Catalyzed by Different Homogeneous or Heterogeneous Catalysts

Ethylene Oligomerization Catalyzed by Different Homogeneous or Heterogeneous Catalysts

1H‐Perfluorohexane—An efficient modifier for ethylene tri‐/tetramerization

Unveiling meta-Alkyloxy/-Silyloxy-Substituted N-Aryl PNP Ligands for Efficient Cr-Catalyzed Ethylene Tetramerization

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