Selective Production of Bio-Based Linear Alpha-Olefin from Wasted

polymers Article Selective Production of Bio-Based Linear Alpha-Olefin from Wasted Fatty Alcohol on Al2O3 for Bio-Based Chemicals Hye-Jin Lee 1,2, Il-Ho Choi 1 , Seung-Wook Kim 2 and Kyung-Ran Hwang 1,* 1 Energy Resource Upcycling Research Laboratory, Korea Institute of Energy Research, Daejeon 34129, Korea; [email protected] (H.-J.L.); [email protected] (I.-H.C.) 2 Department of Chemical and Biological Engineering, Korea University, Seoul 136701, Korea; [email protected] * Correspondence: [email protected]; Tel.: +82-42-860-3504 Abstract: The catalytic dehydration of a bio-based fatty alcohol was performed using Al2O3 prepared by solvothermal synthesis for selective production of long-chain linear-alpha-olefins (LAO). The effect of the synthesis temperature of alumina precursors on the dehydration of 1-octadecanol (C18H38O) was examined based on the textural properties and Lewis acid–base properties of the catalysts. Amorphous alumina synthesized at 325 ◦C showed the highest surface area (233.07 m2/g) and total pore volume (1.237 cm3/g) among the catalysts and the best dehydration results: 93% conversion, 62% selectivity of 1-octadecene (C18H36), and 89% LAO purity. This was attributed to the increased Al/O ratio and atomic concentration of surface O in alumina, which were important factors in the catalytic dehydration of 1-octadecanol through the synergistic catalysis of acid–base pairs. The produced bio-based LAO can be key intermediates for synthesis of oxo alcohols and poly-alpha-olefins, as alternatives to petroleum-based LAO to achieve carbon neutrality in chemical industry. Citation: Lee, H.-J.; Choi, I.-H.; Kim, S.-W.; Hwang, K.-R. Selective Keywords: bio-based alpha-olefins; long-chain alpha-olefins; waste fatty alcohol; dehydration; Production of Bio-Based Linear solvothermal method Alpha-Olefin from Wasted Fatty Alcohol on Al2O3 for Bio-Based Chemicals. Polymers 2021, 13, 2850. https://doi.org/10.3390/ 1. Introduction polym13172850 Linear-alpha-olefins (LAO) are versatile building blocks to produce universal or high-value chemicals used in many industries such as co-monomer for polyethylene Academic Editor: T. M. Indra Mahlia and polypropylene, plasticizer, cosmetics, pharmaceuticals and synthetic lubricants. The market size of LAO was estimated as USD 12.5 billion in 2016 and is expected to grow Received: 29 July 2021 with the increasing demand (USD 19 billion in 2024) [1]. As the consumption of LAO Accepted: 23 August 2021 increases, research on methods to produce LAO has also increased. There are several Published: 25 August 2021 common processes to produce LAO including (I) catalytic oligomerization of fossil-based ethylene [2,3], and (II) dehydrogenation of synthetic n-alkanes from Fischer–Tropsch Publisher’s Note: MDPI stays neutral processing of syngas or direct conversion of syngas to olefins [4–6]. LAO can also be with regard to jurisdictional claims in obtained through the thermal cracking of heavy hydrocarbons (III) such as wax or waste published maps and institutional affil- iations. plastics based on petroleum [7–9]. However, in these processes, the chain length of olefins is not easily controlled, resulting in limited yields for medium (C5-C12) to long-chain (C13+) LAO [10,11]. In addition, because we are facing environmental problems such as global warming and the depletion of fossil resources, many researchers have recently focused on the production of bio-derived rather than petroleum-derived LAO. Copyright: © 2021 by the authors. The bio-derived LAO can be obtained from wasted free fatty acids (FFAs), having a Licensee MDPI, Basel, Switzerland. long-chain hydrocarbon structure and a carboxylic functional group. Currently, such low- This article is an open access article cost feedstock containing significant amounts of FFAs is not suitable to produce bio-diesel distributed under the terms and conditions of the Creative Commons due to the formation of soap and the increasing purification cost in the process of biodiesel Attribution (CC BY) license (https:// production [12,13]. Thus, the wasted FFAs, which are generated from oil refining processes creativecommons.org/licenses/by/ or the kraft paper-making industry in the form of palm sludge oil, palm fatty acid distillate, 4.0/). tall oil fatty acids, etc., appear to be suitable raw materials for the production of valuable Polymers 2021, 13, 2850. https://doi.org/10.3390/polym13172850 https://www.mdpi.com/journal/polymers Polymers 2021, 13, 2850 2 of 15 chemicals [14–16]. Numerous routes to produce LAO based on biomass, as schematically illustrated in Figure1, have been reported. Olefin metathesis (Figure1a) is a highly selective route to produce LAO via self-metathesis of FFAs or cross-metathesis with FFAs and ethylene using ruthenium-based Grubbs’ catalysts [17]. However, only unsaturated FFAs are available for the metathesis and some limitations originating from homogenous catalysts still remain. Ru-complexes immobilized catalysts have thus been employed for olefin metathesis [18] and a two-step process including ethenolysis of intermediates obtained from decarboxylation of FFAs has also been suggested [19]. A decarbonylative dehydration reaction of FFAs (Figure1b) has been explored to produce uncommon, odd- numbered LAO using Pd-based homogenous or heterogeneous catalysts. Some research groups achieved 66%–99% yield and 97% selectivity of LAO. However, a large amount of Pd catalyst (3 mol%) and an expensive solvent (1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)- pyrimidinone) are required to achieve the highest selectivity and best performance [20,21]. Although Liu et al. conducted decarbonylative dehydration of FFAs using a small amount of Pd catalyst (0.05 mol%) under a solvent-free condition and achieved satisfactory results (41%–80% yield, 80%–99% selectivity of LAO), stoichiometric amounts of acetic anhydride and selected phosphine ligands were still required [22]. Meanwhile, bio-based LAO can be synthesized by catalytic hydrogenation of FFAs into fatty alcohol, followed by dehydration of the fatty alcohol (Figure1c). This route allows the synthesis of LAO without carbon loss regardless of the degree of saturation in fatty acids. Chen et al. conducted the hydrogenation of FFAs to corresponding fatty alcohol (99% yield) using a Ru-based catalyst followed by dehydration of the fatty alcohol to LAO (90% yield) using Al2O3 mixed with ThO2. The significant dehydration yield was due to the synergetic effect between (1) the favourable dehydration on the abundant Lewis acid sites (LAS) and Lewis base sites (LBS) on the nano-sized alumina and (2) the hindrance of further undesired isomerization of dehydrated LAO on thoria [23,24]. In fact, dehydration catalysts have been widely investigated for shorter alcohols such as ethylene production from dehydration of ethanol [25–27]. In particular, studies on dehydration of 1-alcohols using Al2O3 with rich LAS have been reported [28–30]. Kostestkyy et al. revealed that Al2O3 was the best catalyst for the dehydration of 1-propanol among metal oxides due to the stronger binding −1 energy of alcohol on Al-LAS (binding energy = −133.0 kJ mol ) than TiO2 and ZrO2 (−70.8 and −83.1 kJ mol−1, respectively) [31]. The dehydration of methanol and ethanol using Al2O3 with various crystalline phases showed that χ- and γ-mixed Al2O3 exhibited higher catalytic activity than pure χ- and γ- Al2O3 due to improved acidity [32,33]. In addition, alumina synthesized by the solvothermal method showed the best catalytic result in ethanol dehydration among various prepared alumina owing to the higher surface area originating from the small crystalline size and large amount of acid sites [34]. A γ-Al2O3 supported cobalt catalyst showed a more active and stable performance than the parent γ-Al2O3 in ethanol dehydration due to enhanced surface hydrophobicity and higher micro-pore acidity of Co/γ-Al2O3 [25]. Connor et al. investigated mixed C2-C4 alcohol dehydration over various acidic catalysts such as Zr-KIT-6, Al-MCM-41, HZSM-5, and SAPO-34 and suggested that Brønsted acid sites (BAS) were more active than LAS under the investigated conditions [26]. Unlike short alcohols, dehydration of C4 alcohol produced 1- and 2-butentes on the γ-Al2O3 or modified γ-Al2O3, meaning that a double-bond shift in olefins makes the selectivity of alpha-olefins low when using long-chain feedstock [27,35]. Moreover, diethyl ether was formed as a byproduct during ethanol dehydration on silica- alumina catalysts and the selectivities of ethylene and ether depended on the nature of Lewis sites with an alumina-like acid-basic neighbor or with a silica-like covalent neighbor in silica–alumina catalysts at relatively low reaction temperatures [36]. This means that the shift of the double bond at the alpha position of olefins (isomerization) and the side reaction (ether formation) should be considered when designing catalysts for selective dehydration of long-chain alcohols to LAO. However, there have been few reports on dehydration catalysts of long-chain alcohols derived from fatty acids for the selective production of long-chain LAO. Mingli et al. studied selective dehydration and hydro- Polymers 2021, 13, 2850 3 of 15 processing for bio-jet fuel production from a medium-chain fatty alcohol and found that the acidic properties and structural features of the tested catalysts (ZSM-22, ZSM-5, and Al-MCF) were important to convert n-decanol into straight decene in the dehydration step. However, alpha-olefin (1-decene) was not observed in the straight decene groups that were mainly produced from the dehydration reaction using Al-MCF catalyst [37]. Figure 1. Various routes for bio-based LAO production; (a) olefin metathesis; (b) decarbonylative dehydration, and (c) hydrogenation and dehydration. In this study,catalytic dehydration of a bio-derived long-chain fatty alcohol (1-octadecanol, C18H38O) was conducted using Al2O3 prepared by solvothermal synthesis for the selective production of bio-LAO (1-octadecene, C18H36).

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