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Olefins from Biomass Intermediates: a Review

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Olefins from Biomass Intermediates: a Review catalysts Review Review OlefinsOlefins fromfrom BiomassBiomass Intermediates:Intermediates: AA ReviewReview 1 1,2, VasilikiVasiliki Zacharopoulou Zacharopoulou1 andand AngelikiAngeliki A.A. LemonidouLemonidou 1,2,** 1 Department of Chemical Engineering, Aristotle University of Thessaloniki, University Campus, 1 Department of Chemical Engineering, Aristotle University of Thessaloniki, University Campus, Thessaloniki 54124, Greece; [email protected] 54124 Thessaloniki, Greece; [email protected] 2 Chemical Process Engineering Research Institute (CERTH/CPERI), P.O. Box 60361 Thermi, 2 Chemical Process Engineering Research Institute (CERTH/CPERI), P.O. Box 60361 Thermi, Thessaloniki 57001, Greece 57001 Thessaloniki, Greece * Correspondence: [email protected]; Tel.: +30‐2310‐996‐273 * Correspondence: [email protected]; Tel.: +30-2310-996-273 Received: 16 November 2017; Accepted: 19 December 2017; Published: Received: 16 November 2017; Accepted: 19 December 2017; Published: 23 December 2017 Abstract:Abstract: Over the last decade, increasing demand for olefinsolefins and theirtheir valuablevaluable productsproducts hashas promptedprompted researchresearch onon novelnovel processesprocesses andand technologiestechnologies forfor theirtheir selectiveselective production.production. As olefinsolefins are predominatelypredominately dependent on fossil resources, their production is limited by thethe finitefinite reservesreserves and the associated economic and environmental concerns.concerns. The need for alternative routes for olefinolefin productionproduction isis imperativeimperative inin orderorder toto meetmeet thethe exceedinglyexceedingly highhigh demand,demand, worldwide.worldwide. BiomassBiomass isis consideredconsidered aa promising alternativealternative feedstockfeedstock thatthat cancan bebe converted into the valuable olefins,olefins, among other chemicalschemicals andand fuels.fuels. Through processes such as fermentation,fermentation, gasification,gasification, crackingcracking andand deoxygenation, biomass derivatives can be effectively converted into C2–C4 olefins. This short deoxygenation, biomass derivatives can be effectively converted into C2–C4 olefins. This short review focusesreview focuses on the conversion on the conversion of biomass-derived of biomass‐ oxygenatesderived oxygenates into the most into valuablethe most olefins,valuable e.g., olefins, ethylene, e.g., propylene,ethylene, propylene, and butadiene. and butadiene. Keywords: olefins;olefins; biomass; ethylene; propylene;propylene; butadiene;butadiene; catalysiscatalysis 1. Introduction The importanceimportance ofof CC22–C–C44 olefinsolefins (i.e.,(i.e., CC22HH44,C, C33H6,, butenes, and CC44H6)) has been highlightedhighlighted because of their numerous applications as key building blocks in the chemical industry, linkedlinked withwith thethe increasingincreasing needs needs of of the the expanding expanding global global population population [1]. These [1]. lowerThese olefinslower areolefins the most are prevalentthe most organicprevalent compounds, organic compounds, with the highest with the production highest production volumes, worldwide, volumes, worldwide, highly dependent highly on dependent crude oil andon crude natural oil gasand products natural gas [2]. products It is estimated [2]. It is that estimated 400 million that 400 tons million of olefins tons are of annuallyolefins are produced, annually usingproduced, one billion using tonsone asbillion hydrocarbon tons as feedstock,hydrocarbon via feedstock, processes suchvia processes as fluid-catalytic such as cracking, fluid‐catalytic steam cracking,cracking, andsteam dehydrogenation cracking, and dehydrogenation [3]. Almost 60% [3]. of the Almost global 60% feedstocks of the global are used feedstocks in FCC are units, used and in approximatelyFCC units, and 40% approximately in steam cracking 40% in processes.steam cracking (Figure processes.1) Produced (Figure olefins 1) Produced can be used olefins in a can wide be spectrumused in a wide of high-end spectrum applications of high‐end such applications as packaging, such construction, as packaging, solvents, construction, coatings, solvents, and synthetic coatings, fibersand synthetic [4]. fibers [4]. FigureFigure 1. 1.Olefin Olefin production production methods methods using using hydrocarbonhydrocarbon feedstocks. Reproduced Reproduced from from [3]. [3 ].2014, 2014, WILEY-VCH Verlag GmbH & Co.WILEY‐VCH Verlag GmbH & Co. Catalysts 2018, 8, 2; doi: 10.3390/catal8010002 www.mdpi.com/journal/catalysts Catalysts 2018, 8, 2; doi:10.3390/catal8010002 www.mdpi.com/journal/catalysts Catalysts 2018, 8, 2 2 of 18 C2H4 constitutes the most predominant olefin in the global market and is primarily produced Catalysts 2018, 8, 2 2 of 19 via naphtha steam cracking, among various hydrocarbon feedstocks, as well as through ethane thermal cracking. Globally, 57% (Figure 2) of the C2H4 volume is produced via naphtha and gas oil steam crackingC2H4 constitutes and 38% the through most predominant ethane and olefin LPG in the(Liquefied global market Petroleum and is primarilyGas) steam produced cracking. Naphthavia naphtha is a liquid steam fraction cracking, obtained among from various petroleum hydrocarbon refining feedstocks, processes, as well such as as through catalytic ethane cracking thermal cracking. Globally, 57% (Figure2) of the C H volume is produced via naphtha and gas and hydrocracking. Depending on its origin, it contains2 4 variable amounts of paraffins, aromatic, and oil steam cracking and 38% through ethane and LPG (Liquefied Petroleum Gas) steam cracking. olefinicNaphtha compounds. is a liquid The fraction ratio obtainedof these components from petroleum can refining indicate processes, the process such that as catalytic the specific cracking fraction can beand used hydrocracking. for the optimum Depending results. on its At origin, high temperatures it contains variable (i.e., amounts 650–750 of °C), paraffins, naphtha aromatic, and gas and oil can yieldolefinic 30 and compounds. 25 wt. % of The C2 ratioH4, respectively. of these components In the case can indicate of ethane, the processadded thatalong the with specific naphtha fraction in the ◦ feed canstream, be used yields for the of optimum C2H4 can results. reach At 80 high wt. temperatures % [5]. Its (i.e.,eminent 650–750 industrialC), naphtha uses and cause gas oilthe can world demandyield for 30 andC2H 254 to wt. incessantly % of C2H4, increase, respectively. as Init can the casebe used of ethane, for significant added along applications, with naphtha such in the as the productionfeed stream, of yieldsintermediate of C2H4 canchemicals, reach 80 wt.mainly % [5]. Itsin eminentthe industry industrial of uses plastics. cause thei.e., world polymers demand (e.g., polyfor‐ethylene), C2H4 to incessantlypropionaldehyde—via increase, as it can hydroformylation, be used for significant vinyl applications, chloride—via such as halogenation the production and of intermediate chemicals, mainly in the industry of plastics. i.e., polymers (e.g., poly-ethylene), de‐hydrohalogenation, alpha‐olefins—via oligomerization, and C2H4 oxide and acetaldehyde—via oxidationpropionaldehyde—via [4,6,7]. In recent hydroformylation, years, bio‐ethanol vinyl has chloride—via been extensively halogenation studied and de-hydrohalogenation,as an alternate feedstock alpha-olefins—via oligomerization, and C2H4 oxide and acetaldehyde—via oxidation [4,6,7]. In recent for C2H4 production [8]. Other bio‐derived compounds such as methanol and dimethyl‐ether, can years, bio-ethanol has been extensively studied as an alternate feedstock for C2H4 production [8]. also be used as a feedstock for C2H4, via Methanol to Olefins (MTO) and Dimethyl‐ether to Olefins Other bio-derived compounds such as methanol and dimethyl-ether, can also be used as a feedstock (DMTO) processes [9,10]. Bio‐ethylene can also be produced via bio‐synthesis from various enzymes for C2H4, via Methanol to Olefins (MTO) and Dimethyl-ether to Olefins (DMTO) processes [9,10]. or microorganismsBio-ethylene can [11]. also be produced via bio-synthesis from various enzymes or microorganisms [11]. FigureFigure 2. 2. CC2H2H4 production4 production methods methods using using hydrocarbon hydrocarbon feedstocks.feedstocks. Reproduced Reproduced from from [3 [3].]. 2014, 2014, WILEY-VCH Verlag GmbH & Co.WILEY‐VCH Verlag GmbH & Co. C3HC6 3isH 6theis thesecond second most most significant significant olefin, olefin, conventionally produced produced via via steam steam cracking, cracking, as a as a co‐product,co-product, or orthrough through fluidfluid catalytic catalytic cracking cracking (FCC). (FCC). (Figure (Figure3)C 2H 4 3)and C gasoline2H4 and production gasoline severelyproduction severelyaffect affect C3H6 production;C3H6 production; recently, recently, steam crackers steam switch crackers to ethane switch feedstocks, to ethane suppressing feedstocks, concurrent suppressing production of C3H6, while its demand outpaces existing steam and fluid catalytic cracking capacity [12]. concurrent production of C3H6, while its demand outpaces existing steam and fluid catalytic C3H6 is mainly used for the production of polypropylene, as well as for the synthesis of numerous cracking capacity [12]. C3H6 is mainly used for the production of polypropylene, as well as for the platform chemicals (e.g., cumene, acrylonitrile, propylene-oxide) [13]. The importance of C H in synthesis of numerous platform chemicals (e.g., cumene, acrylonitrile, propylene‐oxide)3 [13].6 The the C3
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