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Solid Acids for the Reaction of Bioderived Alcohols Into Ethers for Fuel Applications

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Solid Acids for the Reaction of Bioderived Alcohols Into Ethers for Fuel Applications catalysts Review Solid Acids for the Reaction of Bioderived Alcohols into Ethers for Fuel Applications Federica Zaccheria *, Nicola Scotti and Nicoletta Ravasio CNR, Istituto di Scienze e Tecnologie Molecolari, Via C. Golgi 19, 20133 Milano, Italy; [email protected] (N.S.); [email protected] (N.R.) * Correspondence: [email protected]; Tel.: +39-02-50314384 Received: 19 December 2018; Accepted: 1 February 2019; Published: 12 February 2019 Abstract: The use of solids acids in the synthesis of ethers suitable to be used as fuels or fuel additives were reviewed in a critical way. In particular, the role of Brønsted and Lewis acid sites was highlighted to focus on the pivotal role of the acidity nature on the product distribution. Particular emphasis is given to the recently proposed ethers prepared starting from furfural and 5-hydroxymethyl furfural. Thus, they are very promising products that can be derived from lignocellulosic biomass and bioalcohols and possess very interesting chemical and physical properties for their use in the diesel sector. Keywords: ethers; furanics; zeolites; solid acids; Brønsted sites; Lewis sites 1. Introduction Oxygenated fuels, such as alcohols and ethers, represent an important alternative to conventional non-oxygenated ones. In fact, the use of oxygen containing molecules in internal combustion engines provides several advantages in terms of environmental impact, namely in reducing greenhouse gas emissions (GHG), due to the low content of pollutants, like sulfur, and to complete combustion reducing formation of particulate. [1,2]. Their use varies from the role of additives in gasoline to the formulation in diesel blends depending on their structure (Table1). Ethers, such as methyl tert butyl ether (MTBE), have been used as an octane booster instead of tetraethyl lead and to decrease engine emissions. For these reasons, MTBE use has seen a speedy growth until the end of the 1990s and after, while in the past decade, the worldwide market underwent significant changes because of the ban in the US and Canada [3]. Thus, MTBE is toxic, volatile, and flammable and its use entails several concerns for human and water protection [4]. Dimethylether (DME), already in use since 1867 as an anesthetic agent, has been used in diesel engines starting from 1986 and its production is foreseen to gradually increase, particularly on the wave of bio-DME synthesis [5]. Also, ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) have been successfully introduced to replace tetraethyl lead (i.e., a toxic pollutant) in gasoline. The strategic role of oxygenated components in the fuel market is witnessed by the presence of several networks and associations born to promote the responsible diffusion of oxygenated fuels, both alcohols and ether ones. Examples of this approach are the European Fuel Oxygenates Association (EFOA) and the International DME Association (IDA). Catalysts 2019, 9, 172; doi:10.3390/catal9020172 www.mdpi.com/journal/catalysts Catalysts 2019, 9, 172 2 of 21 Catalysts 2018, 8, x FOR PEER REVIEW 2 of 21 Catalysts 2018, 8, x FOR PEER REVIEW 2 of 21 CatalystsCatalystsCatalysts 2018 2018, 82018, ,x 8 FOR,, x8 ,FOR x PEER FOR PEER PEERREVIEW REVIEW REVIEW 2 of2 21of2 21of 21 Catalysts 2018, 8, x FOR PEER REVIEW 2 of 21 Catalysts 2018, 8, x FOR PEER REVIEWTable 1. Most widespread ethers for fuel applications 2 of 21 Catalysts 2018, 8, x FOR PEER REVIEWTable Table1 . Most 1. widespreadMost widespread ethers for ethers fuel applications for fuel applications. 2 of 21 Catalysts 2018, 8, x FOR PEER REVIEWTableTableTable 1 . Most1. Most1. Mostwidespread widespread widespread ethers ethers ethers for for fuel for fuel applications fuel applications applications 2 of 21 Catalysts 2018, 8, x FOREther PEER REVIEWTable 1. Most widespreadStructure ethers for fuel applicationsBio-moiety Fuel 2sector of 21 EtherEther Table 1. Most widespreadStructure Structure ethers for fuel applicationsBio-moiety Bio-moiety Fuel sector Fuel sector Ether Structure Bio-moiety Fuel sector Ether Table 1. Most widespreadStructure ethers for fuel applicationsBio-moiety Fuel sector Ether Structure Bio-moiety Fuel sector Dimethyl ether O Gasoline and Table 1. Most widespread ethers for fuel applications DimethylDimethylEther ether ether StructureO Bio-moietyMethanol GasolineFuelGasoline sector and and diesel DimethylDimethyl ether ether Table 1. Most widespread ethers for fuel applications GasolineGasoline and and DimethylEther etherDME Structure O O O MethanolBio-moietyMethanol GasolineFueldiesel sector and blend DimethylEtherDMEDME ether Structure Bio-moietyMethanolMethanol dieselFuelGasoline sector blend andblend DME diesel blend Methanol O EtherDME Structure Bio-moiety Fueldiesel sector blend DME diesel blend DimethylDME ether Methanol dieselGasoline blend and DimethylEtherDiethyl ether ether Structure O Bio-moiety GasolineFuelGasoline sector and and DiethylDME ether Methanol Gasolinediesel blend and DiethylDiethyl ether ether O Ethanol GasolineGasoline and and diesel DimethylDiethylDiethylDME ether ether ether O O MethanolEthanolEthanol GasolineGasolinedieselGasoline blendand and and DimethylDiethyl ether DEEether O O Ethanol GasolineGasolinediesel and and blend DMEDEE DEE O O MethanolEthanolEthanol diesel blendblend DiethylDMEDEEDEE DEE ether MethanolEthanol dieselGasolinedieseldiesel blend blend and blend DiethylDEEDMEDibutyl ether ether O Ethanol dieseldieselGasolineGasoline blend blend and and DibutylDiethylDibutylDEE ether ether O EthanolButanol GasolinedieselGasoline blend and and diesel DiethylDibutylDibutylDEE ether ether ether O 3 3 ButanolEthanol GasolineGasolinedieselGasoline blendand and and DibutylDiethyl etheretherDBE O 3 O 3 ButanolEthanolButanolButanol GasolineGasolinediesel and and blend DibutylDBEDEE DBEether O3 O 3 3 ButanolButanol dieselGasoline blend andblend DEEDBE DBE 3 3 3O O 3 Ethanol dieseldieseldiesel blend blend blend DibutylDBEDEE ether O 3 Butanol dieseldieselGasoline blend blend and 3 DibutylDBE ether O Butanol Gasolinediesel blend and 3 Dibutyl ether 3 Gasoline and DBE O Butanol diesel blend MethylDibutyl tert- etherbutyl ether 3 3 GasolineOctane and booster DBE O Butanol diesel blend MethylMethylMethyl tert-butyl tert-tert-butylbutyl ether ether ether 3 O 3 Butanolmethanol OctaneOctane Octanebooster booster booster for DBE diesel blend MethylMethyl tert- DBEtert-butylMTBEbutyl ether ether 3 O 3 methanolmethanol OctanedieselOctanefor booster blend boostergasoline MTBE O methanol gasoline MethylMTBE tert-butyl ether O methanolmethanol Octanefor gasoline booster O Methyl tert-MTBEMTBEbutyl ether O O methanol Octaneforfor gasoline gasolinebooster MTBE for gasoline Methyl tert-MTBEbutyl ether O methanol Octanefor gasoline booster Methyl tert-MTBEbutyl ether O methanol Octanefor gasolinebooster Methyl MTBEtert-butyl ether O methanol Octanefor gasoline booster EthylEthyl tertMTBE-butyl tert -butyl ether ether O methanol Octanefor Octanegasoline booster booster EthylEthylEthyl Ethyltert MTBEtert-butyl terttert-butyl-butyl ether ether ether ether O ethanol OctaneforOctaneOctane gasoline Octanebooster booster booster booster for Ethyl tert-butylETBE ether O ethanolethanolethanol Octanefor booster gasoline Ethyl tertETBE-butylETBE ether O ethanolethanol Octanefor gasoline boostergasoline ETBEETBE O forfor gasoline gasoline O Ethyl tert-butyl ether O ethanol Octane booster ETBE for gasoline O O Ethyl tert-butyl ether Octane booster ETBE O ethanol for gasoline Ethyl tert-butyl ether O Octane booster ETBE ethanol for gasoline EthylTert tertETBE-amyl-butyl methylether ether O ethanol Octanefor gasolineOctane booster booster Tert-amyl methylether Octane booster Tert-amyl methylether Octane booster Tert-amylTertETBE-amyl methylether methylether O ethanolnethanol Octanefor Octanegasoline booster booster TertTert-amyl-amyl methylether methylether nethanol OctaneOctane booster booster for Tert-amylETBE methyletherTAME O nethanol Octanefor gasolinefor booster gasoline nethanolnethanol Tert-amylTAME methylether O nethanolnethanol Octanefor gasoline booster TAME O gasoline TAMETAME forfor gasoline gasoline Tert-amylTAME methylether O nethanol forOctane gasoline booster Tert-amylTAME methylether O O O nethanol Octanefor gasoline booster Tert-amyl TAMEmethylether O nethanol Octanefor gasolinebooster Tert-amylTert-TAME amylmethylether ethyl ether nethanol Octanefor gasolineOctane booster booster Tert-Tert-amylTAMEamyl ethyl ethyl ether ether O nethanolethanol Octanefor Octanegasoline booster booster Tert-Tert-amylTert-amylTAMEamyl ethyl TAEEethyl ethyl ether ether ether O ethanol OctaneforOctane gasolinefor Octanebooster boostergasoline booster for Tert-amylTAEE ethyl ether O O ethanolethanolethanolethanol Octanefor gasoline booster TAEETAEE OO forfor gasoline gasolinegasoline Tert-amylTAEE ethyl ether O O ethanol forOctane gasoline booster Tert-amylTAEE ethyl ether O ethanol Octanefor gasoline booster Tert-amyl ethyl ether O ethanol Octane booster Tert-amylTAEE ethyl ether ethanol Octanefor gasoline booster TAEE O ethanol for gasoline TAEE O O for gasoline TAEE OO for gasoline O O O O O O OH O OH O O OH di- and tri-tert-butyl glycerol O O O OH OH di- and tri-tert-butyl glycerol O O OH di-di- anddi- and tri-and tri-tert tri-tert-butyltert-butylether-butyl glycerol glycerol glycerol O O OH Glycerol Diesel additives di- and tri-ethertert-butyl glycerol O OH Glycerol Diesel additives di- andether tri-ethertertether -butyl glycerol O OH GlycerolGlycerolGlycerol DieselDieselDiesel additives additives additives
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