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Glycerol Production and Transformation membranes Review Glycerol Production and Transformation: A Critical Review with Particular Emphasis on Glycerol Reforming Reaction for Producing Hydrogen in Conventional and Membrane Reactors Giuseppe Bagnato 1, Adolfo Iulianelli 2,*, Aimaro Sanna 1 and Angelo Basile 2,* 1 School of Engineering & Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UK; [email protected] (G.B.); [email protected] (A.S.) 2 Institute on Membrane Technology of the Italian National Research Council (ITM-CNR), c/o University of Calabria, via P. Bucci Cubo 17/C, 87036 Rende (CS), Italy * Correspondence: [email protected] (A.I.); [email protected] (A.B.); Tel.: +39-0984-492011 (A.I.); +39-0984-492013 (A.B.) Academic Editor: Edward Gobina Received: 12 January 2017; Accepted: 17 March 2017; Published: 23 March 2017 Abstract: Glycerol represents an emerging renewable bio-derived feedstock, which could be used as a source for producing hydrogen through steam reforming reaction. In this review, the state-of-the-art about glycerol production processes is reviewed, with particular focus on glycerol reforming reactions and on the main catalysts under development. Furthermore, the use of membrane catalytic reactors instead of conventional reactors for steam reforming is discussed. Finally, the review describes the utilization of the Pd-based membrane reactor technology, pointing out the ability of these alternative fuel processors to simultaneously extract high purity hydrogen and enhance the whole performances of the reaction system in terms of glycerol conversion and hydrogen yield. Keywords: glycerol production; glycerol steam reforming; conventional reactor; membrane reactor; hydrogen 1. Introduction The need for replacing fossil fuels is driving the development of renewable fuels such as biodiesel. In the period 2000–2012, biodiesel production increased from 15 to 430 thousand barrels (Figure1)[ 1–3]. In the process of producing biodiesel from the transesterification of vegetable oils, glycerol (propane-1,2,3-triol) is produced as by-product. Typically, the production of 100 kg of biodiesel yields approximately 10 kg of glycerol, with purity of around 50%–55% [1]. The increased production of bio-diesel resulted in a significant fall of glycerol prices from 2000 to 2010 in the European Union (UE) and USA, as can be seen in Figure2. In particular, the price dramatically decreased from about 3200 $/ton in EU and 2000 $/ton in USA to under 500 $/ton and 600 $/ton, respectively. This was mainly due to a new demand in developing countries as China, India, Russia and Latin American countries, where the glycerol was utilized as raw material in the personal care, pharmaceuticals and food and beverage sectors [4–6]. Currently, glycerol is mainly used as an intermediate chemical for the production of a variety of products [7], such as cosmetics, food, pharmaceuticals, etc., as represented in Figure3. Membranes 2017, 7, 17; doi:10.3390/membranes7020017 www.mdpi.com/journal/membranes Membranes 2017, 7, 17 2 of 31 Membranes 2017, 7, 17 2 of 30 Figure 1. Biodiesel and glycerol production vs. years. Figure 1. Biodiesel and glycerol production vs.vs. years. Figure 2. GlycerolGlycerol price trend in USA and UE. With permission of reprint by Wiley fromfrom [[1].1]. Figure 3. Percentage distribution of the main glycerol applications found in the open literature. Figure 3. Percentage distribution of the main glycerol applications found in the open literature. 1.1. Glycerol Production Membranes 2017, 7, 17 3 of 31 Membranes 2017, 7, 17 3 of 30 1.1.Membranes Glycerol 2017 Production, 7, 17 3 of 30 GlycerolGlycerol can can be be produced produced byby usingusing differentdifferent processesprocesses and feedstocks. For For example, example, it itcan can be be Glycerol can be produced by using different processes and feedstocks. For example, it can be obtainedobtained by by propylene propylene synthesis synthesis viavia severalseveral pathwayspathways [8], [8], by by hydrolysis hydrolysis of of oil oil or or by by transesterification transesterification obtained by propylene synthesis via several pathways [8], by hydrolysis of oil or by transesterification ofof fatty fatty acids/oils. acids/oils. Nevertheless,Nevertheless, glycerol production production can can be be also also carried carried out out by by fermentation fermentation with with of fatty acids/oils. Nevertheless, glycerol production can be also carried out by fermentation with yeastyeast such such as as saccharomyces saccharomyces cerevisiae,cerevisiae, candida,candida, bacteria such as as Bacillus Bacillus subtilis subtilis and and algae algae such such as as yeast such as saccharomyces cerevisiae, candida, bacteria such as Bacillus subtilis and algae such as dunalielladunaliella tertiolecta tertiolecta [ 9[9].]. dunaliella tertiolecta [9]. 1.1.1.1.1.1. Glycerol Glycerol via via Propylene Propylene 1.1.1. Glycerol via Propylene AsAs stated stated before, before, several several pathwayspathways cancan be used for producing glycerol glycerol by by propylene propylene [3,10] [3,10 and] and As stated before, several pathways can be used for producing glycerol by propylene [3,10] and FigureFigure4 sketches4 sketches two two of of the the principal principal pathways, pathways, which which involveinvolve thethe useuse ofof O 22 oror Cl Cl2.2 . Figure 4 sketches two of the principal pathways, which involve the use of O2 or Cl2. FigureFigure 4.4. GlycerolGlycerol production via propylene utilization. utilization. Figure 4. Glycerol production via propylene utilization. In the propylene chlorination (Figure 5), allyl chloride is produced at 510 °C in presence of InIn the the propylene propylene chlorinationchlorination (Figure(Figure5 5),), allylallyl chloridechloride isis producedproduced at 510 °C◦C in in presence presence of of hypochlorous acid at 38 °C. The allyl chloride reacts to produce glycerine dichlorohydrine. hypochloroushypochlorous acid acid at 38at ◦C.38 The°C. allylThe chlorideallyl chloride reacts toreacts produce to glycerineproduce dichlorohydrine.glycerine dichlorohydrine. Afterwards, Afterwards, glycerol dichlorohydrine is hydrolysed by caustic soda in a 6% Na2CO3 solution◦ at 96 °C glycerolAfterwards, dichlorohydrine glycerol dichlorohydrine is hydrolysed is byhydrolysed caustic soda by caustic in a 6% soda Na inCO a 6%solution Na2CO at3 solution 96 C or at directly 96 °C or directly to glycerine, taking off the epichlorohydrine as an overhead2 in3 a stripping column. At the toor glycerine, directly to taking glycerine, off the taking epichlorohydrine off the epichlorohydrine as an overhead as an overhead in a stripping in a stripping column. column. At the end,At the the end, the epichlorohydrine is hydrated to glycerine with caustic soda [3] and the process makes epichlorohydrineend, the epichlorohydrine is hydrated is tohyd glycerinerated to with glycerine caustic with soda caustic [3] and soda the process[3] and makesthe process possible makes final possible final glycerol yield of about 90%. glycerolpossible yield final of glycerol about 90%.yield of about 90%. Figure 5. Scheme of the prolylene cholorination process. FigureFigure 5.5. SchemeScheme of the prolylene cholorination process. process. 1.1.2. Hydrolysis of Oil 1.1.2. Hydrolysis of Oil Membranes 2017, 7, 17 4 of 31 Membranes 2017, 7, 17 4 of 30 Membranes 2017, 7, 17 4 of 30 1.1.2. HydrolysisThe hydrolysis of Oil is a process known since 2800 B.C. and the first industrial plant was built up in 1860 [11]. This reaction takes place between triglyceride and alkaline hydroxide (caustic soda) TheThe hydrolysishydrolysis is a process known known since since 2800 2800 B.C. B.C. and and the the first first industrial industrial plant plant was was built built up in up producing glycerol and soap [12] (Figure 6). in1860 1860 [11 [11]. ].This This reaction reaction takes takes place place between between triglyceride triglyceride and and alkaline alkaline hydroxide hydroxide (caustic (caustic soda) soda) producingproducing glycerol glycerol and and soapsoap [[12]12] (Figure(Figure6 6).). Figure 6. Hydrolysis reaction for glycerol production. FigureFigure 6.6. Hydrolysis reaction for glycerol produc production.tion. 1.1.3. Transesterification of Oil 1.1.3.1.1.3. TransesterificationThe Transesterification transesterification ofof Oil Oilreaction of the beaver oil with ethanol to produce glycerol was conducted in 1864TheThe by transesterification transesterification Rochieder [5,13]. reactionreaction Figure ofof7 representsthethe beaver the oil withschematic ethanol ethanol of to tothe produce produce reaction, glycerol glycerol where was wasmethyl conducted conducted-esters ininfrom 1864 1864 triglyceride by by Rochieder Rochieder (oils) [5 ,[5,13]. 13and]. Figuremethanol Figure7 represents 7 (alcohol) represents thereact the schematic to schematic produce of the glycerolof reaction,the reaction, and where fatty where esters methyl-esters methyl (or biodiesel)-estersfrom triglyceridefrom[10,14,15]. triglyceride (oils) and (oils) methanol and methanol (alcohol) (alcohol) react to react produce to produce glycerol glycerol and fatty and esters fatty (or esters biodiesel) (or biodiesel)[10,14,15 ]. [10,14,15]. FigureFigure 7.7. TransesterificationTransesterification reaction for glycerol production production.. Figure 7. Transesterification reaction for glycerol production. HomogeneousHomogeneous andand heterogeneousheterogeneous catalysis can be used to to produce produce bio bio-diesel-diesel and and thereby thereby for for glycerolglycerolHomogeneous
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