Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering

Huber, George W.; Iborra, Sara; Corma, Avelino

doi:10.1002/chin.200652240

Cited by 785 publications

(1,280 citation statements)

References 134 publications

(269 reference statements)

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“…It is estimated that the worldwide production of lignocellulose amounts to 170 Â 10 9 t/year, of which 35À50 wt % is cellulose. 1 Such a tremendous, nonfood, and renewable resource is being considered as the most promising alternative to fossil resources for the sustainable production of fuels and chemicals. Since cellulose has a relatively high O/C ratio, while fuels usually possess a much lower O/C ratio, excess oxygen must be removed when cellulose is transformed into fuels, which would be achieved at the expense of C or H and thereby has a lower efficiency from the viewpoint of atom economy.…”

Section: Introductionmentioning

confidence: 99%

One-Pot Conversion of Cellulose to Ethylene Glycol with Multifunctional Tungsten-Based Catalysts

2013

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W ith diminishing fossil resources and increasing concerns about environmental issues, searching for alternative fuels has gained interest in recent years. Cellulose, as the most abundant nonfood biomass on earth, is a promising renewable feedstock for production of fuels and chemicals. In principle, the ample hydroxyl groups in the structure of cellulose make it an ideal feedstock for the production of industrially important polyols such as ethylene glycol (EG), according to the atom economy rule. However, effectively depolymerizing cellulose under mild conditions presents a challenge, due to the intra-and intermolecular hydrogen bonding network. In addition, control of product selectivity is complicated by the thermal instabilities of cellulosederived sugars. A one-pot catalytic process that combines hydrolysis of cellulose and hydrogenation/hydrogenolysis of cellulose-derived sugars proves to be an efficient way toward the selective production of polyols from cellulose.In this Account, we describe our efforts toward the one-pot catalytic conversion of cellulose to EG, a typical petroleumdependent bulk chemical widely applied in the polyester industry whose annual consumption reaches about 20 million metric tons. This reaction opens a novel route for the sustainable production of bulk chemicals from biomass and will greatly decrease the dependence on petroleum resources and the associated CO 2 emission. It has attracted much attention from both industrial and academic societies since we first described the reaction in 2008. The mechanism involves a cascade reaction. First, acid catalyzes the hydrolysis of cellulose to water-soluble oligosaccharides and glucose (R1). Then, oligosaccharides and glucose undergo CÀC bond cleavage to form glycolaldehyde with catalysis of tungsten species (R2). Finally, hydrogenation of glycolaldehyde by a transition metal catalyst produces the end product EG (R3). Due to the instabilities of glycolaldehyde and cellulose-derived sugars, the reaction rates should be r 1 , r 2 , r 3 in order to achieve a high yield of EG. Tuning the molar ratio of tungsten to transition metal and changing the reaction temperature successfully optimizes this reaction. No matter what tungsten compounds are used in the beginning reaction, tungsten bronze (H x WO 3 ) is always formed. It is then partially dissolved in hot water and acts as the active species to homogeneously catalyze CÀC bond cleavage of cellulose-derived sugars. Upon cooling and exposure to air, the dissolved H x WO 3 is transformed to insoluble tungsten acid and precipitated from the solution to facilitate the separation and recovery of the catalyst. On the basis of this temperature-dependent phase-transfer behavior, we have developed a highly active, selective, and reusable catalyst composed of tungsten acid and Ru/C. Our work has unearthed new understanding of this reaction, including how different catalysts perform and the underlying mechanism. It has also guided researchers to the rational design of catalysts for other reactions inv...

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Section: Introductionmentioning

confidence: 99%

One-Pot Conversion of Cellulose to Ethylene Glycol with Multifunctional Tungsten-Based Catalysts

2013

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“…6,7 For example, propan-2-one (acetone) can be produced from an acetone-butanol-ethanol (ABE) mixture produced by the Clostridial fermentation of sugars or from the bio-oil obtained by fast pyrolysis of biomass feed stocks. 2,7 Butan-2-one can be obtained in more than 90% selectivity by aqueous-phase, acidcatalyzed dehydration of 2,3-butane diol (2, or by the decarboxylation of levulinic acid. 8−10 Finally, pentan-2-one can be produced by the ring opening hydrogenolysis of 2-methylfuran or by the monoalkylation of acetone with ethanol derived from an ABE mixture (Scheme 1).…”

Section: ■ Introductionmentioning

confidence: 99%

“…14,15 We have recently shown that calcined hydrotalcite, HT, is an active and highly selective heterogeneous catalyst for the self-and crosscondensation of biomass-derived C 4 −C 11 methyl ketones to produce cyclic enones, which upon subsequent hydrodeoxygenation produce cyclic alkanes that have properties making them suitable for aviation fuel and lubricants. 6,13,16,17 Hydrotalcite-type layered double hydroxides (LDHs) are inorganic compounds with the chemical composition M 2+ 1−x M 3+ x (OH) 2 (A x/n ) n-·yH 2 O, where M 2+ and M 3+ are divalent and trivalent metal cations, x is the molar ratio of the trivalent cation [M 3+ /(M 2+ + M 3+ )] which can be varied between 17 and 33%, and A n− is an anion with charge n, most often a carbonate ion. 16 The structure of these materials is similar to that of brucite, Mg(OH) 2 , where magnesium is octahedrally surrounded by six oxygens in the form of hydroxides with the octahedral units forming infinite sheets through an edge sharing.…”

Section: ■ Introductionmentioning

confidence: 99%

Effects of Composition and Structure of Mg/Al Oxides on Their Activity and Selectivity for the Condensation of Methyl Ketones

Shylesh¹,

Kim²,

Gokhale

et al. 2016

Ind. Eng. Chem. Res.

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The effects of chemical composition and pretreatment on Mg−Al hydrotalcites and alumina-supported MgO were evaluated for the gas-phase, self-condensation reaction of C 3 −C 5 biomass-derived methyl ketones. We show that the selectivity toward the acyclic dimer enone and the cyclic enone trimer can be tuned by controlling the temperature of hydrotalcite calcination. Methyl ketone cyclization is promoted by Lewis acidic sites present on the hydrotalcite catalysts. XRD and thermal decomposition analysis reveal that the formation of periclase MgO starts above 623 K accompanied by complete disappearance of the hydrotalcite structure and is accompanied by an increase in hydroxyl condensation as the formation of well-crystallized periclase. 27 Al MQMAS and 25 Mg MAS NMR show that at progressively higher temperatures, Al 3+ cations diffuses out of the octahedral brucite layers and incorporate into the tetrahedral and octahedral sites of the MgO matrix thereby creating defects to compensate the excess positive charge generated. The oxygen anions adjacent to the Mg 2+ /Al 3+ defects become coordinatively unsaturated, leading to the formation of new basic sites. A kinetic isotope effect, k H /k D = 0.96, is observed at 473 K for the reaction of (CH 3 ) 2 CO versus (CD 3 ) 2 CO, which suggests that carbon−carbon bond formation leading to the dimer aldol product is the ratedetermining step in the condensation reaction of methyl ketones. We also show that acid−base catalysts having similar reactivity and higher hydrothermal stability to that of calcined hydrotalcites can be achieved by creating defects in MgO crystallites supported alumina as a consequence of the diffusion of Al 3+ cations into MgO. The physical properties of these materials are shown to be very similar to those of hydrotalcite calcined at 823 K.

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“…In addition, the balance between Sn as a Lewis acid and TfOH as a Brønsted acid has a strong influence on product selectivity, therefore indicating that tuning of the Lewis and Brønsted acidic ratio is crucial to achieving the desired degradation of the polysaccharides and of glucose. 1 Reaction conditions: Triose (2.5 mmol), catalyst (10 mol %), methanol (4 mL), 90 °C, over 3 h. 2 Gasliquid chromatography (GLC) yield (mol %) were based on triose.…”

Section: Production Of Alkyl Levulinate From Carbohydrates Using Homomentioning

confidence: 99%

“…As such, various methods have been developed to allow the use of carbohydrates as alternative resources, and these processes could have a significant impact on reducing carbon dioxide emissions. Carbohydrates derived from both crop biomass (i.e., storage polysaccharides, such as starch) and woody biomass (i.e., cell wall polysaccharides, such as cellulose) have been considered for this purpose [1][2][3][4][5][6][7][8]. However, as the global population continues to increase, the use of limited farmland to grow crop biomass instead of food is clearly unrealistic.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Processes for Utilizing Carbohydrates Derived from Algal Biomass

et al. 2017

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Abstract:The high productivity of oil biosynthesized by microalgae has attracted increasing attention in recent years. Due to the application of such oils in jet fuels, the algal biosynthetic pathway toward oil components has been extensively researched. However, the utilization of the residue from algal cells after oil extraction has been overlooked. This residue is mainly composed of carbohydrates (starch), and so we herein describe the novel processes available for the production of useful chemicals from algal biomass-derived sugars. In particular, this review highlights our latest research in generating lactic acid and levulinic acid derivatives from polysaccharides and monosaccharides using homogeneous catalysts. Furthermore, based on previous reports, we discuss the potential of heterogeneous catalysts for application in such processes.

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Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering

Abstract: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Cited by 785 publications

References 134 publications

One-Pot Conversion of Cellulose to Ethylene Glycol with Multifunctional Tungsten-Based Catalysts

One-Pot Conversion of Cellulose to Ethylene Glycol with Multifunctional Tungsten-Based Catalysts

Effects of Composition and Structure of Mg/Al Oxides on Their Activity and Selectivity for the Condensation of Methyl Ketones

Catalytic Processes for Utilizing Carbohydrates Derived from Algal Biomass

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