Abstract
The use of homogeneous rather than heterogeneous catalysts for the hydrodeoxygenation of sugars, sugar alcohols, and their condensates such as furfural, 5-hydroxymethylfurfural, levulinic acid, and isosorbide may offer reaction pathways that have distinct advantages, notably with respect to catalyst deactivation by coking and fouling as observed on many heterogeneous systems with these highly reactive and polar substrates. Homogeneous systems, however, also face unique challenges in ligand, catalyst, and process design. The catalyst systems employed will have to be stable to the required aqueous acidic high-temperature (T > 150 °C) reaction conditions while exhibiting activities that make them kinetically competent over acid-catalyzed decomposition and oligo- and polymerization reactions leading to humin formation. For each of the hydrodeoxygenation reaction cascades for the C3 (glycerol), C4 (erythritol), C5 (xylose and derivatives or levulinic acid), and C6 (glucose and derivatives) value chains, comparatively few homogeneous catalyst systems have been evaluated to date. Key issues remain the thermal and redox stability of the complexes employed against decomposition and reduction to bulk metal acting as a heterogeneous catalysts and the recovery and recycling of the catalyst from the often very complex reaction and product mixtures.
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Schlaf M (2006) Selective deoxygenation of sugar polyols to alpha,omega-diols and other oxygen content reduced materials – a new challenge to homogeneous ionic hydrogenation and hydrogenolysis catalysis. J Chem Soc Dalton Trans 39:4645–4653
Schiweck H et al (2000), Sugar alcohols. In: Ullmann’s encyclopedia of industrial chemistry. Wiley-VCH Verlag GmbH & Co. KGaA
Sabatier P, Mailhe A (1909) New applications of the general method of hydrogenation on divided metals. Annales De Chimie Et De Phys 16:70–107
Schuette HA, Thomas RW (1930) Normal valerolactone. III. Its preparation by the catalytic reduction of levulinic acid with hydrogen in the presence of platinum oxide. J Am Chem Soc 52:3010–3012
Schiavo V, Descotes G, Mentech J (1991) Catalytic-hydrogenation of 5-hydroxymethylfurfural in aqueous-medium. Bull Soc Chim Fr 128(5):704–711
Huber GW, Iborra S, Corma A (2006) Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. Chem Rev 106(9):4044–4098
Corma A, Iborra S, Velty A (2007) Chemical routes for the transformation of biomass into chemicals. Chem Rev 107(6):2411–2502
Alonso DM, Bond JQ, Dumesic JA (2010) Catalytic conversion of biomass to biofuels. Green Chem 12(9):1493–1513
Alonso DM, Wettstein SG, Dumesic JA (2012) Bimetallic catalysts for upgrading of biomass to fuels and chemicals. Chem Soc Rev 41(24):8075–8098
Gallezot P (2012) Conversion of biomass to selected chemical products. Chem Soc Rev 41(4):1538–1558
Climent MJ, Corma A, Iborra S (2014) Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels. Green Chem 16(2):516–547
Besson M, Gallezot P, Pinel C (2014) Conversion of biomass into chemicals over metal catalysts. Chem Rev 114(3):1827–1870
Xiong H, Pham HN, Datye AK (2014) Hydrothermally stable heterogeneous catalysts for conversion of biorenewables. Green Chem 16:4627–4643
Deuss PJ, Barta K, de Vries JG (2014) Homogeneous catalysis for the conversion of biomass and biomass-derived platform chemicals. Catal Sci Technol 4(5):1174–1196
Cornils B, Herrmann WA (1996) Applied homogeneous catalysis with organometallic compounds, vol 1. VCH, Weinheim
Copes JP, McKinley C (1954) Production of 1,4-butanediol from Tetrahydrofuran, General Aniline & Film Corporation, US Patent 2,686,817
Martell AE, Hancock RD, Motekaitis RJ (1994) Factors affecting the stabilities of chelate, macrocyclic and macrobicyclic complexes in solution. Coord Chem Rev 133:39–65
Howells RD, Crown JDM (1977) Trifluoromethanesulfonic acid and derivatives. Chem Rev 77:69–92
Guerbet M (1899) Action des alcools ethylique, isobutylique, isoamylique sur leurs derives sodes. CR Hebd Seances Acad Sci 128:1002–1004
Guerbet M (1909) Condensation de l’alcool isopropylique avec son dérivé sodé; formation du méthylisobutylcarbinol et du diméthyl-2.4-heptanol-6. CR Hebd Seances Acad Sci 149:129–132
Veibel S, Nielsen JI (1967) On the mechanism of the Guerbet reaction. Tetrahedron 23(4):1723–1733
Dowson GRM et al (2013) Catalytic conversion of ethanol into an advanced biofuel: unprecedented selectivity for n-butanol. Angew Chem Int Ed 52(34):9005–9008
Hamid M, Slatford PA, Williams JMJ (2007) Borrowing hydrogen in the activation of alcohols. Adv Synth Catal 349(10):1555–1575
Obora Y, Ishii Y (2011) Iridium-catalyzed reactions involving transfer hydrogenation, addition, n-heterocyclization, and alkylation using alcohols and diols as key substrates. Synlett 1:30–51
Koda K et al (2009) Guerbet reaction of ethanol to n-butanol catalyzed by iridium complexes. Chem Lett 38(8):838–839
Xu GQ et al (2014) Direct self-condensation of bio-alcohols in the aqueous phase. Green Chem 16(8):3971–3977
An industrial scale production of 1,3-propanediol by the fermentation of glucose using genetically modified organisms has been realized by DuPont Tate & Lyle Bioproducts
Pagliaro M et al (2007) From glycerol to value-added products. Angew Chem Int Ed 46(24):4434–4440
Behr A et al (2008) New chemical products on the basis of glycerol. Chimica Oggi-Chem Today 26(1):32–36
Zhou CHC et al (2008) Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals. Chem Soc Rev 37(3):527–549
ten Dam J, Hanefeld U (2011) Renewable chemicals: dehydroxylation of glycerol and polyols. ChemSusChem 4(8):1017–1034
Zhou CH et al (2013) Recent advances in catalytic conversion of glycerol. Catal Rev-Sci Eng 55(4):369–453
Che T (1987) Production of Propanediols, Celanese Corporation, US Patent 4,642,394
Braca G, Galletti AMR, Sbrana G (1991) Anionic ruthenium iodocarbonyl complexes as selective dehydroxylation catalysts in aqueous solution. J Organomet Chem 417:41–49
Drent E, Jager WW (2000) Hydrogenolysis of glycerol. Shell Oil, US Patent 6,080,898
Brem N et al (2010) Carbonylation of glycerol and other polyols: a high throughput study of feasibility. Top Catal 53(1–2):28–34
Coskun T et al (2013) Carbodeoxygenation of biomass: the carbonylation of glycerol and higher polyols to monocarboxylic acids. Chem A Eur J 19(21):6840–6844
Nakamura Y (1979) Carbonylation of polyhydric alcohols. Noguchi Research Foundation, Japanese Patent 54044608A
Bullock RM (2004) Catalytic ionic hydrogenations. Chem A Eur J 10(10):2366–2374
Xie Z, Schlaf M (2005) Direct transformation of terminal vic-diols to primary alcohols and alkanes through hydrogenation catalyzed by [cis-Ru(6,6′-Cl-2-bipy)(2)(OH2)(2)](CF3SO3)(2) in acidic medium. J Mol Catal A Chem 229(1–2):151–158
Lau C-P, Cheng L (1993) Catalytic hydrogenation reactions by [cis-Ru(6,6-Cl2bpy)2(OH2)2](CF3SO2)2 in biphasic media; (6,6-Cl2bpy = 6,6′-dichloro-2,2′-bipyridine). J Mol Catal 84:39–50
Lau CP, Cheng L (1992) Catalytic hydrogenation reactions by cis-[Ru(6,6′-Cl2bpy)2(OH2)2][CF3SO3]2 (6,6′-Cl2bpy = 6,6′-dichloro-2,2′-bipyridine). Inorg Chim Acta 195:133–134
Taher D et al (2009) Acid-, water- and high-temperature stable ruthenium complexes for the total catalytic deoxygenation of glycerol to propane. Chemistry 15:10132–10143
Kubas G (2001) Metal dihydrogen and σ-bond complexes. Structure, theory and reactivity. In: Fackler JJP (ed) Modern inorganic chemistry. Kluwer Academic/Plenum Publishers, New York
Grundler PV et al (2006) Kinetic studies on the first dihydrogen aquacomplex, [Ru(H2)(H2O)5]2+: formation under H2 pressure and catalytic H/D isotope exchange in water. Inorg Chim Acta 359(6):1795–1806
Schlaf M et al (2009) Catalytic deoxygenation of 1,2-propanediol to give n-propanol. Adv Synth Catal 351(5):789–800
Schlaf M et al (2001) Metal-catalyzed selective deoxygenation of diols to alcohols. Angew Chem Int Ed 40:3887–3890
Dykeman RR et al (2007) Catalytic deoxygenation of terminal-diols under acidic aqueous conditions by the ruthenium complexes [([eta]6-arene)Ru(X)(N [intersection] N)](OTf)n, X = H2O, H, [eta]6-arene = p-Me-iPr-C6H4, C6Me6, N [intersection] N = bipy, phen, 6,6′-diamino-bipy, 2,9-diamino-phen, (n = 1, 2): influence of the ortho-amine substituents on catalytic activity. J Mol Chem 277:233–251
Thibault ME et al (2011) Cyclopentadienyl and pentamethylcyclopentadienyl ruthenium complexes as catalysts for the total deoxygenation of 1,2-hexanediol and glycerol. Green Chem 13(2):357–366
See other chapters in this book
Goldberg KI et al (2013) Methods of converting polyols. World Patent WO/2013/130972
Lao DB et al (2013) Partial deoxygenation of glycerol catalyzed by iridium pincer complexes. ACS Catal 3(10):2391–2396
Arceo E et al (2009) An efficient didehydroxylation method for the biomass-derived polyols glycerol and erythritol. Mechanistic studies of a formic acid-mediated deoxygenation. Chem Commun 23:3357–3359
Manzer LE (2003) Production of tetrahydrofuran from tetrahydroxybutane in the presence of an acid and carbon-supported rhenium catalysts. E.T. DuPont Nemours and Company, World Patent WO 2003042200 A1
Lichtenthaler FW (2000) Carbohydrates as organic raw materials. In: Ullmann’s encyclopedia of industrial chemistry. Wiley-VCH Verlag GmbH & Co. KGaA
Van Zandvoort I et al (2013) Formation, molecular structure, and morphology of humins in biomass conversion: influence of feedstock and processing conditions. ChemSusChem 6(9):1745–1758
Assuming that the hydrolysis of 2-methyl-tetrahydrofuran, which is possible under extreme reaction conditions does not take place. See [16].
Adkins H, Connor R (1931) The catalytic hydrogenation of organic compounds over copper chromite. J Am Chem Soc 53:1091–1095
Schniepp LE, Geller HH (1946) Preparation of dihydropyran, δ-hydroxyvaleraldehyde and 1,5-pentanediol from tetrahydrofurfuryl alcohol. J Am Chem Soc 68:1646–1648
Liu S et al (2014) One-pot selective conversion of furfural into 1,5-pentanediol over a Pd-added Ir-ReOx/SiO2 bifunctional catalyst. Green Chem 16(2):617–626
Mizugaki T et al (2014) Direct transformation of furfural to 1,2-pentanediol using a hydrotalcite-supported platinum nanoparticle catalyst. ACS Sus Chem Eng 2(10):2243–2247
Hronec M, Fulajtarová K, Liptaj T (2012) Effect of catalyst and solvent on the furan ring rearrangement to cyclopentanone. Appl Catal Gen 437–438:104–111
Yang Y et al (2013) Conversion of furfural into cyclopentanone over Ni-Cu bimetallic catalysts. Green Chem 15(7):1932–1940
Guo J et al (2014) Selective conversion of furfural to cyclopentanone with CuZnAl catalysts. ACS Sus Chem Eng 2(10):2259–2266
Li X-L et al (2015) Selective conversion of furfural to cyclopentanone or cyclopentanol using different preparation methods of Cu-Co catalysts. Green Chem 15:1038–1046
Gowda AS, Parkin S, Ladipo FT (2012) Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes. Appl Organomet Chem 26(2):86–93
Bozell JJ et al (2000) Production of levulinic acid and use as a platform chemical for derived products. Resour Conserv Recycl 28(3–4):227–239
Lange J-P et al (2010) Valeric biofuels: a platform of cellulosic transportation fuels. Angew Chem Int Ed 49:4479–4483
Ayoub PM, Lange J-P (2008) Process for converting levulinic into pentanoic acid. Shell, World Patent WO 2008/142127
Horváth I et al (2008) γ-Valerolactone – a sustainable liquid for energy and carbon-based chemicals. Green Chem 10:238–242
Horvath IT (2008) Solvents from nature. Green Chem 10(10):1024–1028
Fabos V et al (2009) Bio-oxygenates and the peroxide number: a safety issue alert. Energy Environ Sci 2(7):767–769
Fegyverneki D et al (2010) Gamma-valerolactone-based solvents. Tetrahedron 66(5):1078–1081
Delhomme C et al (2013) Catalytic hydrogenation of levulinic acid in aqueous phase. J Organomet Chem 724:297–299
Li W et al (2012) Highly efficient hydrogenation of biomass-derived levulinic acid to [gamma]-valerolactone catalyzed by iridium pincer complexes. Green Chem 14(9):2388–2390
Blum Y et al (1985) Cyclopentadienone(ruthenium carbonyl complexes – a new class of homogeneous hydrogenation catalysts). Organometallics 4:1459–1461
Shvo Y, Czarkie D, Rahamin Y (1986) A new group of ruthenium complexes: structure and catalysis. J Am Chem Soc 108:7400–7402
Fabos V, Mika LT, Horvath IT (2014) Selective conversion of levulinic and formic acids to gamma-valerolactone with the Shvo catalyst. Organometallics 33(1):181–187
Mehdi H et al (2008) Integration of homogeneous and heterogeneous catalytic processes for a multi-step conversion of biomass: from sucrose to levulinic acid, g-valerolactone, 1,4-pentanediol, 2-methyl-tetrahydrofuran, and alkanes. Topics Catal 48:49–54
The same complex with triflate as the counterion was also employed by the author as for the hydrodeoxygenation of terminal diols to primary alcohols under hydrogen atmosphere in acidic aqueous sulfolane solution. See: Dykeman RR, Luska KL, Thibault ME, Jones MD, Schlaf M, Khanfar M, Taylor N, Britten J, Harrington JF, Mol LJ. Catal A Chem 277:233–251.
Geilen FMA et al (2010) Selective and flexible transformation of biomass-derived platform chemicals by a multifunctional catalytic system. Angew Chem Int Ed 49(32):5510–5514
Geilen FMA et al (2011) Selective homogeneous hydrogenation of biogenic carboxylic acids with [Ru(TriPhos)H]+: a mechanistic study. J Am Chem Soc 133(36):14349–14358
Montgomery R, Wiggins LF (1946) Anhydrides of polyhydric alcohols. IV. Constitution of dianhydrosorbitol. J Chem Soc pp 390–393
Pasini T et al (2014) Substrate and product role in the Shvo’s catalyzed selective hydrogenation of the platform bio-based chemical 5-hydroxymethylfurfural. Dalton Trans 43(26):10224–10234
Yang W, Grochowski MR, Sen A (2012) Selective reduction of biomass by hydriodic acid and its in situ regeneration from iodine by metal/hydrogen. ChemSusChem 5:1218–1222
Grochowski MR, Yang WR, Sen A (2012) Mechanistic study of a one-step catalytic conversion of fructose to 2,5-dimethyltetrahydrofuran. Chem Eur J 18(39):12363–12371
Yang W, Sen A (2011) Direct catalytic synthesis of 5-methylfurfural from biomass-derived carbohydrates. ChemSusChem 4(3):349–352
Yang WR, Sen A (2010) One-step catalytic transformation of carbohydrates and cellulosic biomass to 2,5-dimethyltetrahydrofuran for liquid fuels. ChemSusChem 3(5):597–603
Sullivan RJ et al (2014) Hydrodeoxygenation of 2,5-hexanedione and 2,5-dimethylfuran by water-, air-, and acid-stable homogeneous ruthenium and iridium catalysts. ACS Catal 4:4116–4128
Adduci LL et al (2014) Metal-free deoxygenation of carbohydrates. Angew Chem Int Ed 53(6):1646–1649
McLaughlin MP et al (2013) Iridium-catalyzed hydrosilylative reduction of glucose to hexane(s). J Am Chem Soc 135(4):1225–1227
Yang J, White PS, Brookhart M (2008) Scope and mechanism of the iridium-catalyzed cleavage of alkyl ethers with triethylsilane. J Am Chem Soc 130(51):17509–17518
Frihed TG, Bols M, Pedersen CM (2001) Diethylsilane. In: Encyclopedia of reagents for organic synthesis. Wiley
Rösch L, John P, Reitmeier R (2000) Silicon compounds, organic. In: Ullmann’s encyclopedia of industrial chemistry. Wiley-VCH Verlag GmbH & Co. KGaA
Bridgwater AV (2012) Review of fast pyrolysis of biomass and product upgrading. Biomass Bioenergy 38:68–94
Mortensen PM et al (2011) A review of catalytic upgrading of bio-oil to engine fuels. Appl Catal A 407(1–2):1–19
Bulushev DA, Ross JRH (2011) Catalysis for conversion of biomass to fuels via pyrolysis and gasification: a review. Catal Today 171(1):1–13
Hallman PS, Stephenson TA, Wilkinson G (2007) Tetrakis(triphenylphosphine)dichlororuthenium(II) and Tris(triphenylphosphine)dichlororuthenium(II). In: Inorganic syntheses. Wiley, pp 237–240
Hallman PS, McGarvey BR, Wilkinson G (1968) The preparation and reactions of hydridochlorotris(triphenylphosphine)ruthenium(II) including catalytitic hydrogenation of 1 alkenes. J Chem Soc A 3143–3150
Mahfud FH, Ghijsen F, Heeres HJ (2007) Hydrogenation of fast pyrolyis oil and model compounds in a two-phase aqueous organic system using homogeneous ruthenium catalysts. J Mol Catal A Chem 264(1–2):227–236
Busetto L et al (2011) Application of the Shvo catalyst in homogeneous hydrogenation of bio-oil obtained from pyrolysis of white poplar: new mild upgrading conditions. Fuel 90(3):1197–1207
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Schlaf, M. (2016). Homogeneous Catalysts for the Hydrodeoxygenation of Biomass-Derived Carbohydrate Feedstocks. In: Schlaf, M., Zhang, Z. (eds) Reaction Pathways and Mechanisms in Thermocatalytic Biomass Conversion II. Green Chemistry and Sustainable Technology. Springer, Singapore. https://doi.org/10.1007/978-981-287-769-7_2
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