Catalytic routes towards acrylic acid, adipic acid and ε-caprolactam starting from biorenewables

The majority of bulk chemicals are derived from crude oil, but the move to biorenewable resources is gaining both societal and commercial interest. Reviewing this transition, we first summarise the types of today's biomass sources and their economical relevance. Then, we assess the biobased productions of three important bulk chemicals: acrylic acid, adipic acid and e-caprolactam. These are the key monomers for high-end polymers (polyacrylates, nylon 6.6 and nylon 6, respectively) and are all produced globally in excess of two million metric tons per year. The biobased routes for each target molecule are analysed separately, comparing the conventional processes with their sustainable alternatives. Some processes have already received extensive scientific attention. Other, more novel routes are also being considered. We find several common trends: For all three compounds, there are no commercial methods for direct conversion of biobased feedstocks. However, combinations of biotechnologically produced platform chemicals with subsequent chemical modifications are emerging and showing promising results. We then discuss several distinct strategies for implementing biorenewable processes. For each biotechnological and chemocatalytic route, current efficiencies and limitations are presented, but we urge that these routes should be assessed mainly on their potential and prospects for future application. Today, biorenewable routes cannot yet compete with their petrochemical equivalents. However, given that most of them are still in the early stages of development, we foresee their commercial implementation in the next two decades.

[1]  G. Rothenberg,et al.  Lignin solubilisation and gentle fractionation in liquid ammonia , 2015 .

[2]  Carlos A. Henao,et al.  A sulfuric acid management strategy for the production of liquid hydrocarbon fuels via catalytic conversion of biomass-derived levulinic acid , 2012 .

[3]  Diego Luna,et al.  Biofuels: a technological perspective , 2008 .

[4]  B. Kuster,et al.  Deactivation of platinum catalysts by oxygen. 2. Nature of the catalyst deactivation , 1988 .

[5]  Andreas Martin,et al.  Recent developments in dehydration of glycerol toward acrolein over heteropolyacids , 2012 .

[6]  Hirokazu Kobayashi,et al.  Catalytic transformation of cellulose into platform chemicals , 2014 .

[7]  Bryan G. Reuben,et al.  Industrial Organic Chemicals , 1996 .

[8]  Carol Sze Ki Lin,et al.  Valorisation of bakery waste for succinic acid production. , 2013 .

[9]  Regina Palkovits,et al.  Development of heterogeneous catalysts for the conversion of levulinic acid to γ-valerolactone. , 2012, ChemSusChem.

[10]  J. Tichý Oxidation of acrolein to acrylic acid over vanadium-molybdenum oxide catalysts , 1997 .

[11]  N. R. Shiju,et al.  Hemicellulose hydrolysis catalysed by solid acids , 2013 .

[12]  Kunio Arai,et al.  Dehydration of lactic acid to acrylic acid in high temperature water at high pressures , 2009 .

[13]  J. Dumesic,et al.  Liquid-phase catalytic transfer hydrogenation and cyclization of levulinic acid and its esters to γ-valerolactone over metal oxide catalysts. , 2011, Chemical communications.

[14]  Xiaojian Ma,et al.  Kinetics of Levulinic Acid Formation from Glucose Decomposition at High Temperature , 2006 .

[15]  Yuguo Zheng,et al.  Production of acrylic acid from Acrylonitrile by immobilization of Arthrobacter nitroguajacolicus ZJUTB06-99. , 2009, Journal of microbiology and biotechnology.

[16]  I. Melián-Cabrera,et al.  From 5-Hydroxymethylfurfural (HMF) to Polymer Precursors: Catalyst Screening Studies on the Conversion of 1,2,6-hexanetriol to 1,6-hexanediol , 2012, Topics in Catalysis.

[17]  M. Iwamoto,et al.  Direct and selective production of propene from bio-ethanol on Sc-loaded IN2O3 catalysts. , 2013, Chemistry.

[18]  J. Bart,et al.  Nitric acid reaction of cyclohexanol to adipic acid , 1991 .

[19]  Yuriy Román,et al.  Emerging catalytic processes for the production of adipic acid , 2013 .

[20]  Stefan Albrecht,et al.  R&D decision support by parallel assessment of economic, ecological and social impact -- Adipic acid from renewable resources versus adipic acid from crude oil , 2009 .

[21]  Johnathan E. Holladay,et al.  Top Value Added Chemicals From Biomass. Volume 1 - Results of Screening for Potential Candidates From Sugars and Synthesis Gas , 2004 .

[22]  M. Antal,et al.  Acid-catalysed dehydration of alcohols in supercritical water , 1987 .

[23]  J. Clark,et al.  Comparative study of phenol alkylation mechanisms using homogeneous and silica-supported boron trifluoride catalysts , 2000 .

[24]  I. Hermans,et al.  Continuous D-fructose dehydration to 5- hydroxymethylfurfural under mild conditions. , 2012, ChemSusChem.

[25]  O. Lev,et al.  Pyrolysed carbon supported cobalt porphyrin: a potent catalyst for oxidation of hydrogen sulfide , 2004 .

[26]  M. Dongare,et al.  Catalytic dehydration of lactic acid to acrylic acid using calcium hydroxyapatite catalysts , 2013 .

[27]  Zea Strassberger,et al.  The pros and cons of lignin valorisation in an integrated biorefinery , 2014 .

[28]  A. Zeng,et al.  Microbial Production of 3-Hydroxypropionaldehyde from Glycerol Bioconversion , 2007 .

[29]  Dirk Weuster-Botz,et al.  Succinic acid from renewable resources as a C4 building-block chemical—a review of the catalytic possibilities in aqueous media , 2009 .

[30]  Attilio Converti,et al.  Lactic acid properties, applications and production: A review , 2013 .

[31]  M. Bañares,et al.  New reaction: conversion of glycerol into acrylonitrile. , 2008, ChemSusChem.

[32]  N. R. Shiju,et al.  Toward environmentally benign oxidations: bulk mixed Mo-V-(Te-Nb)-O M1 phase catalysts for the selective ammoxidation of propane. , 2008, ChemSusChem.

[33]  J. Sanders,et al.  Biobased synthesis of acrylonitrile from glutamic acid , 2011 .

[34]  Tapio Salmi,et al.  Production of lactic acid/lactates from biomass and their catalytic transformations to commodities. , 2014, Chemical reviews.

[35]  G. Rothenberg,et al.  Understanding Catalytic Biomass Conversion Through Data Mining , 2010 .

[36]  雅夫 北原,et al.  アクロレインの気相酸化によるアクリル酸の合成I.MoO3:V2O5:Al2O3触媒による酸化 , 1967 .

[37]  J. W. Frost,et al.  Benzene‐Free Synthesis of Adipic Acid , 2002, Biotechnology progress.

[38]  T. Sooknoi,et al.  Direct conversion of glycerol to acrylic acid via integrated dehydration–oxidation bed system , 2012 .

[39]  D. M. Alonso,et al.  Catalytic conversion of biomass to biofuels , 2010 .

[40]  Michael Jerry Antal,et al.  Formation of acrylic acid from lactic acid in supercritical water , 1989 .

[41]  Bharat P. Singh Industrial crops and uses , 2010 .

[42]  Ferdi Schüth,et al.  Acid hydrolysis of cellulose as the entry point into biorefinery schemes. , 2009, ChemSusChem.

[43]  P. Gallezot Alternative Value Chains for Biomass Conversion to Chemicals , 2010 .

[44]  M. D. Soriano,et al.  Glycerol oxidehydration into acrolein and acrylic acid over W-V-Nb-O bronzes with hexagonal structure , 2012 .

[45]  E. Makshina,et al.  Lactic acid as a platform chemical in the biobased economy: the role of chemocatalysis , 2013 .

[46]  James A. Dumesic,et al.  Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides , 2007 .

[47]  Atsushi Takagaki,et al.  Catalytic Transformations of Biomass-Derived Materials into Value-Added Chemicals , 2012, Catalysis Surveys from Asia.

[48]  J. Pronk,et al.  Microbial export of lactic and 3-hydroxypropanoic acid: implications for industrial fermentation processes. , 2004, Metabolic engineering.

[49]  Ulf Schuchardt,et al.  Cooperative effect of cobalt acetylacetonate and silica in the catalytic cyclization and oxidation of fructose to 2,5-furandicarboxylic acid , 2003 .

[50]  N. R. Shiju,et al.  Mesoporous Silica with Site-Isolated Amine and Phosphotungstic Acid Groups: A Solid Catalyst with Tunable Antagonistic Functions for One-Pot Tandem Reactions** , 2011, Angewandte Chemie.

[51]  I. Melián-Cabrera,et al.  Caprolactam from renewable resources: catalytic conversion of 5-hydroxymethylfurfural into caprolactone. , 2011, Angewandte Chemie.

[52]  N. R. Shiju,et al.  Cs exchanged phosphotungstic acid as an efficient catalyst for liquid-phase Beckmann rearrangement of oximes , 2009 .

[53]  A. C. Dimian,et al.  Chapter 14. Biodiesel Manufacturing , 2008 .

[54]  N. R. Shiju,et al.  Glycerol Valorization: Dehydration to Acrolein Over Silica-Supported Niobia Catalysts , 2010 .

[55]  B. Ondruschka,et al.  Oxidation of styrene and cyclohexene under microwave conditions , 2003 .

[56]  W. Bras,et al.  Epoxidation of Cyclohexene over Crystalline and Amorphous Titanosilicate Catalysts , 2005 .

[57]  P. Gallezot,et al.  Conversion of biomass to selected chemical products. , 2012, Chemical Society reviews.

[58]  W. Leuchtenberger,et al.  Biotechnological production of amino acids and derivatives: current status and prospects , 2005, Applied Microbiology and Biotechnology.

[59]  Francesco Cherubini,et al.  Energy- and greenhouse gas-based LCA of biofuel and bioenergy systems: Key issues, ranges and recommendations , 2009 .

[60]  Hao Pang,et al.  Production of Levulinic Acid from Bagasse and Paddy Straw by Liquefaction in the Presence of Hydrochloride Acid , 2008 .

[61]  Y. Wee,et al.  Biotechnological Production of Lactic Acid and Its Recent Applications , 2006 .

[62]  B. G. Hermann,et al.  Today’s and tomorrow’s bio-based bulk chemicals from white biotechnology , 2007, Applied biochemistry and biotechnology.

[63]  K. Vorlop,et al.  Industrial bioconversion of renewable resources as an alternative to conventional chemistry , 2004, Applied Microbiology and Biotechnology.

[64]  Anders Hammer Strømman,et al.  Life cycle assessment of bioenergy systems: state of the art and future challenges. , 2011, Bioresource technology.

[65]  Addison Ault,et al.  The Monosodium Glutamate Story: The Commercial Production of MSG and Other Amino Acids , 2004 .

[66]  Mark E. Davis,et al.  Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural , 2014, Proceedings of the National Academy of Sciences.

[67]  Brigitte Bathe,et al.  Biotechnological manufacture of lysine. , 2003, Advances in biochemical engineering/biotechnology.

[68]  Noyori,et al.  A "Green" route to adipic acid: direct oxidation of cyclohexenes with 30 percent hydrogen peroxide , 1998, Science.

[69]  H. Wittcoff,et al.  Industrial Organic Chemicals: Wittcoff/Industrial Organic Chemicals , 2012 .

[70]  James A. Dumesic,et al.  Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass , 2013 .

[71]  J. Zeikus,et al.  Biotechnology of succinic acid production and markets for derived industrial products , 1999, Applied Microbiology and Biotechnology.

[72]  R. Bothast,et al.  Optimizing aerobic conversion of glycerol to 3-hydroxypropionaldehyde , 1985, Applied and Environmental Microbiology.

[73]  S. Paul,et al.  Glycerol dehydration to acrolein in the context of new uses of glycerol , 2010 .

[74]  J. White,et al.  Manufacturing, composition, and applications of fructose. , 1993, The American journal of clinical nutrition.

[75]  R. V. Gholap,et al.  Carbonylation of 1,4-butanediol diacetate using rhodium complex catalyst: a kinetic study , 1987 .

[76]  M. Xian,et al.  Biosynthetic pathways for 3-hydroxypropionic acid production , 2009, Applied Microbiology and Biotechnology.

[77]  Atsushi Takagaki,et al.  Hydrotalcite-supported gold-nanoparticle-catalyzed highly efficient base-free aqueous oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid under atmospheric oxygen pressure , 2011 .

[78]  N. R. Shiju,et al.  M1 to M2 Phase Transformation and Phase Cooperation in Bulk Mixed Metal Mo–V–M–O (M=Te, Nb) Catalysts for Selective Ammoxidation of Propane , 2008 .

[79]  N. R. Shiju,et al.  Tungstated Zirconia Catalysts for Liquid-Phase Beckmann Rearrangement of Cyclohexanone Oxime: Structure-Activity Relationship , 2009 .

[80]  R. Sheldon Green and sustainable manufacture of chemicals from biomass: state of the art , 2014 .

[81]  I. Nikov,et al.  Palladium on alumina catalyst for glucose oxidation: reaction kinetics and catalyst deactivation , 1995 .

[82]  Darryn W. Rackemann,et al.  The conversion of lignocellulosics to levulinic acid , 2011 .

[83]  Tao Jiang,et al.  Selective Phenol Hydrogenation to Cyclohexanone Over a Dual Supported Pd–Lewis Acid Catalyst , 2009, Science.

[84]  Avelino Corma,et al.  Synergies between bio- and oil refineries for the production of fuels from biomass. , 2007, Angewandte Chemie.

[85]  Satoshi Sato,et al.  Production of acrolein from glycerol over silica-supported heteropoly acids , 2007 .

[86]  N. R. Shiju,et al.  Optimising catalytic properties of supported sulfonic acid catalysts , 2009 .

[87]  N. R. Shiju,et al.  The role of surface basal planes of layered mixed metal oxides in selective transformation of lower alkanes: propane ammoxidation over surface ab planes of Mo-V-Te-Nb-O M1 phase. , 2008, Journal of the American Chemical Society.

[88]  J. Vencl,et al.  Auswahl des Katalysators und Reaktionsbedingungen , 1974 .

[89]  J. Filho,et al.  Catalytic conversion of glycerol to acrolein over modified molecular sieves: Activity and deactivation studies , 2011 .

[90]  Carl T. Lira,et al.  Conversion of lactic acid to acrylic acid in near-critical water , 1993 .

[91]  Thokhir Basha Shaik,et al.  Bioconversion of acrylonitrile to acrylic acid by rhodococcus ruber strain AKSH-84. , 2011, Journal of Microbiology and Biotechnology.

[92]  M. Bañares,et al.  Efficient microwave-promoted acrylonitrile sustainable synthesis from glycerol , 2009 .

[93]  Peter J. Miedziak,et al.  Rubidium- and caesium-doped silicotungstic acid catalysts supported on alumina for the catalytic dehydration of glycerol to acrolein , 2012 .

[94]  S. Vollenweider,et al.  3-Hydroxypropionaldehyde: applications and perspectives of biotechnological production , 2004, Applied Microbiology and Biotechnology.

[95]  S. Paul,et al.  Recent Developments in the Field of Catalytic Dehydration of Glycerol to Acrolein , 2013 .

[96]  Michael Köpke,et al.  2,3-Butanediol Production by Acetogenic Bacteria, an Alternative Route to Chemical Synthesis, Using Industrial Waste Gas , 2011, Applied and Environmental Microbiology.

[97]  Xiaohong Wang,et al.  One pot production of 5-hydroxymethylfurfural with high yield from cellulose by a Brønsted-Lewis-surfactant-combined heteropolyacid catalyst. , 2011, Chemical communications.

[98]  Z. Zhang,et al.  Rare Earth Pyrophosphates: Effective Catalysts for the Production of Acrolein from Vapor-phase Dehydration of Glycerol , 2009 .

[99]  N. R. Shiju,et al.  Enhanced heterogeneous catalytic conversion of furfuryl alcohol into butyl levulinate. , 2014, ChemSusChem.

[100]  M. Dongare,et al.  Nonstoichiometric calcium pyrophosphate: a highly efficient and selective catalyst for dehydration of lactic acid to acrylic acid , 2014 .