Neue Produkte auf der Basis von Glycerin Prof. Dr. Arno Behr Universität Dortmund Nachwachsende Rohstoffe für die Chemie Oldenburg, 28. – 29.3.2007

Triglyceride + 3 Methanol → 3 Methylester + Glycerol “Biodiesel“ by-product in oleochemistry Triglyceride + 3 Methanol → 3 Methylester + Glycerol “Biodiesel“ 1 t biodiesel ~ 110 kg crude glycerol Production of biodiesel in Europe: estimated for 2010: 7 – 8 Mill. t/a Prize of glycerol: decreasing from 1.300 → 500 €/t

Chemical functionalization Present applications of glycerol Glycerol Direct applications Chemical functionalization pharmaceuticals cosmetics soaps sweetener moistening of tobacco triesters glycerol trinitrate polyether glycols alkyd resins

Contents Glycerol Alkyl ethers Alkenyl ethers (telomers) Oligomers Polymers Oxidation products Carbonylation products Other derivatives

Glycerol-tertiary-butyl-ethers (GTBE) R1, R2, R3 = H, But + n [H+]  Acid catalyst Glycerol Isobutene GTBE Monoethers (m-GTBE) n = 1 1-GTBE 2-GTBE Higher ethers (h-GTBE)  diesel-additive n = 2, 3 1,3-GTBE 1,2-GTBE 1,2,3-GTBE

Measurement of kinetics catalyst: p-toluene- sulfonic acid T = 90°C Isobutene : glycerol = 2:1 phase behavior

Reactor Extraction Flash Rectification Process diagram Reactor 70-110 °C 20-30 bar Extraction 30-40 °C 20-30 bar Flash 30-40 °C 1 bar Rectification 75 °C 5 mbar Isobutene recirculation h-GTBE Glycerol Isobutene R1 R2 R1 = recirculation of glycerol, pTS, m-GTBE R2 = recirculation of m-GTBE pTS = p-toluenesulphonic acid

Contents Glycerol Alkyl ethers Alkenyl ethers (telomers) Oligomers Polymers Oxidation products Carbonylation products Other derivatives

Potential applications: detergent precursors Glycerol alkenyl ethers (Telomers) Potential applications: detergent precursors

Triphenylphosphinsulfonate (TPPTS) Plant concept for the production of glycerol telomers catalyst: Pd/ TPPTS Triphenylphosphinsulfonate (TPPTS)

Contents Glycerol Alkyl ethers Alkenyl ethers (telomers) Oligomers Polymers Oxidation products Carbonylation products Other derivatives

Glycerol oligomers The reaction can be carried out both acid and base catalyzed The acid catalyzed reaction leads to unwanted by-products Applications: foods, cosmetics, pharmacy, educt for glycerol esters

Plant concept for the production of glycerol oligomers Reactive distillation: Simultaneous reaction and separation within one apparatus On account of continuous withdrawing of the by-product water the glycerol conversion is increased A higher selectivity can be achieved because of a defined contact time of the glycerol with the heterogeneous catalyst But: Difficult to engineer on account of complex relationships between process parameters catalyst: molecular sieves

Contents Glycerol Alkyl ethers Alkenyl ethers (telomers) Oligomers Polymers Oxidation products Carbonylation products Other derivatives

Hyperbranched polyglycerols Glycerol polymers Hyperbranched polyglycerols

Contents Glycerol Alkyl ethers Alkenyl ethers (telomers) Oligomers Polymers Oxidation products Carbonylation products Other derivatives

Glycerinoxidation Pt-Bi/C Pd/C Pt/C Au/C Sauerstoff Kohlenstoff Dihydroxyaceton Hydroxybrenztraubensäure Glyceraldehyd Glycerinsäure Mesoxalsäure Pd/C Pt/C Au/C Tartronsäure Sauerstoff Kohlenstoff Wasserstoff

Fermentation of glycerol to 3-hydroxypropanal Acrolein Biological pathway: Fermentation of glycerol to 3-hydroxypropanal Thermal reaction to acrolein Chemical pathway: heterogeneous (Y > 70 %) Solid acids (e.g. zeolites, H3PO4, Nafion) homogeneous (Y = -100 %) in scH2O Potential applications: Production of acrylic acid, methionine and glutaraldehyde

Contents Glycerol Alkyl ethers Alkenyl ethers (telomers) Oligomers Polymers Oxidation products Carbonylation products Other derivatives

Glycerincarbonylierung [M]: Übergangsmetall- komplexe (Ir, Rh, …) Anwendungen: Polyester Harze ● ●

Contents Glycerol Alkyl ethers Alkenyl ethers (telomers) Oligomers Polymers Oxidation products Carbonylation products Other derivatives

Monoglycerides Transesterification Application: non-ionic surfactants Esterification catalysts: Faujasite, MCM-41, SBA-15 catalysts: ZnO, MgO

Reaction with different aldehydes or ketones: Acetals and Ketals Reaction with different aldehydes or ketones: formaldehyde acetone butyraldehyde catalyst: cation exchanger (Amberlyst 15) Change in solubility Potential applications: Ignition support for all types of combustion engines and antiknock additive

1,3-Propanediol Biological pathway: enzymatic (Y > 85 %) with microorganisms (Y = 87%) Chemical pathway: heterogeneous (Y < 60 %) Supported metals (Re, Ru, Cu, …) or solid acids highly active but low selectivity homogeneous (Y < 70 %) Noble metals (e.g. Ru, Rh, Pt) Ligands containing P, As, Sb or CO Acids high selective but low activity Potential applications: Polymers, Solvents (esters)

Dihydroxy- butanoic acid Summary Glyceric acid GTBE Telomers Glycerol Oligomers Dihydroxy- butanoic acid Polymers