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Prof. Dr. Arno Behr Universität Dortmund

Neue Produkte auf der Basis von Glycerin. Prof. Dr. Arno Behr Universität Dortmund. Nachwachsende Rohstoffe für die Chemie Oldenburg, 28. – 29.3.2007 . Glycerol by-product in oleochemistry. Triglyceride + 3 Methanol → 3 Methylester + Glycerol “ Biodiesel“ . 1 t biodiesel

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Prof. Dr. Arno Behr Universität Dortmund

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  1. Neue Produkte auf der Basis von Glycerin Prof. Dr. Arno BehrUniversität Dortmund Nachwachsende Rohstoffe für die ChemieOldenburg, 28. – 29.3.2007

  2. Glycerol 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

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

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

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

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

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

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

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

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

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

  12. 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

  13. 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

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

  15. Glycerol polymers Hyperbranched polyglycerols

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

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

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

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

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

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

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

  23. 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

  24. 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)

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

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