Reactive Separation of Formic Acid, Acetic Acid and Water from Biorefinery Feed

Transcription

1 Reactive Separation of Formic Acid, Acetic Acid and Water from Biorefinery Feed D. Painer, S. Lux, M. Siebenhofer 1

2 Outline Introduction Vapor-liquid-equilibrium Chemical reaction Separation concepts I. Selective separation of formic acid II. Total conversion and separation Conclusion 2

3 Biorefinery Characteristics Biomass feedstock Multicomponent azeotropic mixtures Extensive separation processes 3

4 Pulping Condensate Management Extraction Distillation Aqueous Feed Acetic Acid < 60 g/l Formic Acid < 30 g/l Laden Solvent Crude Distillate Acetic Acid < 600 g/l Formic Acid < 300 g/l Raffinate Acetic Acid < 1 g/l Formic Acid < 1 g/l Solvent (e.g. Cyanex 923) regenerated 4

5 Vapor-Liquid-Equilibrium Formic Acid - Water Acetic Acid - Water Water Acetic Acid Formic Acid Acetic Acid Formic Acid Gmehling, J.; Onken, U.; Arlt, W.; Grenzheuser, P.; Weidlich, U.; Kolbe, B.; Rarey, J.: Vapor-Liquid Equilibrium Data Collection. Dechema,

6 Boiling Point Surface Binary azeotrope C Ternary azeotrope C 6

7 Building Blocks of Process Intensification Distillation Chemical reaction Membrane process 7

8 Chemical Reaction Esterification of Formic Acid: Esterification of Acetic Acid: HCOOH + CH 3 OH H + HCOOCH 3 + H 2 O CH 3 COOH + CH 3 OH H+ CH 3 COOCH 3 + H 2 O T = 40 C Methanol : Formic Acid = 1 T = 40 C Methanol : Acetic Acid =

9 Concept I Selective Separation 9

10 Concept I and Validation Reactive Distillation Methyl Formate Methyl Acetate Methanol Methanol Pervaporation Methyl Formate Methyl Acetate Methyl Formate Distillation Methanol Formic Acid Acetic Acid Water Acetic Acid Water Methyl Acetate 10

11 Batch Reactive Distillation Methanol : Formic Acid = 2 : 1 11

12 Continuous Reactive Distillation Methanol : Formic Acid = 2 :1 Bottom Distillate H 2 O AA MF MA MA MF FA MeOH MeOH Bottoms product mol% mol% Distillate mol% Water (H2O) 37.5 Methanol (MeOH) 2.9 Methyl Formate (MF) 0.6 Formic Acid (FA) 1.8 Methyl Acetate (MA) 7.4 Acetic Acid (AA) 49.8 Methanol (MeOH) 6.2 Methyl Formate (MF) 50.3 Methyl Acetate (MA)

13 Pervaporation Retentate Susanne Lux et al. Pervaporation, An Efficient Tool for Separation of Azeotropic Mixtures in Ester Synthesis (565d) Feed Process Intensification By Enhanced Mass and Heat Transfer Wednesday, Membrane Area: November 27.5 cm6: 2 4:18 PM Union Square 19 Membrane: hydrophilic surface properties separation layer: PVA support layer: PAN PERVAP TM MeOH MA MF 13

14 Product Separation Methyl Formate Methyl Acetate Methanol Methyl Acetate Methyl Formate Reactive Distillation Methanol Pervaporation Methyl Formate Methyl Acetate Methyl Formate Distillation Methanol Formic Acid Acetic Acid Water Acetic Acid Water Methyl Acetate Gmehling, J.; Onken, U.; Arlt, W.; Grenzheuser, P.; Weidlich, U.; Kolbe, B.; Rarey, J.: Vapor-Liquid Equilibrium Data Collection. Dechema,

15 Concept II Complete Conversion + Separation 15

16 Concept II Distillation Methyl Formate Methyl Formate Methyl Acetate Formic Acid Acetic Acid Water Methanol Reaction Amberlyst 15 Methyl Formate Methyl Acetate Methanol Water Pervaporation Methyl Acetate Methanol Water 16

17 Esterification Methanol : Acids = 4 : 1 10 w% Amberlyst 15 T = 50 C 17

18 Conclusion Problem Binary high boiling azeotrope Ternary saddle point azeotrope Process Intensification Solver Strategy: Change the state Solution concept I: Selective removal of formic acid Solution concept II: Total conversion and separation 18

19 Reactive Separation of Formic Acid, Acetic Acid and Water from Biorefinery Feed D. Painer, S. Lux, M. Siebenhofer Graz University of Technology Institute of Chemical Engineering and Environmental Technology Inffeldgasse 25c/I, A-8010 Graz 19