Solid Liquid Extraction

Transcription

1 Solid Liquid Solid Liquid Thomas GAMSE Ao.Univ.Prof.Dipl.-Ing.Dr.techn. Institute of Chemical Engineering and Environmental Technology Graz University of Technology Inffeldgasse 25/C, A-8010 Graz, Austria CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

2 Solid Liquid Solid Liquid (Leaching) removal of extractable compounds from solid matrix by a liquid solvent CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

3 Solid Liquid Solid Liquid food industry: production of instant coffee decaffeination of coffee and tea production of flavour and fragrances sugar production edible oil production pharmaceutical and cosmetic industry active ingredients from natural materials environmental technology: decontamination of soils recycling of resources mining, metallurgy: metal production of ores high quality fats from animal cadaver utilisation CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

4 Solid Liquid Solid Liquid Basics underflow = wet solids A = inert material solution = B + C B = resource C = solvent overflow = extract solution = miscella CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

5 Solid Liquid Solid Liquid Basics requirements for solid-extraction 1.) preparation of extraction material: milling, grinding, rolling, pelletising 2.) choice of solvent 3.) high concentration in overflow counter-current extraction 4.) solvent separation from overflow and underflow CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

6 Solid Liquid Solid Liquid Basics requirements for high extraction velocity 1.) high temperature lower viscosity of solvent and extract higher solubility of extract in solvent 2.) short capillary paths 3.) high percolation velocity 4.) for multistep extractions dripping zones for separation underflow - overflow good efficiencies of single steps CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

7 Solid Liquid Solid Liquid Conventional Process Flue Gas Solvent Condensation Solvent thermal separation underflow (drying) mechanical separation of underflow (filter, centrifuge, ) Condensation and Purification of Solvent thermal separation overflow (evaporation, distillation, crystallisation, ) Solid Residue overflow Purification Extract CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

8 Solid Liquid 1.) high solubility and high selectivity 2.) low specific heat capacity, low evaporation enthalpy 3.) non inflammable, no explosive mixtures with air 4.) non toxic 5.) non corrosive Solid Liquid Basics solvent requirements 6.) good penetration in solid matrix, easy and complete removal from underflow for food industry: no influence on taste and smell 7.) chemical and thermal stability constant and not too high boiling temperature CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

9 Solid Liquid Solid Liquid Basics important solvents hydrocarbons (benzines, hexane, ) benzene sulphur hydrocarbons ethyl ether acetone chlorinated hydrocarbons alcohols (ethanol, isopropanol,.) water solvent mixtures CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

10 Solid Liquid Solid Liquid Discontinuous single step extraction process only one extraction step separation overflow - underflow CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

11 Solid Liquid Solid Liquid Discontinuous single step extraction process displacement process extraction separation overflow - underflow next extraction of underflow Step 1 Step 2 Step 3 disadvantage overflow concentration becomes lower step by step CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

12 Solid Liquid single step extraction process displacement process enrichment process Solid Liquid Discontinuous solvent in counter-current flow high enrichment of extractable compounds in overflow cascade operation Step 1 Step 2 Step m Step n CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

13 Solid Liquid Solid Liquid Cascade Operation separator CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

14 Solid Liquid Solid Liquid Cascade Operation CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

15 Solid Liquid Solid Liquid Discontinuous CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

16 Solid Liquid Solid Liquid Continuous percolation process solvent passes through stationary solid bed requirement: good percolation properties of solid material advantages: no mechanical treatment of solid material self filtration effect immersion process total mixing of solvent and solid material advantages: no requirements for percolation properties disadvantages: no self filtration effect CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

17 Solid Liquid Solid Liquid Continuous Continuous Horizontal Extractor CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

18 Solid Liquid Solid Liquid Continuous Hildebrandt Extractor, Screw Extractor CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

19 Solid Liquid Solid Liquid Continuous Bonotto - Extractor CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

20 Solid Liquid Solid Liquid Continuous Bollmann - Extractor CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

21 Solid Liquid Solid Liquid Continuous Kennedy - Extractor CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

22 Solid Liquid Solid Liquid Continuous Rotocell Extractor, Carousel - Extractor CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

23 Solid Liquid Solid Liquid Continuous Rotocell Extractor, Carousel - Extractor CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

24 Solid Liquid Solid Liquid Continuous Lurgi - Extractor CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

25 Solid Liquid Right Angle Triangular Diagram Solid Liquid Diagrams C 1 a... constant underflow b... variable underflow DE.. tie line Y = C / (A + B + C) F E D c Overflow (extract) 0 A a b X = B / (A + B + C) 1 B CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

26 Solid Liquid Ponchon - Savarit -Diagram Solid Liquid Diagrams a... constant underflow b... variable underflow F E a DE.. tie line L = solution = B + C N*L = amount of A L*X, L*Y = amount of B N = A / (B + C) c b D 0 X,Y = B / (B + C) 1 CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

27 Supercritical Fluid Thomas GAMSE Ao.Univ.Prof.Dipl.-Ing.Dr.techn. Institute of Chemical Engineering and Environmental Technology Graz University of Technology Inffeldgasse 25/C, A-8010 Graz, Austria CEEPUS Teaching Staff Mobility, , University of Zagreb CEEPUS Teaching Staff Mobility

28 Supercritical Fluid = oldest and industrial applied application of supercritical fluids many advantages especially for natural plant materials CEEPUS Teaching Staff Mobility

29 Critical Point, Supercritical Fluid P Supercritical Fluid P C solid liquid P TR vapour T TR T C T CEEPUS Teaching Staff Mobility

30 Critical Point, Supercritical Fluid CEEPUS Teaching Staff Mobility

31 Critical Parameters of Different Solvents T C P C Explosive Limit Gas [ C] [bar] [%vol] Ethene Xenon Fluoroform (R23) Chlorotrifluoromethane (R13) Carbon Dioxide Ethane Nitrous Oxide Propene Chlorodifluoromethane (R22) Propane Dichlorodifluoromethane (R12) Chloromethane Butene n-butane CEEPUS Teaching Staff Mobility

32 Physical Properties at different aggregation Gas Supercritical Liquid Fluid Density [kg/dm 3 ] Diffusion coefficient [cm 2 /s] Viscosity [g/cm s] CEEPUS Teaching Staff Mobility

33 Density Behaviour of CO bar 400 bar Dichte [kg/m 3 ] Zweiphasengebiet 0 C 962,63 bei 0 C 20 C 828,80 bei 20 C 31 C 699,90 40 C bei 31 C 60 C KP 281,33 bei 40 C 1082,10 bei 0 C 1020,70 bei 20 C 989,01 bei 31 C 956,73 bei 40 C 80 C ,55 bei 60 C 823,15 bei 80 C ,48 bei 60 C 160,04 bei 80 C Druck [bar] CEEPUS Teaching Staff Mobility

34 Viscosity Behaviour of CO 2 CEEPUS Teaching Staff Mobility

35 Typical Trend of Lines 100 extraction yield [%] T 3 p 3 T 2 p 2 T 1 p 1 T 1 < T 2 < T 3 p 1 < p 2 < p 3 solubility diffusion extraction time [h] CO 2 amount [kg] CEEPUS Teaching Staff Mobility

36 Yield E = k s * a s * V t * c m k s = mass transfer coefficient [m/s] a s = specific interfacial area [m 2 /m 3 ] V t = total bed volume [m 3 ] c m = mean concentration gradient CEEPUS Teaching Staff Mobility

37 Yield E = k s * a s * V t * c m k s = mass transfer coefficient [m/s] Correlation of Sherwood number Sh = k s * d / D 12 = 2 + 1,1 * Sc 1/3 * Re 0,6 for 3 < Re < Sc = / D 12 Re = (v * D) / CEEPUS Teaching Staff Mobility

38 Yield E = k s * a s * V t * c m k s can be influenced by diffusion coefficient D 12 shorter diffusion length d smaller particle size higher specific interfacial area a s CEEPUS Teaching Staff Mobility

39 Yield E = k s * a s * V t * c m k s can be influenced by diffusion coefficient D 12 shorter diffusion length d higher flow rates larger c m higher velocity v higher Re-number better mixing effect, up to fluidised bed CEEPUS Teaching Staff Mobility

40 SFE Conventional Process Conventional Process Flue Gas Solvent Condensation Solvent Condensation and Purification of Solvent Thermal Separation Solid - Solvent (Drying) Mechanical Separation of Solid - Solution (Filter, Centrifuge, ) Thermal Separation (Evaporation, Distillation, Crystallisation, ) Solid Residue Solution Purification Extract CEEPUS Teaching Staff Mobility

41 SFE Conventional Process SFE Process Recompression Solvent Flue Gas Condensation Solvent Recompression Expansion of Solid Residue Condensation and Purification of Solvent Solid Residue Expansion of Solution Extract Purification CEEPUS Teaching Staff Mobility

42 Pump Process = 6, 7 Temperatur [ C] EXTRACT Entropie [kj/kg*k] P = const. 8 H = const. 8 CEEPUS Teaching Staff Mobility

43 Compressor Process Temperature [ C] = 5,6 1 H = const Entropy S [kj/kg*k] EXTRACT 1 P = const. CEEPUS Teaching Staff Mobility

44 INDIA Spices and Herbs Multipurpose plant 2 x 600 litres, 550 bar separators extractors (600 L, 550 bar) CEEPUS Teaching Staff Mobility

45 CO 2 condenser CO 2 storage tank CEEPUS Teaching Staff Mobility

46 GERMANY Decaffeination of Tea 1988 turn-key, 3,000 t/a CEEPUS Teaching Staff Mobility

47 CEEPUS Teaching Staff Mobility

48 ITALY Decaffeination of Coffee 1992 Turn-key, 10,000 t/a Extractors: 3 x 21,5 m bar Washing Column: p = 285 bar D i = 1,4 m H = 22 m Weight = 122 tons CEEPUS Teaching Staff Mobility

49 TAIWAN Rice Treatment Plant 3 x 5,2 m 3, 325 bar, Capacity 90 t per day CEEPUS Teaching Staff Mobility

50 South Korea 2003 Sesame Oil 3 x litres 550 bar CEEPUS Teaching Staff Mobility

51 San Vicente / Spain Cork x Litres 150 bar kg/h CO 2 CEEPUS Teaching Staff Mobility

52 San Vicente / Spain Cork x Litres 150 bar kg/h CO x Litres 150 bar CEEPUS Teaching Staff Mobility

53 Ceret / France Cork x Litres 150 bar CEEPUS Teaching Staff Mobility

54 San Vicente / Spain Cork CEEPUS Teaching Staff Mobility

55 decaffeination of coffee and tea hop extraction pesticides from rice t/a t/a t/a CEEPUS Teaching Staff Mobility

56 Removal of solvents mainly for pharmaceutical products including thermal sensitive substances Attention solvents may act as modifier possible extraction of active compounds CEEPUS Teaching Staff Mobility

57 Dry Cleaning Systems washing systems for electronic industry (wavers,...) mechanical parts clothes operation in most cases with liquid CO 2 CEEPUS Teaching Staff Mobility

58 Dry Cleaning Systems Carbonet R (LCO 2 )-SEPAREX(FR) CEEPUS Teaching Staff Mobility

59 Dry Cleaning Systems SCCO 2 degreasing unit - Chematur Eng. (SW) CEEPUS Teaching Staff Mobility

60 Dry Cleaning Systems LCO 2 Dry Cleaning Alliance Laundry System(US) CEEPUS Teaching Staff Mobility

61 , Usage of good transport properties of supercritical fluids < viscosity, < surface tension > diffusion coefficients Advantage: homogeneous distribution in solid matrices no residual solvent after treatment faster process CEEPUS Teaching Staff Mobility

62 , long term pharmaceuticals of biodegradable polymer with drug polymer drug SC-CO 2 CEEPUS Teaching Staff Mobility

63 , dose rate long term pharmaceuticals of biodegradable polymer with drug uniform concentration of drug over cross section constant drug concentration over time toxical dose dose without effect time CEEPUS Teaching Staff Mobility

64 , long term pharmaceuticals treatment of old books 1 st Step: CO 2 of degradation substances 2 nd Step: of paper CEEPUS Teaching Staff Mobility

65 , long term pharmaceuticals treatment of old books wood impregnation Denmark, Start Up 2002 Volume: 3 x l, Pressure: 170 bar Capacity: m 3 / a CEEPUS Teaching Staff Mobility

66 , long term pharmaceuticals treatment of old books wood impregnation dyeing Disadvantages of Conventional Process with Water agents for treatment of hydrophobic materials drying process energy intensive large amount of waste water ( liters/kg textile) Advantages of CO 2 - good penetration of dyestuff into the material excess dyestuff can be reused CEEPUS Teaching Staff Mobility

67 , long term pharmaceuticals treatment of old books wood impregnation dyeing CEEPUS Teaching Staff Mobility

68 , long term pharmaceuticals treatment of old books wood impregnation dyeing Taipei, Taiwan, Startup 2014 CEEPUS Teaching Staff Mobility

69 , long term pharmaceuticals treatment of old books wood impregnation dyeing impregnation of hip and knee endoprosthesis UHMW-PE CEEPUS Teaching Staff Mobility

70 of Hip and Knee Endoprosthesis of finished hip cups 170 C, 300 bar, 12 h impregnation time CEEPUS Teaching Staff Mobility

71 of Hip and Knee Endoprosthesis of finished hip cups 170 C, 300 bar, 12 h impregnation time CEEPUS Teaching Staff Mobility

72 Conclusion Supercritical Fluid industrial applied application marketing essential for new products and extraction plants competition with existing processes and plants high pressure not common in most companies convincing management training of personal CEEPUS Teaching Staff Mobility

73 ESS-HPT 2016 The European Summer School in High Pressure Technology 14 Days Intensive Course 3 rd 10 th July 2016 University Maribor/SI 11 th July 2016 Visit of NATEX Company, Transfer to Graz 12 th 17 th July 2016 Graz University of Technology/A All participants have to present their research topic (10 min + 5 min discussion) and have to send in advance an abstract (max. 4 pages) for the book of abstracts. Costs (including accommodation and full board): Universities: Companies: 1 week: weeks: Deadline Registration: 29 th April 2016 Further Information: [email protected] CEEPUS Teaching Staff Mobility

74 NATEX Prozesstechnologie GesmbH Werkstrasse 7, A 2630 Ternitz, AUSTRIA Tel: Fax: [email protected] Web: CEEPUS Teaching Staff Mobility

75 Thomas Gamse Ao.Univ.Prof.Dipl.-Ing.Dr.techn. Department of Chemical Engineering and Environmental Technology Graz University of Technology Inffeldgasse 25/C, A-8010 Graz Tel: CEEPUS Teaching Staff Mobility