SRP Pilot Plant Update James R. Fair Process Science & Technology Center

Transcription

1 SRP Pilot Plant Update James R. Fair Process Science & Technology Center Frank Seibert Austin, TX October 18, 2016

2 Topics Funding Pilot Plant Upgrades 2016 Projects

3 3

4 SRP Pilot Plant Staff & Students Eric Chen C2P3 Research Engineer Henry Bautista Technician/Mechanical Robert Montgomery Technician/Electrical Jarett Spinhirne Chemist/Part Time August Brauer Mechanical/Part Time Di Song Aurore Mercelat Bailee Roach Melissa Donahue Jeff Weinfeld Nash Mock Graduate Students

5 2016 Pilot Plant Funding PSTC Funding ($100K) - Phillips 66 ($25K) - Raschig ($25K) - Tier I Projects ($50K) Industrial Contract Funding ($550K) Rochelle-Related CO2 Capture ($125K) Total ($775K) Additional= $140K Emerson Process Management (Donated Equipment)

6 Pilot Plant Upgrades Refined Feed System for New Dividing Wall Distillation System Four New MicroMotion TM Mass Flowmeters for DWC Distillation System Modify Air/Water Structure for Easier Packing Installation Rosemount Analytical Online Gas Chromatograph for Distillation System Additional Online IR CO 2 Analyzer for Air/Water System DeltaV Data Acquisition for Oldershaw and Oil Recovery Systems Increasing Effective Height of Absorber (35 ft 50 ft)* Replacing Process Computers, Hardware and Instrumentation* *Within 2-3 months

7 2016 Pilot Activities 1. Liquid-Liquid Extraction 2. DWC Distillation 3. Lab Scale Distillation Study: Pro-Pak & RSR#0.1 (SRP)* 4. Viscosity Effect on Liquid Film Mass Transfer in Packings 5. Oil Recovery from Oil in Water Emulsions and Slurries 6. CO2 Capture 7. Distillation and Air/Water Packing Characterization* * PSTC Funds 7

8 Distillation Packing Studies (Added to Distillation Database) Raschig RSR#0.6 Raschig RSP250X Raschig RSP 350Y with 2 IDS Elements Raschig RSP 250Y with 2 IDS Elements AMACS ACS S-100 Knitted Mesh Structured Packing (a p =1,920 m 2 /m 3 )* * To be completed in October

9 HETP, cm DP/Z, mbar/m Raschig RSR# Raschig RSR#0.6 Total Reflux Cyclohexane/n-Heptane 0.33 bar Raschig RSR#0.6 Total Reflux Cyclohexane/n-Heptane 1.65 bar 0.33 bar bar bar bar bar bar f-factor, m/s (kg/m 3 ) f-factor, m/s (kg/m 3 ) 0.5 9

10 HETP, cm DP/Z, mbar/m Raschig RSP250X Raschig RSP250X Total Reflux Cyclohexane/n-Heptane 1.65 bar 0.33 bar bar Raschig RSP250X Total Reflux Cyclohexane/n-Heptane 1.65 bar 0.33 bar bar bar bar f-factor, m/s (kg/m 3 ) f-factor, m/s (kg/m 3 )

11 HETP, cm DP/Z, mbar/m Raschig 350Y with Two IDS Elements Raschig RSP350Y Total Reflux Cyclohexane/n-Heptane 1.65 bar 0.33 bar bar Raschig RSP350Y Total Reflux Cyclohexane/n-Heptane 1.65 bar 0.33 bar bar bar bar f-factor, m/s (kg/m 3 ) f-factor, m/s (kg/m 3 )

12 HETP, cm DP/Z, mbar/m Raschig 250Y with Two IDS Elements Raschig RSP250Y with IDS Total Reflux Cyclohexane/n-Heptane bar Raschig RSP250Y with IDS Total Reflux Cyclohexane/n-Heptane 1.65 bar 0.33 bar bar bar bar bar bar f-factor, m/s (kg/m 3 ) f-factor, m/s (kg/m 3 )

13 Packing Characterization Studies (Added to A/W Database) Raschig RSR#1.5 GTC GT-OPTIMPAK TM 250Y Sulzer Mellagrid 64Y Montz B1-250 MN 13

14 Pressure Drop, inh2o/ft packing Raschig RSR# gpm/ft gpm/ft gpm/ft2 15 gpm/ft gpm/ft2 5 gpm/ft Dry F-factor (ft/s) (lb/ft 3 ) 0.5 Fractional area, a e /a p Gas Rates 1.94 ft/s 3.22 ft/s 4.83 ft/s 6.45 ft/s 8.06 ft/s Liquid Load (gpm/ft 2 ) 14

15 k L, ft/s k G, ft/s Raschig RSR# E E-04 y = 7E-05x R² = E E E y = x R² = E E Liquid Load, GPM/ft Gas Velocity, ft/s 15

16 Pressure Drop, inh2o/ft packing GTC GT-OPTIMPAK TM 250Y gpm/ft gpm/ft2 20 gpm/ft2 15 gpm/ft2 10 gpm/ft2 5 gpm/ft2 Dry Fractional area, a e /a p Gas Rates 1.94 ft/s 3.22 ft/s 4.83 ft/s 6.45 ft/s 8.06 ft/s F-factor (ft/s) (lb/ft 3 ) Liquid Load (gpm/ft 2 ) 16

17 k L, ft/s k G, ft/s GTC GT-OPTIMPAK TM 250Y 4.0E E E E-04 y = 7E-05x R² = E E E E-05 ug = 1.91 FT/S ug = 3.25 FT/S ug = 4.25 FT/S y = x R² = E Liquid Load, GPM/ft Gas Velocity, ft/s 17

18 Pressure Drop, inh2o/ft packing Sulzer Mellagrid 64Y gpm/ft gpm/ft2 20 gpm/ft2 15 gpm/ft2 10 gpm/ft2 5 gpm/ft2 Dry Fractional area, a e /a p Gas Rates 1.94 ft/s 3.22 ft/s 4.84 ft/s 6.45 ft/s 8.06 ft/s F-factor (ft/s) (lb/ft 3 ) Liquid Load (gpm/ft 2 ) 18

19 k L, ft/s Sulzer Mellagrid 64Y 2.0E E E E E E-04 y = 4E-05x R² = k G, ft/s L = 15 GPM/FT2 L = 10 GPM/FT2 L = 20 GPM/FT2 y = x R² = E E E E E Liquid Load, GPM/ft Gas Velocity, ft/s 19

20 Pressure Drop, inh2o/ft packing Montz B1-250 MN gpm/ft2 25 gpm/ft gpm/ft2 15 gpm/ft2 10 gpm/ft2 5 gpm/ft2 Dry Fractional area, a e /a p Gas Rates 1.94 ft/s 3.22 ft/s 4.83 ft/s 6.45 ft/s 8.06 ft/s F-factor (ft/s) (lb/ft 3 ) Liquid Load (gpm/ft 2 ) 20

21 k L, ft/s Montz B1-250 MN 4.5E E E E-04 y = 4E-05x R² = E E E E-04 Superficial Gas Velocities, ft/s E E Liquid Load, GPM/ft 2 21

22 Effective Area Model Prediction Test System: Air/CO2/0.1 N NaOH

23 Sh G Model Prediction Test System: Air/SO2/0.1 N NaOH Sh G,model GTC350Z MP250Y MP250X GTC350Y A350Y B350X RSP200X GTC500Y MP2X RSP250Y MP125Y Sh G +20% y = x -20% * Re G Mi ScG Average deviation: 12% Sh G,exp 23

24 Sh L Model Prediction Test System: Air/Toluene/Water MP2X MP250Y GTC350Y GTC350Z MP250X A350Y +20% y = x -20% 160 B350X RSP200X Sh L,model 80 GTC500Y RSP250Y Sh L * Re L Sc L Mi Average deviation: 22% Sh L,exp 24 24

25 Predicted HETP, cm Prediction of Distillation HETP Cyclohexane/n-Heptane Total Reflux 0.165, 0.33, 1.65 and 4.14 bar % % Measured HETP, cm 25

26 Perry s Chemical Engineers Handbook Revision of Chapter 15 Liquid-Liquid Extraction and Co-authors: Tim Frank and Bruce Holden (Dow) and Seibert 26

27 Presentations SRP Update Effect of Physical Properties on Sieve Tray Extractor Performance SRP Databases and Computer Programs Performance Comparison of Different Pressure Drop Correlations Effect of Liquid Viscosity on Liquid Film Mass Transfer Coefficient (Seibert) (Seibert) (Seibert) (Wolf-Zollner) (Di Song) Hydrophobic Microporous Membrane Contactor for the Recovery of Insoluble Oil From Emulsions (Aurore Mercelat) 27

28 Effect of Physical Properties on Sieve Tray Extractor Performance Frank Seibert PSTC Review Meeting Austin, TX October 19, 2014

29 Background Industrial Popularity of Sieve Tray Extractors New Applications New Solvents Physical Property Effects???

30 Sieve Tray Extractor Advantages Light liquid out Simple Column contacting High throughput Static operation (no moving parts) Reliable mass transfer scale-up Good relative efficiency at large-scale Low capital cost Amenable to modelling Heavy liquid in Light liquid in Operating interface Perforated plate Downspout Coalesced dispersed Heavy liquid out 3

31 Measured Tray Efficiencies and Capacities* Chemical System Dispersed Phase * Data obtained by Separations Research Program m solv, cp Eo, % HETS, cm (U c + U d ) FL, cm/s toluene/acetone/water toluene butanol/succinic acid/water butanol SCO2/ethanol/water SCO SCO2/isopropanol/water SCO MIBK/acetic acid/water MIBK hexane/methanol/water hexane sulfolane/toluene/heptane sulfolane

32 Important Physical Properties Slope of the equilibrium line (solute), m Interfacial tension, s Densities, r Density difference, Dr Viscosities, m Diffusion Coefficients, D 5

33 Diffusion Coefficient Estimation D AB M B T V A f m B = diffusion coefficient of solute A into B, cm2/s = molecular weight of B = absolute temperature, K = molal volume of solute A at its normal boiling temperature = association factor of solvent B, 2.6 for water, 1 for most hydrocarbons = viscosity of B, cp Ref. Wilke, C.R., and P. Chang: AIChE J., 1:264 (1955) 6

34 Force Balance on a Drop F drag F buoyancy F buoyancy F gravity F drag = 0 F gravity F buoyancy ρ c π 6 d 3 vs g F gravity ρ d π 6 d 3 vs g F drag 1 2 C D ρ c π 4 d 2 vs U 2 So 7

35 Drop Velocity and Diameter C D = Drag coefficient on drop flowing through continuous phase d vs = Sauter mean drop diameter, cm g = acceleration due to gravity (=981), cm/s 2 U so = characteristic drop velocity, cm/s Dr = density difference, g/cm 3 r C = density of the continuous phase, g/cm 3 s = interfacial tension, dynes/cm 8

36 Characteristic Drop Velocity 9

37 Empirical Tray Efficiency Model Modified Treybal Model Z T d o U D, U C s = Tray Spacing, ft = Hole Diameter, ft = Superficial Velocity of Dispersed and Continuous Phases = Interfacial Tension, dynes/cm m, Dr and D? s?? 10

38 Mechanistic Tray Efficiency Model 11

39 Predicted Tray Efficiencies Baseline Physical Properties Physical Property Continuous Phase Dispersed Phase Density, g/cm Viscosity, cp 1 1 Diffusion Coefficient, cm 2 /s 1.0E E-05 Interfacial Tension, dynes/cm Slope of the equil line (m dc ), (g/cm 3 )/(g/cm 3 ) % of Flood Extraction Factor =1.5 12

40 Predicted Tray Efficiency Effect of Density Difference 13

41 Predicted Tray Efficiency Effect of Viscosity 14

42 Predicted Efficiency Effect of Interfacial Tension 15

43 Analysis of Predictive Results E = Overall Tray Efficiency, % 16

44 Need More High Viscosity Data Sulfolane/Heptane & 25C 17

45 Mass Transfer Physical Properties Sulfolane/Toluene/Heptane Dilute Toluene Parameter Heptane-Rich Sulfolane-Rich Density, g/ml Viscosity, cp Dr = 0.58 g/cm 3 Toluene Diffusion Coefficient, cm 2 /s 3.42E E-6 Interfacial Tension, dynes/cm 9.2 Slope of Equilibrium Line, dc d /dc c 0.52 Concentrated Toluene Parameter Heptane-Rich Sulfolane-Rich Density, g/ml Viscosity, cp Toluene Diffusion Coefficient, cm 2 /s 3.14E E-6 Interfacial Tension, dynes/cm 6.2 Slope of Equilibrium Line, dc d /dc c 0.58 Interfacial Tension Determined from Samples Dr = 0.50 g/cm 3 18

46 Superficial Dispersed Phase Velocity at Flood, cm/s Flooding Example Heptane Dispersed No Toluene No Coalescer Superficial Continuous Phase Velocity at Flood, cm/s 19

47 Superficial Dispersed Phase Velocity at Flood, cm/s Flooding Example Sulfolane Dispersed No Toluene No Coalescer Superficial Continuous Phase Velocity at Flood, cm/s 20

48 Effect of Toluene on Flooding Sulfolane Dispersed No Coalescer Superficial Dispersed Phase Velocity, cm/s Superficial Continuous Phase Velocity, cm/s 21

49 Superficial Dispersed Phase Velocity at Flood, cm/s Effect of Coalescer on Flooding Sulfolane Dispersed No Toluene Stainless Steel Coalecser Not Flood Points 1.5 No Coalescer Carbon Coalescer Superficial Continuous Phase Velocity at Flood, cm/s 22

50 Overall Tray Efficiency, % Sieve Tray Efficiency Effect of Interfacial Tension and % of Flood Low Interfacial Tension (60%) (60%) High Interfacial Tension (80%) 10 (80-90%) 7.5 (40%) Dispersed Phase = Sulfolane Mass Flow Ratio of Sulfolane/Heptane (solute-free) = U c, cm/s 23

51 Superficial Dispersed Phase Velocity at Flood, cm/s LLE 8.03 Prediction No Coalescer No Toluene Sulfolane Dispersed 9.4 dynes/cm Experimental Predicted by LLE Superficial Continuous Phase Velocity at Flood, cm/s 24

52 Superficial Dispersed Phase Velocity, at Flood cm/s LLE 8.03 Prediction Stainless Coalescer with Toluene Sulfolane Dispersed 2.1 dynes/cm Operating Flow Ratio Region Experimental Sulfolane Drops Coalesced with Stainless Packing Predicted by LLE 8.03 with Coalescer Superficial Continuous Phase Velocity at Flood, cm/s 25

53 Predicted (Uc+Ud) at Flood, cm/s Revised LLE Sieve Tray Flooding Model (9.0) Comparisons Based on LLE % % 1A 1B 2A 2B 3A 3B 4A 4B 5A 5B 6A 6B 7A 7B Experimental (Uc+Ud) at Flood, cm/s 26

54 Predicted Overall Tray Efficiency, % Predicted Tray Efficiency Sulfolane(d)/Toluene/Heptane(c) % % LLE 9.0, With Contaminant LLE 9.0, No Contaminant Experimental Overall Tray Efficiency, % 27

55 LLE 9.0 Modeling Adjustments Hydraulics: Coalescence flooding prediction (U df ) - also dependent on viscosities and presence of contaminant Mass Transfer: 1) Weber Number correction is not used if average drop diameter < hole diameter 2) For surfactant option, correction factor on dispersed phase film mass transfer coefficient,

56 Summary Sieve Tray Efficiency depends on s, Dr and m, especially m SRP has added to the available database regarding high Dr and m LLE Model 8.03 required slight adjustment Version

57 Thank You? 30

58 SRP Databases and Computer Programs Process Science and Technology Center Fall Meeting Frank Seibert Separations Research Program October 19, 2016 Austin, Texas

59 Frank Seibert Process Science and Technology Center Fall 2016 Overview SRP Computer Programs - LLE Distil 2.2 Air/Water Database Distillation Database Other Programs

60 SRP Distillation/Extraction/Reactive System Frank Seibert Process Science and Technology Center Fall 2016

61 LLE 9.0 SRP Computer Distil 2.2 Programs

62 Frank Seibert Process Science and Technology Center Fall 2016 LLE 9.0 EXCEL-Based program for rigorous hydraulic and mass transfer calculations Spray Packing Sieve Trays Baffle Trays Membrane Extraction

63 Distil 2.2 Frank Seibert Process Science and Technology Center Fall 2016 EXCEL-Based program for rigorous hydraulic and mass transfer calculations Sieve Trays Baffle Tray Co-Flo Tray Random and Structured Packing Choice of Model Options

64 Air/Water Database

65 Air/Water Database Frank Seibert Process Science and Technology Center Fall NaOH + CO Na CO H2 O Entrainment Collector AIR OUTLET 0.1 N NaOH FEED u Ls = 1-35 gpm/ft 2 T I-5 Packed Bed 10 ft CO ppm in ambient air T P-7 T AIR INLET u Gs = ft/s L 200 gal 750 L SOLUTION OUTLET Variable Speed Drive Controlled Water Flow

66 Frank Seibert Process Science and Technology Center Fall 2016 Air/Water Database Data* provided in databases include: Air Rate Liquid Rate Pressure Drop Temperature Measurements F-Factor NTU og HTU og K og A Effective surface area & fractional area k L A & k L k G A & k G Liquid Holdup * All calculations are corrected for temperature, diffusion coefficient, viscosity, and ionic strength where applicable.

67 Frank Seibert Process Science and Technology Center Fall 2016 Air/Water Database Mass Transfer Area ( )

68 Air/Water Database Frank Seibert Process Science and Technology Center Fall 2016 Mass Transfer Film Coefficient

69 Frank Seibert Process Science and Technology Center Fall 2016 Air/Water Database Packing List Random Packings 1 Stainless Steel Pall Rings 2 Stainless Steel Pall Rings CMR #2A (Plastic) CMR #2A (Metal) #25 IMTP* #40 IMTP Amistco SB 2-Pac 2540 Amistco SB 2-Pac 4050 Raschig-Jaeger RSR#0.5 1 Pall Rings (Plastic) Raschig RSR#0.7 Raschig RSR#0.3 Raschig RSR#1.5 * Scrubbing only Includes Mass Transfer Film Coefficients

70 Frank Seibert Process Science and Technology Center Fall 2016 Air/Water Database Montz B1-250 Montz B1-500P* Montz B1-500 Montz A3-500* Montz B1-350* Montz B Raschig RSP300 Koch-Glitsch Flexipac AQ Style 20 Mellapak 250Y Mellapak 500Y Raschig RSP250wSE A350X A500Y GTC GT-PAK 500Y MellaGrid 64Y * Scrubbing only Packing List Structured Packings Mellapak 2Y Mellapak 250X MellapakPlus 252Y Mellapak 125Y Mellapak 250Y (Smooth) Mellapak 2X Koch-Glitsch Flexipac 1.6YHC Raschig RSP250 (2010) GTC GT-GTPAK 350Z Mellapak 250X Mellapak 250Y B350Y Raschig RSP200X GTC GT-OPTIM PAK 250Y Montz B1-250 MN Includes Mass Transfer Film Coefficients

71 Frank Seibert Process Science and Technology Center Fall 2016 Air/Water Database Example Effective Area Plot

72 Air/Water Database k G, ft/s Frank Seibert Process Science and Technology Center Fall 2016 Example k G Plot Gas Velocity, ft/s 15 GPM/ft2 20 GPM/ft2

73 k L, ft/s Frank Seibert Process Science and Technology Center Fall 2016 Air/Water Database Example k L Plot 2.0E E E E E E E E E E E+00 ug = 4.87 ft/s ug = 3.25 ft/s ug = 1.95 ft/s Liquid Load, GPM/ft 2

74 Distillation Database

75 Distillation Database Distillation Column Overhead Condenser Cooling Water Collector Plate Reflux returned by gravity Distributor Pressure Drop Transmitter calibrated from 0-30 in H 2 O packed height DPC Steam Packing Support Lug Reboiler Condensate Frank Seibert Process Science and Technology Center Fall 2016

76 HETP, in Frank Seibert Process Science and Technology Center Fall 2016 Distillation Database 30 Raschig RSP 250wSE f-factor, ft/s(lb/ft3) psia 4.83 psia 24 psia 60 psia

77 Frank Seibert Process Science and Technology Center Fall 2016 Distillation Database 10 1 Raschig RSP 250wSE Cyclohexane/n-Heptane DP/Z, in H2O/ft psia 4.83 psia 24 psia 60 psia f-factor, ft/s(lb/ft3)0.5

78 Distillation Database Frank Seibert Process Science and Technology Center Fall 2016 Distillation Packing Database 41 Structured Packings 16 Random Packings Different distributors, packing heights, orientation, corrugation angle, metallurgy 1-3 Packings added per year (Vendor Sponsored)

79 Frank Seibert Process Science and Technology Center Fall 2016 Distillation Database Distillation Database includes: EXCEL Worksheets Raw Input Summary of Calculations Calculated Parameters and Properties HETP & DP Plots -Includes English and SI units

80 Distillation Database Structured Packings - Distillation Flexipac 1Y Flexipac 1Y HC Flexipac 2Y Mellapak 250Y Mellapak 500Y Sulzer BX Gempak 2A Gempak 2AT Maxpak 90Angle RSP300 RSP250wSE Montz A3-500 Montz B1-250 Montz 250 ML Montz B Montz B1-350 Montz 350 ML Montz B1-250 (1995) Montz BSH-400 Montz BSH Intalox 1T Intalox 2T RSP300 (2009) RSP200 RSP250 (2009) RSP350Y RSP200X RSP150 RSP500 RSP350X Baretti 250 RMP N250Y RMP S350 GT-OPTIM PAK 250Y GT-OPTIM PAK 350Y RMP SP RMP SP RSP 250X RSP 350Y(2IDS) RSP250Y(2IDS) AMACS ACS S-100 Frank Seibert Process Science and Technology Center Fall 2016

81 Frank Seibert Process Science and Technology Center Fall 2016 Distillation Database Random Packings - Distillation 1-in Pall Rings 1.5-in Pall Rings 2-in Pall Rings 1.5-in Polished PR Kenning 25 Lantec QPac-1 Fleximax 300 IMTP 40 Amistco SB 2-Pac 2540 Amistco SB 2-Pac 4050 RSR #0.5 RSR#1 RSR #0.1 RSR #0.3 RSR #1.5 RSR #0.6

82 Other Programs Frank Seibert Process Science and Technology Center Fall 2016 Membrane2001 (Freeman) PSA Calc (Ritter)

83 SRP Frank Seibert (512)

84 Performance comparison of different pressure drop correlations Verena Wolf-Zöllner PSTC Meeting, Austin, Texas, October 18-19, 2016

85 Overview Introduction Background Pressure Drop Models First Modeling Results Conclusion and Outlook 10/18/2016 Verena Wolf-Zoellner 1

86 Introduction Pressure drop models? Bozzano 2007 Existing models = only useable for validated packings 10/18/2016 SRP Bravo, Rocha, Fair (Verschoof) Verena Wolf-Zoellner 2

87 Background Newly developed packing reliable calculation? Existing models = only usable for validated packings 10/18/2016 Verena Wolf-Zoellner 3

88 Modeling SRP-Model Delft-Model NNA-Model of Piché et al. Source: Engel 1999 Billet and Schultes-Model Maćkowiak-Model Engel-Model 10/18/2016 Verena Wolf-Zoellner 4

89 Pressure loss [Pa/m] Billet and Schultes-Model 1000 Hiflow Plus #2 - Billet and Schultes Mean deviation = 15% B=0 (Experiment) B=0 (B&S 1999) B=30 (Experiment) B=30 (B&S 1999) B=40 (Experiment) B=40 (B&S 1999) B=60 (Experiment) B=60 (B&S 1999) B=80 (Experiment) B=80 (B&S 1999) B=100 (Experiment) B=100 (B&S 1999) B=120 (Experiment) B=120 (B&S 1999) 1 10 F-Factor [Pa 0.5 ] 04/28/2015 Verena Wolf-Zoellner 5 B Irrigation density [m 3 /(m 2 *h)]

90 Pressure loss [Pa/m] Billet and Schultes-Model Hiflow Plus #1 - Billet and Schultes Mean deviation = 35% B=0 (Experiment) B=0 (B&S 1999) B=30 (Experiment) B=30 (B&S 1999) B=40 (Experiment) B=40 (B&S 1999) B=60 (Experiment) B=60 (B&S 1999) B=80 (Experiment) B=80 (B&S 1999) B=100 (Experiment) B=100 (B&S 1999) B=120 (Experiment) B=120 (B&S 1999) 1 10 F-Factor [Pa 0.5 ] 04/28/ B Irrigation density [m 3 /(m 2 *h)]

91 Billet and Schultes-Model Wet pressure loss Wetting factor Dry resistance coefficient Loading zone Reduced cross-sectional area 10/18/2016 Verena Wolf-Zoellner 7

92 Modeling Billet & Schultes 1991 Wetting factor Billet & Schultes 1999 Dependence of packing geometry Dependence of operating conditions and packing geometry 10/18/2016 Verena Wolf-Zoellner 8

93 Pressure loss Δp/H [Pa/m] Pressure loss Δp/H [Pa/m] Modeling Influence of the geometrical surface area Billet und Schultes Influence of the geometrical surface area This work B=0 B=30 B=60 B=80 B=100 B= Geometrical surface area a geo [m 2 /m 3 ] Geometrical surface area a geo [m 2 /m 3 ] 10/18/2016 Verena Wolf-Zoellner 9 B Irrigation density [m 3 /(m 2 *h)]

94 Pressure loss [Pa/m] Modeling Hiflow Plus #1 - This work B=0 (Experiment) B=0 (This work) B=30 (Experiment) B=30 (This work) B=40 (Experiment) B=40 (This work) B=60 (Experiment) B=60 (This work) B=80 (Experiment) B=80 (This work) B=100 (Experiment) B=100 (This work) B=120 (Experiment) B=120 (This work) Mean deviation= 15% F-Factor [Pa 0.5 ] 10/18/2016 Verena Wolf-Zoellner 10 B Irrigation density [m 3 /(m 2 *h)]

95 Deviation [%] Deviation [%] Modeling Random Packing & HFP Mean deviation of the wet pressure loss [%] Raflux 25-5 Raflux 50-5 RMSR 25-3 RMSR 50-4 RMSR 70-5 B&S 1991 B&S 1999 This Wolf work 2014 Raflux ( Pall Ring) RMSR ( IMTP) Mean deviation of the wet pressure loss [%] B&S 1991 B&S 1999 This Wolf work Hiflow Ring 10/18/2016 Hiflow P 0 Hiflow Plus #1 Hiflow Plus #2 Hiflow 50-0 Hiflow 50-6 Hiflow 38-1 Hiflow

96 Modeling Structured Packing 10/18/

97 Databank Random Packing 1 Stainless Steel Pall Rings 2 Stainless Steel Pall Rings CMR #2A (Plastic) CMR #2A (Metal) #40 IMTP Amistco SB 2-Pac 2540 Amistco SB 2-Pac Pall Rings (Plastic) Raschig-Jäger RSR #0.3 Raschig-Jäger RSR #0.5 Raschig-Jäger RSR #0.7 10/18/2016 Verena Wolf-Zoellner 13

98 Databank Structured Packing Montz B1-250 Montz A3-500 Koch-Glitsch Flexipak AQ Style 20 Koch-Glitsch Flexipak 1Y + high vis. Koch-Glitsch Flexipac 1.6Y HC Raschig RSP250wSE Raschig RSP200X Raschig RSP250 Raschig RSP300 A350X A500Y B350Y GTC GT-PAK TM 350Y GTC GT-PAK TM 350Z GTC GT-PAK TM 500Y GTC GT-OPTIM PAK TM 250Y Mellapak 2X Mellapak 2Y Mellapak 125Y Mellapak 250X + high viscosity Mellapak 250Y Mellapak 250Y (smooth) Mellapak Plus 252Y Mellapak 500Y Mellagrid 64Y 10/18/2016 Verena Wolf-Zoellner 14

99 Pressure Drop Modeling Huge Databank Billet & Schultes 1991 & 1999 & Wolf 2014 Delft SRP Maćkowiak Engel 1999/2000 Stichlmair /18/2016 Verena Wolf-Zoellner 15

100 Databank Structured Packing Montz B1-250 Montz A3-500 Koch-Glitsch Flexipak AQ Style 20 Koch-Glitsch Flexipak 1Y + high vis. Koch-Glitsch Flexipac 1.6Y HC Raschig RSP250wSE Raschig RSP200X Raschig RSP250 Raschig RSP300 A350X A500Y B350Y GTC GT-PAK TM 350Y GTC GT-PAK TM 350Z GTC GT-PAK TM 500Y GTC GT-OPTIM PAK TM 250Y Mellapak 2X Mellapak 2Y Mellapak 125Y Mellapak 250X + high viscosity Mellapak 250Y Mellapak 250Y (smooth) Mellapak Plus 252Y Mellapak 500Y Mellagrid 64Y 10/18/2016 Verena Wolf-Zoellner 16

101 Pressure Loss Modeling 10/18/2016 Verena Wolf-Zoellner 17

102 Pressure loss [Pa/m] Mellapak 252Y- Engel Experiments vs modelling results Mellapak 252Y Mean deviation = 33% Hold-up (u L ) is given in gpm/ft 2 - m 3 /(m 2 *h) ul= 0 / 0 (exp.) ul= 0 / 0 (Engel) ul= 1 / 2.4 (exp.) ul= 1 / 2.4 (Engel) ul= 2.5 / 6.1 (exp.) ul= 2.5 / 6.1 (Engel) ul=3.75/ 9.1 (exp.) ul=3.75/ 9.1 (Engel) ul= 5 / 12.2 (exp.) ul= 5 / 12.2 (Engel) ul= 7.5 / 18.3 (exp.) ul= 7.5 / 18.3 (Engel) ul= 10 / 24.5 (exp.) ul= 10 / 24.5 (Engel) ul= 15 / 36.6 (exp.) ul= 15 / 36.6 (Engel) ul= 20 / 48.9 (exp.) ul= 20 / 48.9 (Engel) ul= 25 / 61.1 (exp.) ul= 25 / 61.1 (Engel) ul= 30 / 73.3 (exp.) ul= 30 / 73.3 (Engel) 1 F-Factor [Pa 0.5 ] 10 Engel 10/18/2016 Verena Wolf-Zoellner 18

103 Pressure loss [Pa/m] Mellapak 252Y- Wolf Experiments vs modelling results Mellapak 252Y Mean deviation = 28% Hold-up (u L ) is given in gpm/ft 2 - m 3 /(m 2 *h) ul= 0 / 0 (exp.) ul= 0 / 0 (W-14) ul= 1 / 2.4 (exp.) ul= 1 / 2.4 (W-14) ul= 2.5 / 6.1 (exp.) ul= 2.5 / 6.1 (W-14) ul=3.75/ 9.1 (exp.) ul=3.75/ 9.1 (W-14) ul= 5 / 12.2 (exp.) ul= 5 / 12.2 (W-14) ul= 7.5 / 18.3 (exp.) ul= 7.5 / 18.3 (W-14) ul= 10 / 24.5 (exp.) ul= 10 / 24.5 (W-14) ul= 15 / 36.6 (exp.) ul= 15 / 36.6 (W-14) ul= 20 / 48.9 (exp.) ul= 20 / 48.9 (W-14) ul= 25 / 61.1 (exp.) ul= 25 / 61.1 (W-14) ul= 30 / 73.3 (exp.) ul= 30 / 73.3 (W-14) 1 F-Factor [Pa 0.5 ] 10 Wolf /18/2016 Verena Wolf-Zoellner 19

104 Hold-up Modeling 10/18/2016 Verena Wolf-Zoellner 20

105 First Outcome Billet & Schultes & Wolf Needs constants Good results for HFP, random packing, sheet structured packings Bad performance for RSP200X and high liquid viscosity Flooding point prediction would need a modification 10/18/2016 Verena Wolf-Zoellner 21

106 First Outcome Delft and SRP Only for sheet structured packings No packing specific constants needed Delft Only correlation which can predict trustable results at high liquid viscosity Maćkowiak Works well for X-types Predicts flooding much too early for Y-types 10/18/2016 Verena Wolf-Zoellner 22

107 First Outcome Engel Needs dry pressure drop Agreeable mean deviation bad prediction of real pressure loss trends Stichlmair Needs constants Poor pressure drop prediction Predicts hold-up very well 10/18/2016 Verena Wolf-Zoellner 23

108 Conclusion and Outlook Many pressure drop correlations Only reasonable results for validated packings Modeling of huge databank of SRP with available models Advantages and disadvantages of models Modification of existing model or development of a new pressure drop correlation 10/18/2016 Verena Wolf-Zoellner 24

109 Performance comparison of different pressure drop correlations Verena Wolf-Zöllner

110 Research Summary: Effect of µ L on mass transfer for packings Di Song Dr. Gary Rochelle & Dr. Frank Seibert University of Texas at Austin

111 Contents Objective & Motivation Packings & PCCC process Mass transfer theory Literature review Methods Viscosity enhancer Wetted-wall column Pilot column Results Kinetics model Packing list Effect of µ L on a e Effect of µ L on k L Random vs Structured Conclusions 1

112 Objective Determine how µ L affects mass transfer for packings Motivation Many industrial separations (including PCCC) encounter viscous liquids Packed columns have wide application and large CAPEX & OPEX 2

113 Industrial applications with viscous liquid Electrolyte solutions Crude oil Organic/polymer solution Ionic liquids PCCC Amine soln. (α = 0.4) 5m PZ 8m PZ 8m MEA H 2 O 40 C 3.6 cp 11.4 cp 2.4 cp 0.65 cp Slower diffusion of CO 2 to bulk liquid Slower diffusion of free amine to L-G interface (surface depletion) Slower diffusion of loaded amine back to bulk liquid (P * CO2) Less liquid turbulence 3

114 Why is μ L important? Solvent 1 Solvent 2 Knowing how μ L affects mass transfer gives more μ L 1 4 accurate predictions of k L & a e, help save money k L ( μ L -0.8 ) from inefficient/insufficient column design a e ( k L -1 ) 1 3 4

115 Two-film theory Bulk gas Gas film Liquid film Bulk liquid [A] P A,b P A,i C A,i=P A,i/H A Gas-phase resistance = 1/k g Liquid-phase resistance = H A /k L G/L interface C A,b Overall resistance = 1/K g = 1/k g + H A /k L = 1/k g + 1/k g 5

116 μ L affects k L in two ways k L = C 1 μ α D β D = C 2 μ γ k L (k L a) = C 3 μ α+βγ α Direct influence via the turbulence of liquid βγ Indirect influence via D of mass transfer species μ L affects a e? 6

117 α Predictions in literature Empty Solid Random Structured Δμ L < 5 cp Δμ L > 5 cp k L (k L a) = C μ α D β Column I.D. (cm) 7

118 Limitations of existing models Insignificant variance of μ L Limited column size Sh = Sh 0 Re Re 0 a Sc Sc 0 b Few structured packing investigated k L d D = C 0 d v ρ μ a μ ρ D b Unreliable (lack of) a e data k L = C 0 d a 1 ρ a b v a D 1 b μ b a 8

119 Works of previous group members Robert E. Tsai (2010) Investigated a e of structured packings (L, G, μ L, σ) System: CO 2 /NaOH/H 2 O/PEG μ L : 1 15 cp Result: a e is not affected by μ L Chao Wang (2015) Investigated a e, k G, k L of structured/random packings (L, G) System: CO 2 /NaOH/H 2 O; SO 2 /NaOH/H 2 O; Toluene/H 2 O No variance of μ L 9

120 Research approach 10 Stage Target data k g ' a e k L Objective Provide kinetic data for stage 2 Provide area data for stage 3 Provide raw data for k L correlation System μ L range CO 2 + NaOH/H 2 O Toluene + H 2 O + viscosity enhancer + viscosity enhancer 1 60 cp Equipment WWC Pilot PVC column Packing N/A Various random and structured packings

121 Why glycerol? Structure M w 100 cp wt % to (20 C) Tested? Dissolve in H 2 O Newtonian? Affect D? Affect kinetics? PEG 0.4 M 2.2 Yes Hard No No No Glycerol No Easy Yes Yes Yes Blue preferable; Red undesirable 11

122 Wetted wall column (WWC) 12 [CO 2 ] WWC CO 2 Analyzer SS tube O.D.: 1.26 cm SS tube L: 9.1 cm Rxn chamber O.D.: 2.54 cm Outer chamber O.D.: 10.2 cm CO 2 flux k g (known a e ) Solv. Tank [CO 2 ] Bypass N 2 1L CO 2

123 Pilot packed column a e : Ambient CO 2 /NaOH/H 2 O/glycerol k L : Air/Toluene/H 2 O/glycerol Blower ACFM H: 25 ft Z max : 10 ft I.D.: 16.8 in Air Outlet Trutna collector Liquid Inlet F40 Distributor Air Inlet Storage Tank (V max : 250 gal) Liquid Outlet Bypass Pump (L: gpm/ft 2 ) 13

124 k g ' 10 7 (mol/m 2 s Pa) k g measured by WWC C 20 C 40 C calculated k g ' measured k g ' for 0.1 N NaOH measured k g ' for 0.1 N NaOH w/ 0.05 N Na 2 CO 3 measured k g ' for 0.3 N NaOH 4 CO 2 + NaOH/H 2 O/glycerol Glycerol (wt%) 14

125 Equilibrium and Rxns for CO 2 /NaOH/H 2 O-Glycerol k g = k Alk Alk D CO2,L H CO2 k Alk = k OH OH Alk + k Glycerol Glycerol Alk 15

126 k Alk (10 3 L/mol s) Measured and calculated k Alk C C C M NaOH 1 st exp. 0.1 M NaOH 2 nd exp. 0.1 M NaOH 3 rd exp. 0.3 M NaOH exp. 8 Calculated k Alk Glycerol (mole fraction) 16

127 Packing list Packing characterization (1 cp) (k L, k G, a e, ΔP, h) GT-OPTIMPAK 250Y Montz B1 250 MN Mella Grid 64Y RSR 1.5 RSR 0.5 a e of aq. glycerol (1-60 cp) GT-OPTIMPAK 250Y k L of aq. glycerol (1-60 cp) GT-PAK 500Y GT-PAK 350Y GT-OPTIMPAK 250Y MP 250X MP 250Y RSP 250Y Montz B1 250 MN MP 125Y RSR 1.5 RSR

128 Fractional area (a e /a P ) The effect of µ L on a e 1.1 a e a P = 1.41 ρ L σ g1 3 u L a P Tsai SRP1601 SRP cp (k g ' = 4.5 x 10-7 mol/m 2 s Pa) 3-5 cp (k g ' = 3.7 x 10-7 mol/m 2 s Pa) 0.5 G = 5.1 m 3 /min cp (k g ' = 2.3 x 10-7 mol/m 2 s Pa) cp (k g ' = 1.1 x 10-7 mol/m 2 s Pa) Liquid load (m 3 /m 2 hr) 18

129 Measured k L using calculated a e (m/s) The effect of µ L on k L E-05 1 cp 6 ft packing 1 cp 10 ft packing 3-5 cp 10 ft packing cp 10 ft packing cp 10 ft packing MP 125Y +50% -50% GT-PAK 350Y GT-OPTIMPAK 250Y MP 250Y 5E-06 MP 250X AAD = 57% Sh=1.79 Re0.74 Sc0.5 Mi0.42 GT-PAK 500Y 5E-07 5E-07 5E-06 5E Calculated k L from dimensionless Wang (m/s) 19

130 Measured k L using calculated a e (m/s) The effect of µ L on k L cp 6 ft packing 1 cp 10 ft packing 3-5 cp 10 ft packing cp 10 ft packing MP 125Y +50% -50% 5E cp 10 ft packing MP 250Y GT-OPTIMPAK 250Y 5E-06 MP 250X GT-PAK 500Y AAD = 20% GT-PAK 350Y Sh=0.236 Re0.57 Sc0.5 Ga0.37 Ka Mi0.42 5E-07 5E-07 5E-06 5E Calculated k L from new dimensionless model (m/s) 20

131 Measured k L with other factors deducted Total dependence on µ L of k L y = 5E-05x Universally applicable Direct = Indirect = System-specific based on D-µ relationship GT-PAK 500Y GT-PAK 350Y MP 250Y GT-OPTIMPAK 250Y 1 cp 6 ft packing 1 cp 10 ft packing 3-5 cp 10 ft packing cp 10 ft packing cp 10 ft packing MP 125Y MP 250X Liquid viscosity (cp) 21

132 α Compared to literature predictions k L (k L a) = C μ α D β Empty Solid Random Structured Δμ L < 5 cp Δμ L > 5 cp This work Column I.D. (cm) 22

133 Measured k L with other factors deducted Random vs. Structured 0.01 y = x Effect of µ L on k L for structured and random packings are the same RSR cp 6 ft packing 3-5 cp 10 ft packing cp 10 ft packing cp 10 ft packing Liquid viscosity (cp) 23

134 Avg. ratio to random packing Effect of packing type 1.2 µ L = 1 cp RSR 1.5 (a P = 120 m 2 /m 3 ) MP 125Y (a P = 125 m 2 /m 3 ) kl ae klae k L a e k L a e 24

135 Avg. ratio to random packing Effect of packing type µ L = 1 cp Random: RSR 0.5 (a P = 250 m 2 /m 3 ) Structured: MP 250Y (a P = 250 m 2 /m 3 ) Structured: MP 250X (a P = 250 m 2 /m 3 ) Hybrid: RSP 250Y (a P = 250 m 2 /m 3 ) kl ae klae k L a e k L a e 25

136 Conclusions The µ L does not affect a e for GT-OPTIMPAK 250Y and probably other structured packings. The direct dependence of k L on µ L is for structured packings. This is believed to be universally applicable for Newtonian liquids. The indirect dependence of k L on µ L is for glycerol solutions. This is system-specific based on the D-µ relationship. The effect of µ L on k L is the same for random and structured packings. Compared to literature correlations, it has large equipment size, the largest µ L range, and the largest packing database, and measured a e data. No consistent conclusion can be drawn for the effect of packing type/geometry on liquid film mass transfer due to personal error and experimental technique change. 26

137 Acknowledgments Dr. Gary Rochelle Dr. Frank Seibert Dr. Eric Chen Rochelle group Texas Carbon Management Program Separation Research Program 27

138 Thank you! Di Song 28