Ebulliometric Determination of Vapour-Liquid Equilibria

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Ebulliometric Determination of Vapour-Liquid Equilibria Powered By Docstoc
					Ebulliometric Determination
of Vapour-Liquid Equilibria
for Pure Alkanolamines and
their Aqueous Solutions
     Inna Kim and prof. Hallvard F.
     Svendsen
     NTNU, Trondheim, Norway
Outline
 Experimental set-up and procedure
 Results:
   Pure components
   Binary aqueous solutions
   Ternary aqueous solutions
 Thermodynamic consistency test
 Summary

           11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Experimental set-up and procedure

• Experimental set-up
                       3                     2
                       T    T                        P




                                                                 P




                                                 P

            1                       5
                             4

                                                            N2




                                        6




   1 - ebulliometer; 2 - pressure controller; 3 – thermocouples;
   4 - cold trap; 5 - buffer vessel; 6 - Vacuum pump
                            11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Results: pure components


Vapour pressure: H2O                                                         (RMS* = 0.59)

                     1500
                                                                                                 Osborne N.S. et al., 1934

                                                                                                 Stimson H.F., 1969
                     1200
                                                                                                 Nov. 29, 2006 (EB1)

                                                                                                 Nov. 29, 2006 (EB2)
                     900
           P /mbar




                                                                                                 Dec. 05, 2006(EB1)

                                                                                                 Dec. 05, 2006(EB2)
                     600                                                                         Jan.15, 2007 (EB1)

                                                                                                 Mar 07, 2007 (EB1)
                     300                                                                         "Riedel eq [Perry's Eng.
                                                                                                 Handb.]"
                                                                                                 Points from different dates

                       0
                            20        40            60            80           100


                                                      T/ o C




          * Root Mean Square (RMS) deviation = √(Σ(Yexp-Ypred)2))/n

                                 11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
         Results: pure components


 Vapour pressure of pure components

                                       MEA                                                             MDEA                                                                   MAPA*
                             (RMS = 1.716)                                                         (RMS = 5.934)                                                      (RMS = 70 (4.16))
         1200                                                                  300                                                                        1400

                                                                                           exp
                     exp                                                                                                                                  1200
         1000                                                                  250         DIPPR
                     DIPPR                                                                 Austgen (DIPPR)                                                            exp
                                                                                                                                                          1000
                     Dow                                                                                                                                              DIPPR
          800                                                                  200
                     Austgen (DIPPR)                                                                                                                                  BASF
                                                                                                                                                           800




                                                                                                                                              Ptot/mbar
P/mbar




                                                                      P/mbar




          600                                                                  150
                                                                                                                                                           600

          400                                                                  100
                                                                                                                                                           400

          200                                                                   50                                                                         200


            0                                                                    0                                                                           0
                60      80        100    120     140   160      180                  120         140         160            180   200   220                      40   60      80   100    120   140   160

                                                                                                                                                                                    o
                                                                                                                                                                                   T/ C
                                        T/ o C                                                                     T/ o C




                     *Methylaminopropylamine,                    CH3NHCH2CH2CH2NH2, (CAS No. 6291-84-5)

                                                             11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Results: binary aqueous solutions

Ptot-xy diagram: MEA(1)+H2O(2)
               8                                                                     20
                                                             o                                                                      o
                                          MEA(1) - H2O(2): 40 C                                                   MEA(1) - H2O(2): 60 C
               7

               6                                                                     15

               5
   P tot/kPa




                                                                         P tot/kPa
               4                                                                     10

               3

               2                                                                      5

               1

               0                                                                      0
                    0   0.2   0.4              0.6    0.8          1                       0   0.2   0.4              0.6    0.8          1
                                    x 1, y 1                                                               x 1, y 1




               50                                                                    120
                                                             o                                                                      o
                                           MEA(1) - H2O(2): 80 C                                                MEA(1) - H2O(2): 100 C
                                                                                     100
               40

                                                                                     80
               30                                                                                                                             ○, * - exp [this work]
 Ptot/kPa




                                                                       Ptot/kPa




                                                                                     60
                                                                                                                                              ×, □ - 60, 78, 92 ºC
               20
                                                                                     40                                                              [Nath and Bender, 1983]
               10                                                                                                                             ◊, ∆ - 90 ºC [Tochigi, 1999]
                                                                                     20
                                                                                                                                              —     - Wilson
               0                                                                      0
                    0   0.2   0.4              0.6    0.8          1                       0   0.2   0.4              0.6    0.8          1   ---   - NRTL
                                    x 1, y 1                                                               x 1, y 1



                                                       11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Results : binary aqueous solutions

Activity coefficients: MEA(1)+H2O(2)
     1.2                                                          1.2
                                                                                                                               MEA (1) – H2O (2)
      1                                                            1                                                                        Wilson
     0.8                                                          0.8                                                          λ12              3506

     0.6                                                          0.6
                                                                                                                               λ21              -5682
γi




                                                             γi
                                                                                                                                            NRTL*
     0.4                                                          0.4
                                                                                                                               a12          -0.488
     0.2                                                          0.2
                                MEA(1) - H2O(2): 40 C
                                                     o                                                          o
                                                                                             MEA(1) - H2O(2): 60 C             b12          -699.6
                                                 ;
      0                                                            0                                                           a21              2.83
           0   0.2   0.4         0.6       0.8           1              0   0.2   0.4          0.6      0.8           1
                           x1                                                           x1
                                                                                                                               b21          89.272
                                                 ;                                                                             α12               0.2


      1                                                            1                                                      *Temperature dependent
                                                                                                                          parameters: τ12=
     0.8                                                          0.8
                                                                                                                          a12+b12/T; τ21= a21+b21/T
     0.6                                                          0.6
γi




                                                             γi




     0.4                                                          0.4                                                         ○, * - exp [this work]
                                                                                                                              ×, □ - 60, 78, 92 ºC
     0.2                                                          0.2
                                MEA(1) - H2O(2): 80 C
                                                     o                                                          o
                                                                                             MEA(1) - H2O(2): 100 C                   [Nath and Bender, 1983]
      0                                                            0                                                          ◊, ∆ - 90 ºC [Tochigi, 1999]
           0   0.2   0.4         0.6       0.8           1              0   0.2   0.4          0.6      0.8           1
                           x1                                                           x1
                                                                                                                              —      - Wilson
                                           11th Meeting of the International Post-Combustion CO2 Capture Network,--- - NRTL 20-21, 2008
                                                                                                                  Vienna, May
Thermodynamic consistency test

Pressure, vapour phase composition and
activity coefficients (MEA): residuals (a),
model vs experiment (b)
                         1                                                                                    0.2                                                                   0.4

                       0.8
                                                                                                             0.15                                                                   0.3
                       0.6
                                                                                                              0.1                                                                   0.2
                       0.4

                                                                                                             0.05                                                                   0.1
                       0.2


(a)




                                                                                                                                                                     δ ln(γ1/γ2)
          δ P/kPa




                                                                                                 2
                                                                                                 δ y*10
                         0                                                                                      0                                                                     0

                       -0.2
                                                                                                             -0.05                                                                  -0.1

                       -0.4
                                                                                                              -0.1                                                                  -0.2
                       -0.6

                                                                                                             -0.15                                                                  -0.3
                       -0.8

                        -1                                                                                    -0.2                                                                  -0.4
                              0        0.1     0.2          0.3         0.4     0.5        0.6                       0   0.1    0.2     0.3     0.4    0.5    0.6                          0          0.1        0.2            0.3           0.4       0.5         0.6
                                                            x1                                                                          x1                                                                                      x1




                       100                                                                                    0.06                                                                   11

                        90                                                                                                                                                           0.9
                                                                                                                                                                                    0.9
                                                                                                              0.05                                                                   0.8
                        80                                                                                                                                                          0.8

                        70                                                                                                                                                           0.7
                                                                                                                                                                                    0.7
                                                                                                              0.04
                                                                                                                                                                                     0.6


(b)
                        60                                                                                                                                                          0.6
         P model/kPa




                                                                                                                                                                           1model
                                                                                                                                                                     γ1 model
                                                                                                  y 1model




                        50                                                                                    0.03                                                                   0.5
                                                                                                                                                                                    0.5




                                                                                                                                                                      γ
                        40                                                                                                                                                           0.4
                                                                                                                                                                                    0.4
                                                                                                              0.02                                                                   0.3
                        30                                                                                                                                                          0.3

                        20                                                                                                                                                           0.2
                                                                                                                                                                                    0.2
                                                                                                              0.01
                        10                                                                                                                                                           0.1
                                                                                                                                                                                    0.1

                         0                                                                                       0                                                                    0
                                                                                                                                                                                     0 0        0.1     0.2    0.3      0.4     0.5     0.6     0.7   0.8     0.9   1
                              0   10     20   30     40      50    60     70   80     90   100                       0   0.01   0.02    0.03    0.04   0.05   0.06                    0        0.1     0.2    0.3      0.4     0.5     0.6     0.7    0.8     0.9   1
                                                          Pexp/kPa                                                                     y 1exp                                                                                  γ
                                                                                                                                                                                                                              γ11exp
                                                                                                                                                                                                                                 exp




      ○ - NRTL ; + - Wilson                                                    11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Results : binary aqueous solutions

Activity coefficients: MEA(1)+H2O(2)
      1.2                                                         1.2


       1                                                           1


      0.8                                                         0.8


      0.6                                                         0.6
 γi




                                                             γi
      0.4                                                         0.4


      0.2                                                         0.2
                                                   o                                                           o
                                 MEA(1) - H2O(2): 40 C
                                              ;                                              MEA(1) - H2O(2): 60 C
       0                                                           0
            0   0.2   0.4         0.6       0.8          1              0   0.2   0.4         0.6       0.8          1
                            x1                                                          x1

                                              ;


       1                                                           1
                                                                                                                         ○, * - exp [this work]
      0.8                                                         0.8
                                                                                                                         ×, □ - 60, 78, 92 ºC
      0.6                                                         0.6                                                           [Nath and Bender, 1983]
 γi




                                                             γi




                                                                                                                         ◊, ∆ - 90 ºC [Tochigi, 1999]
      0.4                                                         0.4
                                                                                                                         —     - Wilson
      0.2                                                         0.2
                                                   o
                                 MEA(1) - H2O(2): 80 C                                   MEA(1) - H2O(2): 100 C
                                                                                                               o         ---   - NRTL
       0                                                           0
            0   0.2   0.4         0.6       0.8          1              0   0.2   0.4         0.6       0.8          1
                            x1                                                          x1


                                           11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Results : binary aqueous solutions

Activity coefficients: MDEA(1)+H2O(2)
     1.4                                                        1.4
                                                   o                                                      o
                            MDEA(1) - H2O(2): 40 C                                     MDEA(1) - H2O(2): 60 C
     1.2                                                        1.2
                                                                                                                          MDEA (1) – H2O (2)
      1                                                          1
                                                                                                                                     Wilson
     0.8                                                        0.8
                                                                                                                          λ12         18784
γi




                                                           γi
     0.6                                                        0.6
                                                                                                                          λ21        -20107
     0.4                                                        0.4
                                                                                                                                      NRTL*
     0.2                                                        0.2
                                              ;                                                                           a12         -1.193
      0                                                          0
           0   0.2   0.4        0.6     0.8            1              0   0.2   0.4        0.6     0.8          1         b12        -531.72
                           x1                                                         x1
                                              ;                                                                           a21         7.281
                                                                                                                          b21        -909.68
     1.8                                                        1.8
                                                   o                                                      o
     1.6                    MDEA(1) - H2O(2): 80 C              1.6                   MDEA(1) - H2O(2): 100 C             α12           0.2
     1.4                                                        1.4

     1.2                                                        1.2

      1                                                          1
γi




                                                           γi




     0.8                                                        0.8

     0.6                                                        0.6
                                                                                                                    ○, * - exp [this work]
     0.4                                                        0.4
                                                                                                                    —     - Wilson
     0.2                                                        0.2
                                                                                                                    ---   - NRTL
      0                                                          0
           0   0.2   0.4        0.6     0.8            1              0   0.2   0.4        0.6     0.8          1
                           x1                                                         x1

                                        11th      Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Results : binary aqueous solutions

Activity coefficients: MAPA(1)+H2O(2)
     1.2                                                          1.2
                                                     o                                                       o
                                MAPA(1) - H2O(2): 40 C                                   MAPA(1) - H2O(2): 60 C             MAPA (1) – H2O (2)
      1                                                            1
                                                                                                                                       Wilson
     0.8                                                          0.8
                                                                                                                            λ12         14375
     0.6                                                          0.6                                                       λ21        -10167
γi




                                                             γi
     0.4                                                          0.4                                                                   NRTL*

     0.2                                                          0.2
                                                                                                                            a12        -1.783-
                                                 ;
                                                                                                                            b12        -290.91
      0                                                            0
           0   0.2   0.4          0.6      0.8           1              0   0.2   0.4        0.6     0.8          1
                                                                                                                            a21        13.776
                           x1                                                           x1
                                                 ;                                                                          b21        -3912.66
                                                                                                                            α12          0.2

      1                                                            1


     0.8                                                          0.8


     0.6                                                          0.6
γi




                                                             γi




                                                                                                                      ○, * - exp [this work]
     0.4                                                          0.4                                                 ×, □ - 50, 70, 100 ºC [BASF]

     0.2                                                          0.2                                                 —     - Wilson
                                                     o                                                      o
                            MAPA(1) - H2O(2): 80 C                                      MAPA(1) - H2O(2): 100 C       ---   - NRTL
      0                                                            0
           0   0.2   0.4          0.6      0.8           1              0   0.2   0.4        0.6     0.8          1
                           x1                                                           x1
                                            11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Results : ternary aqueous solutions

MEA(1)+MDEA(2)+H2O(3) system
            12.0                                                                 3.0
                                                                                                                                   MEA
                                                  10% MEA - 30% MDEA
            11.5                                                                                                                   H2O
                                                  20% MEA - 20% MDEA
                                                                                 2.5
                                                  30% MEA - 10% MDEA                                                               MDEA
            11.0
                                                                                 2.0
            10.5
                                              ;
ln (Ptot)




            10.0                                                                 1.5




                                                                            γi
             9.5                              ;                                  1.0

             9.0
                                                                                 0.5
             8.5


             8.0                                                                 0.0
              0.0026 0.0027 0.0028 0.0029    0.003   0.0031 0.0032 0.0033           0.00   0.02   0.04   0.06        0.08   0.10    0.12   0.14


                                       1/T                                                                      x1
               (a) Total pressure vs temperature                                 (b) Activity coefficients vs composition:
               and composition
                                                                                 ■ - MEA (red – 100ºC, green – 80ºC); ▲- H2O;
                                                                                 ♦ - MDEA (red – 100ºC, green – 80ºC),


                                             11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Results : ternary aqueous solutions

MDEA(1)+MAPA(2)+H2O(3) system
           7                                                                     9

          6.8                                                                    8
                                                   25MDEA-10MAPA
          6.6                                                                    7
                                                   25MDEA-15MAPA
          6.4
                                                                                 6
                                                   25MDEA-20MAPA
          6.2                                  ;                                 5
 ln (P)




           6




                                                                            γi
                                                                                 4
          5.8
                                               ;                                 3
          5.6
                                                                                 2
          5.4

          5.2                                                                    1

           5                                                                     0
           0.0026     0.0027   0.0028         0.0029     0.0030    0.0031        0.040      0.045   0.050   0.055   0.060   0.065   0.070


                                        1/T                                                                 x1


                (a) Total pressure vs temperature                                        (b) Activity coefficients vs composition:
                and composition
                                                                                         ♦ - MDEA (red – 100ºC, green – 80ºC),
                                                                                         ■ - MAPA; ▲- H2O


                                          11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Summary
   Ebulliometry – a simple and fast method for
   measuring VLE.
   VLE of pure components and binary and ternary                                               1500


   aqueous solutions was measured. Accuracy of the                                             1200



   results is limited by purity of the substances used                                          900




                                                                                     P/ mbar
   and by the precision of the analytical methods                                               600




   used for the sample analyses
                                                                                                300


                                                                                                     01



   Activity coefficients were calculated and fitted to
                                                                                                      20                    40                      60               80                  100
                                                                                                     0.8
                                                                                                                                                         o
                                                                                                                                                     T/ C



   Wilson and NRTL models
                                                                                                     0.6




                                                                                               γi
                                                                                                     0.4
                                                                                                          3



   Thermodynamic consistency test shows that                                                         0.2
                                                                                                       2




   measured data are consistent
                                                                                                          1
                                                                                                          0
                                                                                                            0      0.1     0.2         0.3    0.4        0.5   0.6     0.7         0.8    0.9   1
                                                                                                                                                         x1
                                                                                                          0




                                                                                                δ P/kPa
                                                                                                          -1


                                                                                                          -2


                                                                                                          -3




* The results were submitted for publication to                                                           -4


                                                                                                          -5
                                                                                                               0    0.05         0.1         0.15        0.2
                                                                                                                                                         x1
                                                                                                                                                                0.25         0.3         0.35   0.4



   the J. Chem. Eng. Data


                    11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
Acknowledgements
This work has been financially supported by the European
  Commission through the CASTOR Integrated Project
        (Contract № SES6-CT-2004-502856) and
   the BIGCO2 project, performed under the strategic
     Norwegian research program Climit. The authors
acknowledge the partners: Norsk Hydro, Statoil, GE Global
    Research, Statkraft, Aker Kværner, Shell, TOTAL,
ConocoPhillips, ALSTOM, the Research Council of Norway
(178004/I30 and 176059/I30) and Gassnova (182070) for
                      their support




               11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008
        THANK YOU
FOR YOUR ATTENTION !


         Questions?


   11th Meeting of the International Post-Combustion CO2 Capture Network, Vienna, May 20-21, 2008