Inna Kim and Hallvard F. Svendsen Norwegian University of Science and Technology (NTNU)
30
Research Review Meeting, Austin, 10-11/I-2008 1 Thermal measurements: Heat of absorption of CO 2 and Vapour-Liquid Equilibria in alkanolamine-water solutions Inna Kim and Hallvard F. Svendsen Norwegian University of Science and Technology (NTNU) Trondheim, NORWAY
description
Thermal measurements: Heat of absorption of CO 2 and Vapour-Liquid Equilibria in alkanolamine-water solutions. Inna Kim and Hallvard F. Svendsen Norwegian University of Science and Technology (NTNU) Trondheim, NORWAY. Outline. Heat of absorption Background Experimental set-up Results - PowerPoint PPT Presentation
Transcript of Inna Kim and Hallvard F. Svendsen Norwegian University of Science and Technology (NTNU)
Ingen lysbildetittelVapour-Liquid Equilibria in
Norwegian University of Science and Technology (NTNU)
Trondheim, NORWAY
Even though amine sweetening of gases and liquids has been used for many decades, the process is still being refined and improved to be more efficient.
*
*
Habs
The overall challenge of the project is to bring the cost down to the point where it becomes an attractive option in mitigation of global warming.
The cost of the process stems from several components. There is the cost of building the plant and purchasing the solvents. There are also the operational costs, in particular, the energy required to run the process.
Thermal energy is required to heat the solvent entering the stripper, to generate the heat required to release CO2 and to generate steam for dilution of the striper.
Information on the heats of reaction of acid gases (mainly CO2 and H2S) in aqueous solutions of alkanolamines is of prime importance for designing unit operations for acid gas removal, because it is directly related to the steam requirements of the amine regeneration stage.
*
Integrated over some loading interval (direct measurement)
Isothermal flow calorimeter
Background
In literature the heat of absorption is referred to as an Integral or Differential Habs.
Integral (calorimetric measurements)
The technique involved mixing varying amounts of acid gas with a fixed flow of clean amine solution, then using a flow calorimeter to measure the cooling required to exit at the same temperature and pressure as the inlet.
“Enthalpy of solution” calculated as the total energy required to maintain the inlet conditions divided by the total number of moles of acid gas flowing in the system.
These values are integral in loading and differential in temperature
Differential (from solubility measurements using Gibbs-Helmholtz equation)
En approximate value of the differential enthalpy of solution of CO2 in the aqueous alkanolamine solution is calculated by use of the following form of the Gibbs-Helmholtz equation, where xCO2 is the mole fraction or equilibrium loading of CO2.
*
VLE data: ln(pCO2) vs 1/T:
Fitted with a line,
1 [Hoff K.A., Mejdell T., Svendsen H.., 2005]
a
b
Background
To calculate differential Habs from VLE data, log of experimental vapour pressure (ln Pvap) is plotted against reciprocal temperature (1/T). We can fit these data points with a straint line (Fig. a) or second order polynomial (Fig. b). Both curves seems to fit the data very well.
However, if we do now differentiation to calculate the Habs, we will have constant Habs ( independent on temperature) in the first case and Habs with very strong temperature dependency in the second case.
It is a common practice to use a line fitted to the data.
*
Temperature profile for the Dome 5
North Caroline plant 2
“The increase in heat of absorption of up to 20% from the absorber to the stripper temperature may cause a deficient duty calculation with the reboiler if a constant heat of absorption at the lower value is used”2
2 [Jerry A. Bullin et al., Bryan Research & Engineering Inc. Bryan, TX, GPA 2007]
Background
Impact of temperature on the heat of absorption has not been sufficiently appreciated previously. According to the given reference, the increase in heat of absorption of up to 20% from the absorber to the stripper temperature may cause a deficient duty calculation with the reboiler if a constant heat of absorption at the lower value is used.
Knowledge of the effects of acid gas loading and other parameters on the heat of absorption can be used to more accurately predict and improve calculations in designing and operating amine sweetening facilities. Improved values for the heat of absorption allow more accurate calculations of the temperature profiles as well as exit rich amine temperatures from absorbers.
A nice example was provided in the article (ref) for the Dome North Caroline plant. The picture to the right, contains measured absorber temperature profiles for five sets of operating conditions.
*
3 - Vacuum pump
4 - Feed bottle
This work considers the impact of acid gas loading on the heats of absorption for CO2.
Since the heats of absorption vary with temperature, amine type, and solution concentration, the impact of those parameters is also investigated.
The Habs values of CO2 with MEA were measured using a reaction calorimeter with a reactor volume of 2 L.
Different from the previous works, the relatively big volume of the reaction system made it possible to feed the acid gas in several steps from zero loading until the maximum loading, when no more CO2 enters the reactor at the set pressure (the absorption rate equals zero).
The acid gas in each loading interval was then absorbed by the amine solution preloaded in the previous loading interval. The loading span was kept rather low (0.03-0.07 mol CO2/mol amine), which gives Habs values that are semi-differential in loading.
The measurements were performed over 40-120 °C.
*
(an example of on-line data)
Here is an example of on-line data for CO2 absorption with 30 wt% MEA at 40oC.
The red solid line represents CO2 flow (integration gives an amount of CO2 fed in each loading interval)
The blue solid line represents Heat flow. Integrated over each loading interval it gives an amount of heat removed by the cooling system to keep the system at constant temperature, which is equal to the heat of physical absorption of CO2, its dissollution in the amine solution and chemical reaction with the amine.
It maybe seen from the pressure curve when all CO2 fed to the reactor is absorbed. When pressure goes up, CO2 is accumulated in the gas phase.
*
Results
MEA was selected as a “base case”. Heat of absorption of CO2 with MEA was measured at 40-120oC.
Experimental data are compared here with the differential enthalpy calculated from solubility data. Those data are close to the experimental values of the Habs at 40o.
It maybe seen a strong temperature dependency of the Habs.
Also Habs is almost constant upto the loading of about 0.5mol CO2/mol-amine, then it is drops very fast.
Chart1
0.037
0.0425
0.0357
0.05
0.05
0.0811
0.0918
0.0784
0.1
0.2
0.1244
0.1369
0.1206
0.2
0.4
0.1653
0.1808
0.1633
0.3
0.6
0.2103
0.2252
0.2106
0.4
0.8
0.2499
0.2761
0.2609
0.5
1
0.2899
0.3261
0.3099
0.6
1.2
0.3373
0.3745
0.3652
0.7
0.3752
0.4242
0.4097
0.8
0.4169
0.472
0.4454
0.9
0.4628
0.518
0.446
1
0.5073
0.5697
0.0511
0.543
0.594
0.1053
0.5757
0.6049
0.1521
0.6044
0.047
0.2276
0.6335
0.0904
0.2709
0.6514
0.1587
0.3385
0.6781
0.2033
0.3895
0.041
0.2419
0.4388
0.0843
0.2821
0.489
0.1244
0.333
0.5136
0.1674
0.3783
0.032
0.2109
0.423
0.0804
0.2555
0.4637
0.1187
0.3101
0.504
0.1606
0.3522
0.5451
0.2048
0.3968
0.5832
0.2486
0.4514
0.6212
0.2844
0.4935
0.6477
0.3247
0.5353
0.0405
0.3624
0.576
0.0871
0.4037
0.6082
0.1292
0.4482
0.6396
0.1706
0.4837
0.6615
0.2132
0.5033
0.6842
0.2526
0.704
0.3036
0.7153
0.3503
0.3891
0.4258
0.4686
0.5074
0.5585
0.5951
0.6286
40ºC
80ºC
120ºC
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
0.604
51.026
46.839
77.498
13-15.09.2005
0.047
93.363
4.388
93.363
0.228
113.214
28.024
112.373
40oC, 10MPa
80oC, 10MPa
120oC, 10MPa
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
30wt% MEA, 40oC [Mathonat et al., 1998]
30wt% MEA, 80oC [Mathonat et al., 1998]
30wt% MEA, Ingetral Habs, 80ºC
30wt% MEA, Ingetral Habs, 120ºC
30wt% MEA, 120oC [Mathonat et al., 1998]
MAPA
0.175
0.0857
0.1297
0.2003
0.1189
0.072
0.1724
0.2122
0.2022
0.1974
0.1706
0.1549
0.2499
0.1628
0.0876
0.2387
0.2586
0.2652
0.2197
0.1733
0.1715
0.2995
0.2066
0.1002
0.2586
0.2652
0.3183
0.2421
0.2568
0.1742
0.3016
0.2911
0.1189
0.305
0.2918
0.3437
0.2858
0.2618
0.2139
0.3533
0.3631
0.1502
0.3581
0.3437
0.3581
0.3039
0.3449
0.2186
0.3736
0.4131
0.2066
0.3713
0.3581
0.3979
0.3483
0.3889
0.2581
0.4508
0.4382
0.2911
0.4575
0.423
0.423
0.3491
0.3918
0.2631
0.599
0.5133
0.3631
0.4758
0.4575
0.4758
0.4373
0.4329
0.3024
0.7471
0.5822
0.4131
0.557
0.4758
0.5287
0.4817
0.483
0.3066
0.9017
0.651
0.4382
0.6366
0.4973
0.608
0.5262
0.521
0.3466
1.0563
0.7261
0.4757
0.6609
0.608
0.7402
0.5335
0.5632
0.3908
1.2108
0.8012
0.5133
0.7161
0.7402
0.9151
0.5688
0.6879
0.4351
1.3654
0.8764
0.5258
0.7402
0.8459
0.9946
0.6133
0.7796
0.5169
1.52
1.1643
0.5571
0.793
1.0045
1.114
0.6948
0.8695
0.5236
1.8291
1.1768
0.5822
0.7957
1.114
1.2731
0.8782
0.9613
0.566
2.1318
1.4523
0.7261
0.8459
1.2731
1.5118
1.0616
1.0511
0.6102
2.4152
1.7527
0.8764
0.8753
1.5118
1.9097
1.4303
1.4162
0.6914
2.0532
1.0266
1.0045
1.9097
2.2678
1.7972
1.7565
0.8739
2.3537
1.1768
1.1367
1.9826
2.164
2.4939
1.2707
2.9546
1.4523
1.2689
2.4584
2.5188
2.8607
1.4396
2.0532
1.5068
2.8893
3.2276
1.8196
2.6541
1.7447
3.2598
3.5944
2.1997
1.9826
3.6303
2.2205
4.0009
2.4849
2.7229
2.9607
3.7009
40oC, 10MPa
80oC, 10MPa
120oC, 10MPa
α, [mol-CO2/mol-MEA]
Habs, [kJ/mol-MEA]
12.3
7.8
13.6
18.8
11.7
7.4
12.7
22.6
23.7
13.4
15.9
15.4
21.4
14.8
9.1
17.8
31
26.2
14.5
15.4
16.9
24.9
19.8
10.5
19.8
25.8
34.3
16.7
23.5
17.8
25.9
26.8
12.5
22.6
29.2
34.5
20.5
23.2
22.4
28.8
33.5
15.3
27.3
37.1
36.2
22.8
31.3
22.2
31
39.4
22.6
26.4
38.6
40
23.7
35.1
25.5
36.5
39.6
29.2
35.2
46.7
42.6
25.6
33.9
26.5
47.2
43.9
36.1
38.8
44
45.8
32.6
38.6
30.4
50.2
46.5
43.5
38.6
47.4
46.7
34.6
41.1
30.4
53.6
50
42.3
42.1
39.8
47.9
37.7
44.4
34.4
57.1
52.7
39.8
48
51.7
48.6
40.8
46.2
38.2
56.9
54.3
42.5
49.8
50.1
48.8
39.5
50.2
41.9
57.1
54.2
46.9
46.5
53.5
48.8
47.2
51.9
47.2
58
54.9
48.7
50.1
53.1
48.7
49.1
51.5
47.8
57.5
54.8
49.8
50.7
54.5
48.7
53.4
51.8
47.7
57.5
54.9
49.9
49.9
54.6
48.5
55.9
52.1
47.5
57.5
54.8
50.9
51.1
54.5
48.2
56.3
51.5
47.9
54.6
51.1
50.9
54.5
47.9
56
50.1
47.1
54.3
50.3
51.4
53.4
56
52.6
49.9
54.2
49.3
50.8
53.9
56.6
51.8
48.1
49.7
51.1
57.1
51.2
46.6
50.7
51
56.6
50.1
43.2
51.4
56.8
51.4
56.8
51.2
51.2
51.1
50.8
DEEA
0.037
0.0425
0.0784
0.0811
0.0918
0.1206
0.1244
0.1369
0.1633
0.1653
0.1808
0.2106
0.2103
0.2252
0.2609
0.2499
0.2761
0.3099
0.2899
0.3261
0.3652
0.3373
0.3745
0.4097
0.3752
0.4242
0.4454
0.4169
0.472
0.446
0.4628
0.518
0.5073
0.5697
0.543
0.594
0.5757
0.6049
0.6044
0.6335
0.6514
0.6781
84.0786
95.2577
119.6583
83.0149254007
93.2705555556
111.914844942
82.6557075563
91.3061011687
112.2656112064
82.3813070175
92.3693889934
113.7423075024
82.1998504517
91.9158289964
111.5555381372
82.358194918
92.5958299529
110.5386911907
82.4164915833
93.2632279975
109.4471383625
81.8426056626
93.3810386382
109.2945612155
82.3066881663
93.515980976
108.0335303547
82.559700024
93.9949551059
108.0365807623
82.3755347018
93.3533478958
81.6028123596
91.0823641039
80.142760442
89.6255437542
78.8180974466
88.7720201686
77.498391413
75.7975232202
74.7032044059
73.0497217814
DEEA-MAPA
0.175
0.2003
0.1724
0.037
0.1974
0.2499
0.2387
0.0811
0.2197
0.2995
0.2586
0.1244
0.2421
0.3016
0.305
0.1653
0.2858
0.3533
0.3581
0.2103
0.3039
0.3736
0.3713
0.2499
0.3483
0.4508
0.4575
0.2899
0.3491
0.599
0.4758
0.3373
0.4373
0.7471
0.557
0.3752
0.4817
0.9017
0.6366
0.4169
0.5262
1.0563
0.6609
0.4628
0.5335
1.2108
0.7161
0.5073
0.5688
1.3654
0.7402
0.543
0.6133
1.52
0.793
0.5757
0.6948
1.8291
0.7957
0.6044
0.8782
2.1318
0.8459
0.6335
1.0616
2.4152
0.8753
0.6514
1.4303
1.0045
0.6781
1.7972
1.1367
2.164
1.2689
2.5188
1.5068
2.8893
1.7447
3.2598
1.9826
3.6303
2.2205
4.0009
2.4849
2.7229
2.9607
3.7009
40oC, 10MPa
80oC, 10MPa
120oC, 10MPa
40oC, 10MPa
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
03-04.04.2006
0.196
83.505
17.021
83.505
38835.000
0.047
86.367
4.030
86.367
1.254
53.324
97.507
77.121
2/6/06
0.422
79.251
33.439
95.747
1.401
43.356
103.853
73.592
2.142
27.614
123.870
108.801
13-14.12.2005
0.263
81.037
21.296
81.037
2.510
14.546
129.220
102.133
8 wt %
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
X = Am
X = CO2
MAPA 80º (I)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
3 wt %
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
38845.000
0.145
83.148
12.021
12/16/05
0.140
110.630
15.471
110.630
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Date
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
32 wt %
0.673
78.022
58.032
86.206
05-06.01.2006
0.085
93.947
7.985
93.947
0.727
72.463
61.932
85.189
0.682
75.498
60.399
88.599
16-17.01.2006
0.072
81.022
5.792
81.022
0.772
70.895
66.787
86.532
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
1/18/06
0.054
205.122
11.038
1/12/06
0.055
271.219
14.777
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
15-16.11.2005
0.070
83.331
5.851
83.331
12/20/05
0.064
78.973
5.032
78.973
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
X = Am
X = CO2
32% DEEA-8% MAPA 80º
0.900
58.441
68.071
75.652
21-22.12.2005
0.065
92.088
5.964
92.088
0.956
45.700
70.638
73.891
0.129
98.110
12.270
95.085
0.998
43.630
72.485
72.609
0.195
102.157
19.030
97.483
1.021
41.342
73.440
71.902
0.261
96.701
25.397
97.286
0.323
89.393
30.898
95.781
10/20/06
0.068
122.563
9.622
122.563
0.386
86.197
36.396
94.199
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
1/2/06
0.048
171.012
8.207
12/28/05
0.067
165.523
11.106
0.144
125.280
20.672
125.280
0.195
109.300
26.338
121.041
0.247
91.207
31.008
114.844
0.292
76.938
34.479
108.982
0.329
57.136
36.588
103.158
0.342
39.262
37.132
100.564
0
0
0
0
#REF!
#REF!
#REF!
#REF!
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Results
In our experiments with 30 wt% MDEA solution, Habs stronly depends on loading at the loadings below 0.3 mol CO2/mol-amine. The higher the temperature the higher is Habs.
After the loading of 0.3-0.35, it shows much less dependency on temperature but slowly decreases with loading.
Chart1
0.0908
0.0694
0.09
0.05
0.02
0.2858
0.29
0.29
0.2129
0.1435
0.1711
0.1
0.03
0.3565
0.3617
0.3617
0.3153
0.2221
0.2543
0.2
0.09
0.3801
0.3857
0.3857
0.4966
0.2983
0.3433
0.3
0.25
0.4302
0.4811
0.4365
0.6377
0.3915
0.372
0.4
0.5
0.4741
0.5806
0.4811
0.7572
0.4782
0.026
0.5
0.75
0.504
0.5862
0.5114
0.8704
0.5699
0.059
0.6
1.2
0.5722
0.6801
0.5806
0.9204
0.6569
0.0779
0.7
1.49
0.5777
0.7797
0.5862
0.0734
0.7473
0.1029
0.8
1.99
0.6515
0.8792
0.661
0.1567
0.8254
0.1277
0.9
2.98
0.6703
0.9356
0.6801
0.2365
0.0552
0.1564
1
0.7252
0.9787
0.7359
0.3029
0.1162
0.047
1.1
0.7684
1.055
0.7733
0.3783
0.175
0.0914
1.2
0.8583
1.0783
0.7797
0.4655
0.2343
0.139
0.8665
1.1745
0.8107
0.5466
0.293
0.1816
0.9646
1.2939
0.8792
0.6225
0.3504
1.0627
2.6118
0.8855
0.6988
0.411
1.1292
2.9074
0.9356
0.779
0.4727
1.1526
3.6485
0.9573
0.8874
0.5279
1.4084
4.4248
0.9787
0.9557
0.5813
1.4469
5.265
1.055
0.9812
0.0613
1.6998
6.028
1.1745
0.0909
0.1255
1.7412
1.4131
0.2068
0.254
1.9912
1.5278
0.3597
0.3172
2.0293
2.6118
0.496
0.3755
2.574
2.9074
0.598
0.4465
2.8654
3.2031
0.6829
0.5058
3.4988
0.7685
0.5581
0.8564
0.6097
0.9458
0.0861
0.1708
0.2773
0.3866
0.4594
0.5561
0.6413
40ºC
80ºC
120ºC
40oC, 5MPa [Mathonat, 1995]
80oC, 5MPa [Mathonat, 1995]
120oC, 5MPa [Mathonat, 1995]
* taken out at integration
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
0.081
99.662
8.292
101.878
0.077
92.372
7.162
93.586
0.117
89.412
10.758
92.146
0.270
94.351
25.217
93.397
0.303
93.294
28.329
93.386
0.341
88.628
31.670
92.860
0.380
91.079
35.209
92.678
0.417
88.143
38.515
92.270
0.454
81.857
41.468
91.441
0.491
72.983
44.202
90.035
0.530
70.194
46.936
88.575
0.570
58.745
49.268
86.496
0.601
44.123
50.661
84.268
MEA-AMP
0.0374
0.0359
0.0372
0.0773
0.0814
0.0801
0.1165
0.1252
0.1212
0.1597
0.1748
0.1649
0.2033
0.2503
0.2084
0.2435
0.2932
0.2709
0.2839
0.3365
0.3107
0.3243
0.3822
0.3489
0.3631
0.4267
0.3924
0.4072
0.4714
0.4314
0.4475
0.5151
0.4773
0.4905
0.5585
0.5148
0.5324
0.5934
0.5292
0.5735
0.62
0.6107
0.6397
40º
93.2186
104.6873
138.1985
90.338
99.6619
104.6962
94.9529
100.177
100.8886
88.9189
98.0683
108.6683
90.2089
100.1228
103.2075
92.37
100.545
103.7627
95.5343
96.6384
98.7469
90.6042
103.7893
93.81
83.248
88.8002
91.779
90.0994
91.4649
84.791
92.7065
76.5132
79.8064
77.2651
60.8646
74.5256
72.219
57.7255
49.8246
54.6256
36.1894
40.6549
24.3494
MDEA
0.0374
0.0359
0.0372
0.0773
0.0814
0.0801
0.1165
0.1252
0.1212
0.1597
0.1748
0.1649
0.2033
0.2503
0.2084
0.2435
0.2932
0.2709
0.2839
0.3365
0.3107
0.3243
0.3822
0.3489
0.3631
0.4267
0.3924
0.4072
0.4714
0.4314
0.4475
0.5151
0.4773
0.4905
0.5585
0.5148
0.5324
0.5934
0.5292
0.5735
0.62
0.6107
0.6397
40ºC
80ºC
120ºC
* taken out at integration
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
0.144
95.275
13.842
96.443
0.109
109.853
12.243
112.371
0.087
126.438
11.796
126.438
0.202
93.421
19.314
95.566
0.162
106.374
17.859
110.417
0.140
106.110
17.375
118.809
0.260
90.141
24.512
94.362
0.215
106.443
23.471
109.439
0.211
107.176
25.017
114.882
0.319
91.888
29.905
93.906
0.264
103.497
28.607
108.323
0.266
108.815
31.012
113.627
0.377
93.214
35.363
93.798
0.317
103.644
34.057
107.546
0.317
108.455
36.523
112.798
0.434
92.897
40.631
93.680
0.370
102.996
39.563
106.889
0.368
108.381
41.979
112.192
0.493
89.530
45.903
93.184
0.423
96.093
44.619
105.543
0.484
101.408
53.744
109.605
0.556
81.603
51.063
91.867
0.475
96.905
49.722
104.588
0.536
95.601
58.756
108.236
0.613
77.217
55.493
90.496
0.570
84.657
57.739
101.277
0.584
105.918
63.855
108.044
0.683
69.078
60.322
88.304
0.622
86.259
62.190
100.030
0.633
99.694
68.734
107.399
0.744
61.624
64.050
86.134
0.675
84.599
66.693
98.814
0.679
83.129
72.514
105.772
0.834
45.817
68.185
81.768
0.728
77.653
70.792
97.279
0.724
78.624
76.088
104.069
0.909
35.115
70.823
77.913
0.783
64.595
74.382
94.959
0.758
58.042
78.035
102.028
0.988
21.942
72.562
73.428
0.837
66.394
77.965
93.116
15-16.08.2007
0.053
117.672
6.283
117.672
09-11.07.2007
0.073
78.240
5.677
78.240
0.902
42.779
80.736
89.506
0.109
95.159
11.599
106.158
0.135
81.008
10.7535
79.521
09-10.08.2007
0.067
95.795
6.412
95.795
0.163
93.033
16.553
101.861
0.203
91.162
16.9258
83.405
0.134
94.254
12.691
95.026
0.225
107.867
23.313
103.533
0.267
89.612
22.7018
84.902
0.207
91.689
19.417
93.844
0.285
96.468
29.091
102.049
0.336
83.815
28.4891
84.679
0.262
89.425
24.333
92.916
0.347
101.519
35.338
101.955
0.407
86.440
34.5947
84.985
0.364
81.696
32.641
89.778
0.401
104.689
41.017
102.325
0.476
74.965
39.7459
83.538
0.428
91.738
38.554
90.072
0.454
110.959
46.864
103.328
0.541
69.357
44.2860
81.825
0.493
79.698
43.691
88.714
0.510
113.431
53.241
104.442
0.609
67.522
48.8482
80.236
0.554
72.182
48.144
86.873
0.566
84.805
57.967
102.508
0.677
68.792
53.5146
79.090
0.617
73.526
52.729
85.524
0.620
74.126
62.035
99.996
0.751
49.109
57.1861
76.105
0.676
71.427
57.001
84.278
0.685
71.707
66.679
97.324
0.734
57.844
60.355
82.190
0.746
59.480
70.279
94.249
0.791
53.991
63.424
80.162
0.804
64.434
74.009
92.101
0.864
47.734
76.875
89.018
MEA
0
0
0
0
#REF!
#REF!
#REF!
#REF!
97.8886
115.0917
143.9914
95.2753
109.8531
126.4375
93.4208
106.3738
106.1098
90.1413
106.4432
107.1759
91.8878
103.4966
108.815
93.214
103.6439
108.455
92.897
102.9955
108.3809
89.5304
96.0933
101.4075
81.6028
96.9047
95.6012
77.2166
84.6571
105.918
69.0779
86.2592
99.6935
61.6242
84.5991
83.1292
45.8169
77.6527
78.6242
35.1154
64.5948
58.0423
21.9422
66.3939
42.779
MAPA
0.0641
0.0524
0.0428
0.1435
0.109
0.0874
0.2021
0.1617
0.1399
0.2598
0.2145
0.2112
0.3185
0.2641
0.2663
0.377
0.3167
0.3171
0.4337
0.3701
0.3675
0.4926
0.4228
0.4835
0.5558
0.4754
0.5359
0.6132
0.5701
0.5841
0.6831
0.6217
0.633
0.7436
0.6749
0.6785
0.8339
0.7277
0.7239
0.909
0.7833
0.7575
0.9882
0.8373
0.902
40ºC
80ºC
120ºC
97.8886
115.0917
0
96.4426347038
112.371472844
126.4375
95.5664372093
110.4167581942
118.8091636883
94.3615472286
109.4386515618
114.8818355587
93.9056321193
108.32268883
113.6265496433
93.7983098939
107.545599179
112.7980579313
93.6804766659
106.8890866252
112.1922762721
93.1842535323
105.5434434011
109.6048221923
91.8673268262
104.5876211401
108.235555906
90.495911758
101.2769381863
108.0443109228
88.3042575026
100.0304924883
107.3992008847
86.1335427649
98.8140899393
105.7716621371
81.76780006
97.2786750859
104.0690861169
77.913459857
94.9587166348
102.0275019406
73.427602965
93.1164855368
89.5058033703
DEEA
0.0641
0.0524
0.0428
0.1435
0.109
0.0874
0.2021
0.1617
0.1399
0.2598
0.2145
0.2112
0.3185
0.2641
0.2663
0.377
0.3167
0.3171
0.4337
0.3701
0.3675
0.4926
0.4228
0.4835
0.5558
0.4754
0.5359
0.6132
0.5701
0.5841
0.6831
0.6217
0.633
0.7436
0.6749
0.6785
0.8339
0.7277
0.7239
0.909
0.7833
0.7575
0.9882
0.8373
0.902
40ºC
80ºC
120ºC
30% MDEA 40ºC, 2MPa *
30% MDEA 80ºC, 2MPa *
30% MDEA 120ºC, 2MPa *
40oC, 5MPa [Mathonat, 1995]
80oC, 5MPa [Mathonat, 1995]
120oC, 5MPa [Mathonat, 1995]
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
50 wt% MDEA, 75ºC
5/1/07
0.091
57.705
5.240
57.705
11-13.07.2005
0.090
95.198
8.558
95.198
29-30.06.2005
0.036
115.551
8.558
115.551
11/16/06
0.068
115.164
8.794
115.164
23-24.10.2006
0.090
145.320
13.081
145.320
10 bar
0.870
50.357
45.637
52.434
0.508
52.488
34.708
68.364
0.238
79.058
34.708
92.970
4/26/06
0.026
328.272
8.544
0.597
48.963
39.122
65.541
0.103
168.193
22.400
181.732
0.378
51.373
21.180
55.985
0.838
38.572
49.654
59.246
0.478
58.275
43.295
81.963
0.981
44.426
50.033
50.993
0.491
49.202
31.757
64.743
6/24/06
0.055
160.685
8.871
160.685
0.536
45.881
33.831
63.152
35%, 76.7º [Oscarson et al., 2000]
0.528
57.930
46.599
88.274
0.856
39.988
39.776
46.445
40 wt% MDEA, 40ºC
50 wt% MDEA, 40ºC
8.7732
15.8793
26.1557
30.4698
34.1108
38.1897
41.4504
44.087
46.6274
47.611
0.0909
0.2068
0.3597
0.496
0.598
0.6829
0.7685
0.8564
0.9458
1.0335
53.3333
52.7568264023
50.2761540172
49.333525746
48.4156407525
47.8093758383
47.1837243982
46.4451217188
45.6958251639
44.4650954523
0
0
0
0
10
10
10
10
20
20
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30
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50
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540
550
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890
890
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930
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970
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980
980
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980
990
990
990
990
1000
1000
1000
1000
1010
1010
1010
1010
1020
1020
1020
1020
1030
1030
1030
1030
1040
1040
1040
1040
1050
1050
1050
1050
1060
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1060
1060
1070
1070
1070
1070
1080
1080
1080
1080
1090
1090
1090
1090
1100
1100
1100
1100
1110
1110
1110
1110
1120
1120
1120
1120
1130
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1180
1190
1190
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1190
1200
1200
1200
1200
1210
1210
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1210
1220
1220
1220
1220
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1300
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1390
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1590
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1383
Norwegian University of Science and Technology (NTNU)
Trondheim, NORWAY
Even though amine sweetening of gases and liquids has been used for many decades, the process is still being refined and improved to be more efficient.
*
*
Habs
The overall challenge of the project is to bring the cost down to the point where it becomes an attractive option in mitigation of global warming.
The cost of the process stems from several components. There is the cost of building the plant and purchasing the solvents. There are also the operational costs, in particular, the energy required to run the process.
Thermal energy is required to heat the solvent entering the stripper, to generate the heat required to release CO2 and to generate steam for dilution of the striper.
Information on the heats of reaction of acid gases (mainly CO2 and H2S) in aqueous solutions of alkanolamines is of prime importance for designing unit operations for acid gas removal, because it is directly related to the steam requirements of the amine regeneration stage.
*
Integrated over some loading interval (direct measurement)
Isothermal flow calorimeter
Background
In literature the heat of absorption is referred to as an Integral or Differential Habs.
Integral (calorimetric measurements)
The technique involved mixing varying amounts of acid gas with a fixed flow of clean amine solution, then using a flow calorimeter to measure the cooling required to exit at the same temperature and pressure as the inlet.
“Enthalpy of solution” calculated as the total energy required to maintain the inlet conditions divided by the total number of moles of acid gas flowing in the system.
These values are integral in loading and differential in temperature
Differential (from solubility measurements using Gibbs-Helmholtz equation)
En approximate value of the differential enthalpy of solution of CO2 in the aqueous alkanolamine solution is calculated by use of the following form of the Gibbs-Helmholtz equation, where xCO2 is the mole fraction or equilibrium loading of CO2.
*
VLE data: ln(pCO2) vs 1/T:
Fitted with a line,
1 [Hoff K.A., Mejdell T., Svendsen H.., 2005]
a
b
Background
To calculate differential Habs from VLE data, log of experimental vapour pressure (ln Pvap) is plotted against reciprocal temperature (1/T). We can fit these data points with a straint line (Fig. a) or second order polynomial (Fig. b). Both curves seems to fit the data very well.
However, if we do now differentiation to calculate the Habs, we will have constant Habs ( independent on temperature) in the first case and Habs with very strong temperature dependency in the second case.
It is a common practice to use a line fitted to the data.
*
Temperature profile for the Dome 5
North Caroline plant 2
“The increase in heat of absorption of up to 20% from the absorber to the stripper temperature may cause a deficient duty calculation with the reboiler if a constant heat of absorption at the lower value is used”2
2 [Jerry A. Bullin et al., Bryan Research & Engineering Inc. Bryan, TX, GPA 2007]
Background
Impact of temperature on the heat of absorption has not been sufficiently appreciated previously. According to the given reference, the increase in heat of absorption of up to 20% from the absorber to the stripper temperature may cause a deficient duty calculation with the reboiler if a constant heat of absorption at the lower value is used.
Knowledge of the effects of acid gas loading and other parameters on the heat of absorption can be used to more accurately predict and improve calculations in designing and operating amine sweetening facilities. Improved values for the heat of absorption allow more accurate calculations of the temperature profiles as well as exit rich amine temperatures from absorbers.
A nice example was provided in the article (ref) for the Dome North Caroline plant. The picture to the right, contains measured absorber temperature profiles for five sets of operating conditions.
*
3 - Vacuum pump
4 - Feed bottle
This work considers the impact of acid gas loading on the heats of absorption for CO2.
Since the heats of absorption vary with temperature, amine type, and solution concentration, the impact of those parameters is also investigated.
The Habs values of CO2 with MEA were measured using a reaction calorimeter with a reactor volume of 2 L.
Different from the previous works, the relatively big volume of the reaction system made it possible to feed the acid gas in several steps from zero loading until the maximum loading, when no more CO2 enters the reactor at the set pressure (the absorption rate equals zero).
The acid gas in each loading interval was then absorbed by the amine solution preloaded in the previous loading interval. The loading span was kept rather low (0.03-0.07 mol CO2/mol amine), which gives Habs values that are semi-differential in loading.
The measurements were performed over 40-120 °C.
*
(an example of on-line data)
Here is an example of on-line data for CO2 absorption with 30 wt% MEA at 40oC.
The red solid line represents CO2 flow (integration gives an amount of CO2 fed in each loading interval)
The blue solid line represents Heat flow. Integrated over each loading interval it gives an amount of heat removed by the cooling system to keep the system at constant temperature, which is equal to the heat of physical absorption of CO2, its dissollution in the amine solution and chemical reaction with the amine.
It maybe seen from the pressure curve when all CO2 fed to the reactor is absorbed. When pressure goes up, CO2 is accumulated in the gas phase.
*
Results
MEA was selected as a “base case”. Heat of absorption of CO2 with MEA was measured at 40-120oC.
Experimental data are compared here with the differential enthalpy calculated from solubility data. Those data are close to the experimental values of the Habs at 40o.
It maybe seen a strong temperature dependency of the Habs.
Also Habs is almost constant upto the loading of about 0.5mol CO2/mol-amine, then it is drops very fast.
Chart1
0.037
0.0425
0.0357
0.05
0.05
0.0811
0.0918
0.0784
0.1
0.2
0.1244
0.1369
0.1206
0.2
0.4
0.1653
0.1808
0.1633
0.3
0.6
0.2103
0.2252
0.2106
0.4
0.8
0.2499
0.2761
0.2609
0.5
1
0.2899
0.3261
0.3099
0.6
1.2
0.3373
0.3745
0.3652
0.7
0.3752
0.4242
0.4097
0.8
0.4169
0.472
0.4454
0.9
0.4628
0.518
0.446
1
0.5073
0.5697
0.0511
0.543
0.594
0.1053
0.5757
0.6049
0.1521
0.6044
0.047
0.2276
0.6335
0.0904
0.2709
0.6514
0.1587
0.3385
0.6781
0.2033
0.3895
0.041
0.2419
0.4388
0.0843
0.2821
0.489
0.1244
0.333
0.5136
0.1674
0.3783
0.032
0.2109
0.423
0.0804
0.2555
0.4637
0.1187
0.3101
0.504
0.1606
0.3522
0.5451
0.2048
0.3968
0.5832
0.2486
0.4514
0.6212
0.2844
0.4935
0.6477
0.3247
0.5353
0.0405
0.3624
0.576
0.0871
0.4037
0.6082
0.1292
0.4482
0.6396
0.1706
0.4837
0.6615
0.2132
0.5033
0.6842
0.2526
0.704
0.3036
0.7153
0.3503
0.3891
0.4258
0.4686
0.5074
0.5585
0.5951
0.6286
40ºC
80ºC
120ºC
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
0.604
51.026
46.839
77.498
13-15.09.2005
0.047
93.363
4.388
93.363
0.228
113.214
28.024
112.373
40oC, 10MPa
80oC, 10MPa
120oC, 10MPa
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
α, mol-CO2/mol-MEA
Habs, kJ/mol-CO2
Habs, kJ/mol-MEA
30wt% MEA, 40oC [Mathonat et al., 1998]
30wt% MEA, 80oC [Mathonat et al., 1998]
30wt% MEA, Ingetral Habs, 80ºC
30wt% MEA, Ingetral Habs, 120ºC
30wt% MEA, 120oC [Mathonat et al., 1998]
MAPA
0.175
0.0857
0.1297
0.2003
0.1189
0.072
0.1724
0.2122
0.2022
0.1974
0.1706
0.1549
0.2499
0.1628
0.0876
0.2387
0.2586
0.2652
0.2197
0.1733
0.1715
0.2995
0.2066
0.1002
0.2586
0.2652
0.3183
0.2421
0.2568
0.1742
0.3016
0.2911
0.1189
0.305
0.2918
0.3437
0.2858
0.2618
0.2139
0.3533
0.3631
0.1502
0.3581
0.3437
0.3581
0.3039
0.3449
0.2186
0.3736
0.4131
0.2066
0.3713
0.3581
0.3979
0.3483
0.3889
0.2581
0.4508
0.4382
0.2911
0.4575
0.423
0.423
0.3491
0.3918
0.2631
0.599
0.5133
0.3631
0.4758
0.4575
0.4758
0.4373
0.4329
0.3024
0.7471
0.5822
0.4131
0.557
0.4758
0.5287
0.4817
0.483
0.3066
0.9017
0.651
0.4382
0.6366
0.4973
0.608
0.5262
0.521
0.3466
1.0563
0.7261
0.4757
0.6609
0.608
0.7402
0.5335
0.5632
0.3908
1.2108
0.8012
0.5133
0.7161
0.7402
0.9151
0.5688
0.6879
0.4351
1.3654
0.8764
0.5258
0.7402
0.8459
0.9946
0.6133
0.7796
0.5169
1.52
1.1643
0.5571
0.793
1.0045
1.114
0.6948
0.8695
0.5236
1.8291
1.1768
0.5822
0.7957
1.114
1.2731
0.8782
0.9613
0.566
2.1318
1.4523
0.7261
0.8459
1.2731
1.5118
1.0616
1.0511
0.6102
2.4152
1.7527
0.8764
0.8753
1.5118
1.9097
1.4303
1.4162
0.6914
2.0532
1.0266
1.0045
1.9097
2.2678
1.7972
1.7565
0.8739
2.3537
1.1768
1.1367
1.9826
2.164
2.4939
1.2707
2.9546
1.4523
1.2689
2.4584
2.5188
2.8607
1.4396
2.0532
1.5068
2.8893
3.2276
1.8196
2.6541
1.7447
3.2598
3.5944
2.1997
1.9826
3.6303
2.2205
4.0009
2.4849
2.7229
2.9607
3.7009
40oC, 10MPa
80oC, 10MPa
120oC, 10MPa
α, [mol-CO2/mol-MEA]
Habs, [kJ/mol-MEA]
12.3
7.8
13.6
18.8
11.7
7.4
12.7
22.6
23.7
13.4
15.9
15.4
21.4
14.8
9.1
17.8
31
26.2
14.5
15.4
16.9
24.9
19.8
10.5
19.8
25.8
34.3
16.7
23.5
17.8
25.9
26.8
12.5
22.6
29.2
34.5
20.5
23.2
22.4
28.8
33.5
15.3
27.3
37.1
36.2
22.8
31.3
22.2
31
39.4
22.6
26.4
38.6
40
23.7
35.1
25.5
36.5
39.6
29.2
35.2
46.7
42.6
25.6
33.9
26.5
47.2
43.9
36.1
38.8
44
45.8
32.6
38.6
30.4
50.2
46.5
43.5
38.6
47.4
46.7
34.6
41.1
30.4
53.6
50
42.3
42.1
39.8
47.9
37.7
44.4
34.4
57.1
52.7
39.8
48
51.7
48.6
40.8
46.2
38.2
56.9
54.3
42.5
49.8
50.1
48.8
39.5
50.2
41.9
57.1
54.2
46.9
46.5
53.5
48.8
47.2
51.9
47.2
58
54.9
48.7
50.1
53.1
48.7
49.1
51.5
47.8
57.5
54.8
49.8
50.7
54.5
48.7
53.4
51.8
47.7
57.5
54.9
49.9
49.9
54.6
48.5
55.9
52.1
47.5
57.5
54.8
50.9
51.1
54.5
48.2
56.3
51.5
47.9
54.6
51.1
50.9
54.5
47.9
56
50.1
47.1
54.3
50.3
51.4
53.4
56
52.6
49.9
54.2
49.3
50.8
53.9
56.6
51.8
48.1
49.7
51.1
57.1
51.2
46.6
50.7
51
56.6
50.1
43.2
51.4
56.8
51.4
56.8
51.2
51.2
51.1
50.8
DEEA
0.037
0.0425
0.0784
0.0811
0.0918
0.1206
0.1244
0.1369
0.1633
0.1653
0.1808
0.2106
0.2103
0.2252
0.2609
0.2499
0.2761
0.3099
0.2899
0.3261
0.3652
0.3373
0.3745
0.4097
0.3752
0.4242
0.4454
0.4169
0.472
0.446
0.4628
0.518
0.5073
0.5697
0.543
0.594
0.5757
0.6049
0.6044
0.6335
0.6514
0.6781
84.0786
95.2577
119.6583
83.0149254007
93.2705555556
111.914844942
82.6557075563
91.3061011687
112.2656112064
82.3813070175
92.3693889934
113.7423075024
82.1998504517
91.9158289964
111.5555381372
82.358194918
92.5958299529
110.5386911907
82.4164915833
93.2632279975
109.4471383625
81.8426056626
93.3810386382
109.2945612155
82.3066881663
93.515980976
108.0335303547
82.559700024
93.9949551059
108.0365807623
82.3755347018
93.3533478958
81.6028123596
91.0823641039
80.142760442
89.6255437542
78.8180974466
88.7720201686
77.498391413
75.7975232202
74.7032044059
73.0497217814
DEEA-MAPA
0.175
0.2003
0.1724
0.037
0.1974
0.2499
0.2387
0.0811
0.2197
0.2995
0.2586
0.1244
0.2421
0.3016
0.305
0.1653
0.2858
0.3533
0.3581
0.2103
0.3039
0.3736
0.3713
0.2499
0.3483
0.4508
0.4575
0.2899
0.3491
0.599
0.4758
0.3373
0.4373
0.7471
0.557
0.3752
0.4817
0.9017
0.6366
0.4169
0.5262
1.0563
0.6609
0.4628
0.5335
1.2108
0.7161
0.5073
0.5688
1.3654
0.7402
0.543
0.6133
1.52
0.793
0.5757
0.6948
1.8291
0.7957
0.6044
0.8782
2.1318
0.8459
0.6335
1.0616
2.4152
0.8753
0.6514
1.4303
1.0045
0.6781
1.7972
1.1367
2.164
1.2689
2.5188
1.5068
2.8893
1.7447
3.2598
1.9826
3.6303
2.2205
4.0009
2.4849
2.7229
2.9607
3.7009
40oC, 10MPa
80oC, 10MPa
120oC, 10MPa
40oC, 10MPa
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
03-04.04.2006
0.196
83.505
17.021
83.505
38835.000
0.047
86.367
4.030
86.367
1.254
53.324
97.507
77.121
2/6/06
0.422
79.251
33.439
95.747
1.401
43.356
103.853
73.592
2.142
27.614
123.870
108.801
13-14.12.2005
0.263
81.037
21.296
81.037
2.510
14.546
129.220
102.133
8 wt %
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
X = Am
X = CO2
MAPA 80º (I)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
3 wt %
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
38845.000
0.145
83.148
12.021
12/16/05
0.140
110.630
15.471
110.630
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Date
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
32 wt %
0.673
78.022
58.032
86.206
05-06.01.2006
0.085
93.947
7.985
93.947
0.727
72.463
61.932
85.189
0.682
75.498
60.399
88.599
16-17.01.2006
0.072
81.022
5.792
81.022
0.772
70.895
66.787
86.532
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
1/18/06
0.054
205.122
11.038
1/12/06
0.055
271.219
14.777
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
15-16.11.2005
0.070
83.331
5.851
83.331
12/20/05
0.064
78.973
5.032
78.973
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
X = Am
X = CO2
32% DEEA-8% MAPA 80º
0.900
58.441
68.071
75.652
21-22.12.2005
0.065
92.088
5.964
92.088
0.956
45.700
70.638
73.891
0.129
98.110
12.270
95.085
0.998
43.630
72.485
72.609
0.195
102.157
19.030
97.483
1.021
41.342
73.440
71.902
0.261
96.701
25.397
97.286
0.323
89.393
30.898
95.781
10/20/06
0.068
122.563
9.622
122.563
0.386
86.197
36.396
94.199
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
1/2/06
0.048
171.012
8.207
12/28/05
0.067
165.523
11.106
0.144
125.280
20.672
125.280
0.195
109.300
26.338
121.041
0.247
91.207
31.008
114.844
0.292
76.938
34.479
108.982
0.329
57.136
36.588
103.158
0.342
39.262
37.132
100.564
0
0
0
0
#REF!
#REF!
#REF!
#REF!
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Hdiff (kJ/mol CO2)
Hint (kJ/mol X)
Results
In our experiments with 30 wt% MDEA solution, Habs stronly depends on loading at the loadings below 0.3 mol CO2/mol-amine. The higher the temperature the higher is Habs.
After the loading of 0.3-0.35, it shows much less dependency on temperature but slowly decreases with loading.
Chart1
0.0908
0.0694
0.09
0.05
0.02
0.2858
0.29
0.29
0.2129
0.1435
0.1711
0.1
0.03
0.3565
0.3617
0.3617
0.3153
0.2221
0.2543
0.2
0.09
0.3801
0.3857
0.3857
0.4966
0.2983
0.3433
0.3
0.25
0.4302
0.4811
0.4365
0.6377
0.3915
0.372
0.4
0.5
0.4741
0.5806
0.4811
0.7572
0.4782
0.026
0.5
0.75
0.504
0.5862
0.5114
0.8704
0.5699
0.059
0.6
1.2
0.5722
0.6801
0.5806
0.9204
0.6569
0.0779
0.7
1.49
0.5777
0.7797
0.5862
0.0734
0.7473
0.1029
0.8
1.99
0.6515
0.8792
0.661
0.1567
0.8254
0.1277
0.9
2.98
0.6703
0.9356
0.6801
0.2365
0.0552
0.1564
1
0.7252
0.9787
0.7359
0.3029
0.1162
0.047
1.1
0.7684
1.055
0.7733
0.3783
0.175
0.0914
1.2
0.8583
1.0783
0.7797
0.4655
0.2343
0.139
0.8665
1.1745
0.8107
0.5466
0.293
0.1816
0.9646
1.2939
0.8792
0.6225
0.3504
1.0627
2.6118
0.8855
0.6988
0.411
1.1292
2.9074
0.9356
0.779
0.4727
1.1526
3.6485
0.9573
0.8874
0.5279
1.4084
4.4248
0.9787
0.9557
0.5813
1.4469
5.265
1.055
0.9812
0.0613
1.6998
6.028
1.1745
0.0909
0.1255
1.7412
1.4131
0.2068
0.254
1.9912
1.5278
0.3597
0.3172
2.0293
2.6118
0.496
0.3755
2.574
2.9074
0.598
0.4465
2.8654
3.2031
0.6829
0.5058
3.4988
0.7685
0.5581
0.8564
0.6097
0.9458
0.0861
0.1708
0.2773
0.3866
0.4594
0.5561
0.6413
40ºC
80ºC
120ºC
40oC, 5MPa [Mathonat, 1995]
80oC, 5MPa [Mathonat, 1995]
120oC, 5MPa [Mathonat, 1995]
* taken out at integration
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
0.081
99.662
8.292
101.878
0.077
92.372
7.162
93.586
0.117
89.412
10.758
92.146
0.270
94.351
25.217
93.397
0.303
93.294
28.329
93.386
0.341
88.628
31.670
92.860
0.380
91.079
35.209
92.678
0.417
88.143
38.515
92.270
0.454
81.857
41.468
91.441
0.491
72.983
44.202
90.035
0.530
70.194
46.936
88.575
0.570
58.745
49.268
86.496
0.601
44.123
50.661
84.268
MEA-AMP
0.0374
0.0359
0.0372
0.0773
0.0814
0.0801
0.1165
0.1252
0.1212
0.1597
0.1748
0.1649
0.2033
0.2503
0.2084
0.2435
0.2932
0.2709
0.2839
0.3365
0.3107
0.3243
0.3822
0.3489
0.3631
0.4267
0.3924
0.4072
0.4714
0.4314
0.4475
0.5151
0.4773
0.4905
0.5585
0.5148
0.5324
0.5934
0.5292
0.5735
0.62
0.6107
0.6397
40º
93.2186
104.6873
138.1985
90.338
99.6619
104.6962
94.9529
100.177
100.8886
88.9189
98.0683
108.6683
90.2089
100.1228
103.2075
92.37
100.545
103.7627
95.5343
96.6384
98.7469
90.6042
103.7893
93.81
83.248
88.8002
91.779
90.0994
91.4649
84.791
92.7065
76.5132
79.8064
77.2651
60.8646
74.5256
72.219
57.7255
49.8246
54.6256
36.1894
40.6549
24.3494
MDEA
0.0374
0.0359
0.0372
0.0773
0.0814
0.0801
0.1165
0.1252
0.1212
0.1597
0.1748
0.1649
0.2033
0.2503
0.2084
0.2435
0.2932
0.2709
0.2839
0.3365
0.3107
0.3243
0.3822
0.3489
0.3631
0.4267
0.3924
0.4072
0.4714
0.4314
0.4475
0.5151
0.4773
0.4905
0.5585
0.5148
0.5324
0.5934
0.5292
0.5735
0.62
0.6107
0.6397
40ºC
80ºC
120ºC
* taken out at integration
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
0.144
95.275
13.842
96.443
0.109
109.853
12.243
112.371
0.087
126.438
11.796
126.438
0.202
93.421
19.314
95.566
0.162
106.374
17.859
110.417
0.140
106.110
17.375
118.809
0.260
90.141
24.512
94.362
0.215
106.443
23.471
109.439
0.211
107.176
25.017
114.882
0.319
91.888
29.905
93.906
0.264
103.497
28.607
108.323
0.266
108.815
31.012
113.627
0.377
93.214
35.363
93.798
0.317
103.644
34.057
107.546
0.317
108.455
36.523
112.798
0.434
92.897
40.631
93.680
0.370
102.996
39.563
106.889
0.368
108.381
41.979
112.192
0.493
89.530
45.903
93.184
0.423
96.093
44.619
105.543
0.484
101.408
53.744
109.605
0.556
81.603
51.063
91.867
0.475
96.905
49.722
104.588
0.536
95.601
58.756
108.236
0.613
77.217
55.493
90.496
0.570
84.657
57.739
101.277
0.584
105.918
63.855
108.044
0.683
69.078
60.322
88.304
0.622
86.259
62.190
100.030
0.633
99.694
68.734
107.399
0.744
61.624
64.050
86.134
0.675
84.599
66.693
98.814
0.679
83.129
72.514
105.772
0.834
45.817
68.185
81.768
0.728
77.653
70.792
97.279
0.724
78.624
76.088
104.069
0.909
35.115
70.823
77.913
0.783
64.595
74.382
94.959
0.758
58.042
78.035
102.028
0.988
21.942
72.562
73.428
0.837
66.394
77.965
93.116
15-16.08.2007
0.053
117.672
6.283
117.672
09-11.07.2007
0.073
78.240
5.677
78.240
0.902
42.779
80.736
89.506
0.109
95.159
11.599
106.158
0.135
81.008
10.7535
79.521
09-10.08.2007
0.067
95.795
6.412
95.795
0.163
93.033
16.553
101.861
0.203
91.162
16.9258
83.405
0.134
94.254
12.691
95.026
0.225
107.867
23.313
103.533
0.267
89.612
22.7018
84.902
0.207
91.689
19.417
93.844
0.285
96.468
29.091
102.049
0.336
83.815
28.4891
84.679
0.262
89.425
24.333
92.916
0.347
101.519
35.338
101.955
0.407
86.440
34.5947
84.985
0.364
81.696
32.641
89.778
0.401
104.689
41.017
102.325
0.476
74.965
39.7459
83.538
0.428
91.738
38.554
90.072
0.454
110.959
46.864
103.328
0.541
69.357
44.2860
81.825
0.493
79.698
43.691
88.714
0.510
113.431
53.241
104.442
0.609
67.522
48.8482
80.236
0.554
72.182
48.144
86.873
0.566
84.805
57.967
102.508
0.677
68.792
53.5146
79.090
0.617
73.526
52.729
85.524
0.620
74.126
62.035
99.996
0.751
49.109
57.1861
76.105
0.676
71.427
57.001
84.278
0.685
71.707
66.679
97.324
0.734
57.844
60.355
82.190
0.746
59.480
70.279
94.249
0.791
53.991
63.424
80.162
0.804
64.434
74.009
92.101
0.864
47.734
76.875
89.018
MEA
0
0
0
0
#REF!
#REF!
#REF!
#REF!
97.8886
115.0917
143.9914
95.2753
109.8531
126.4375
93.4208
106.3738
106.1098
90.1413
106.4432
107.1759
91.8878
103.4966
108.815
93.214
103.6439
108.455
92.897
102.9955
108.3809
89.5304
96.0933
101.4075
81.6028
96.9047
95.6012
77.2166
84.6571
105.918
69.0779
86.2592
99.6935
61.6242
84.5991
83.1292
45.8169
77.6527
78.6242
35.1154
64.5948
58.0423
21.9422
66.3939
42.779
MAPA
0.0641
0.0524
0.0428
0.1435
0.109
0.0874
0.2021
0.1617
0.1399
0.2598
0.2145
0.2112
0.3185
0.2641
0.2663
0.377
0.3167
0.3171
0.4337
0.3701
0.3675
0.4926
0.4228
0.4835
0.5558
0.4754
0.5359
0.6132
0.5701
0.5841
0.6831
0.6217
0.633
0.7436
0.6749
0.6785
0.8339
0.7277
0.7239
0.909
0.7833
0.7575
0.9882
0.8373
0.902
40ºC
80ºC
120ºC
97.8886
115.0917
0
96.4426347038
112.371472844
126.4375
95.5664372093
110.4167581942
118.8091636883
94.3615472286
109.4386515618
114.8818355587
93.9056321193
108.32268883
113.6265496433
93.7983098939
107.545599179
112.7980579313
93.6804766659
106.8890866252
112.1922762721
93.1842535323
105.5434434011
109.6048221923
91.8673268262
104.5876211401
108.235555906
90.495911758
101.2769381863
108.0443109228
88.3042575026
100.0304924883
107.3992008847
86.1335427649
98.8140899393
105.7716621371
81.76780006
97.2786750859
104.0690861169
77.913459857
94.9587166348
102.0275019406
73.427602965
93.1164855368
89.5058033703
DEEA
0.0641
0.0524
0.0428
0.1435
0.109
0.0874
0.2021
0.1617
0.1399
0.2598
0.2145
0.2112
0.3185
0.2641
0.2663
0.377
0.3167
0.3171
0.4337
0.3701
0.3675
0.4926
0.4228
0.4835
0.5558
0.4754
0.5359
0.6132
0.5701
0.5841
0.6831
0.6217
0.633
0.7436
0.6749
0.6785
0.8339
0.7277
0.7239
0.909
0.7833
0.7575
0.9882
0.8373
0.902
40ºC
80ºC
120ºC
30% MDEA 40ºC, 2MPa *
30% MDEA 80ºC, 2MPa *
30% MDEA 120ºC, 2MPa *
40oC, 5MPa [Mathonat, 1995]
80oC, 5MPa [Mathonat, 1995]
120oC, 5MPa [Mathonat, 1995]
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
α, mol-CO2/mol-MDEA
Habs, kJ/mol-MDEA
Habs, kJ/mol-CO2
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
Hdiff, (kJ/mol CO2)
Hint, (kJ/mol X)
50 wt% MDEA, 75ºC
5/1/07
0.091
57.705
5.240
57.705
11-13.07.2005
0.090
95.198
8.558
95.198
29-30.06.2005
0.036
115.551
8.558
115.551
11/16/06
0.068
115.164
8.794
115.164
23-24.10.2006
0.090
145.320
13.081
145.320
10 bar
0.870
50.357
45.637
52.434
0.508
52.488
34.708
68.364
0.238
79.058
34.708
92.970
4/26/06
0.026
328.272
8.544
0.597
48.963
39.122
65.541
0.103
168.193
22.400
181.732
0.378
51.373
21.180
55.985
0.838
38.572
49.654
59.246
0.478
58.275
43.295
81.963
0.981
44.426
50.033
50.993
0.491
49.202
31.757
64.743
6/24/06
0.055
160.685
8.871
160.685
0.536
45.881
33.831
63.152
35%, 76.7º [Oscarson et al., 2000]
0.528
57.930
46.599
88.274
0.856
39.988
39.776
46.445
40 wt% MDEA, 40ºC
50 wt% MDEA, 40ºC
8.7732
15.8793
26.1557
30.4698
34.1108
38.1897
41.4504
44.087
46.6274
47.611
0.0909
0.2068
0.3597
0.496
0.598
0.6829
0.7685
0.8564
0.9458
1.0335
53.3333
52.7568264023
50.2761540172
49.333525746
48.4156407525
47.8093758383
47.1837243982
46.4451217188
45.6958251639
44.4650954523
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![[Adam D.M. Svendsen] Intelligence Cooperation and](https://static.fdocuments.in/doc/165x107/55cf8f89550346703b9d3a56/adam-dm-svendsen-intelligence-cooperation-and.jpg)
