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Abstract
In this work, the activation energy of for the formation reaction of tert-amyl ethyl ether
(TAEE) from isoamylenes (2-methyl-1-butene and 2-methyl-2-butene) and the
ethanol was determined as equivalent to 90.67 kJ/mol. The reaction was studied in
the presence of Amberlyst 15 resin as a catalyst in a stirred batch reactor. The
calculation was based on an elementary reaction model without consideration of
reaction equilibrium.
Table of contents
1.
Introduction ............................................................................................... 1
2.
3.
Results ...................................................................................................... 5
4.
Discussion .............................................................................................. 14
5.
Conclusions ............................................................................................ 14
6.
7.
References ............................................................................................. 15
1. Introduction
In this particular work the activation energy of the formation reaction of tert-amyl ethyl ether
(TAEE) from isoamylenes and the ethanol was studied. Ethers, TAEE and tert-amyl methyl
ether (TAME) are used as oxygenates in gasoline fuel. Due to their high octane number, they
offer excellent fuel properties for instance enhancement of fuel burning. Also use of
oxygenates in gasoline contribute to reduction of emissions such as CO, hydrocarbons (HC),
volatile organic compounds (VOCs) and particulates (PM) [1, 2]. Furthermore, substitution of
ethers such as TAEE in gasoline instead of ethanol is said to provide better energy efficiency
(meaning less consumption of fuel) and consequently notable reduction in CO2 emissions
[2, 3]. The studied reaction is presented in Scheme I.
Scheme I
The reaction shown in Scheme I was assumed to behave as an elementary reaction which
proceeds according to reaction Equation (1), where A, B and C represents ethanol
isoamylenes, and tert-amyl ethyl ether respectively.
+
(1)
Calculation methods
Determination of response factors
In the gas chromatographic (GC) analytical method, cyclohexane was used as the internal
standard. The GC response factor for each component was determined using Equation (2)
and based on the slopes of the given calibration curves (See Appendix A, Table A-1).
(2)
,
,
(3)
,
Determination of the reaction rate and kinetic constant
For a batch reactor the reaction rate can be expressed as in Equation (4). Conversion of
ethanol (component A) was used in calculations and was obtained according to equation (5).
Based on the reaction conversion, Equations (6) and (7) were deduced.
= =
, = 0 (1 )
0
(1 )
0
(0 )
0
(4)
(5)
0 , 0 & ,
, .
0 ,
0
= 0 (1 )
(1 )
0
= .
(1 )2
(6)
(7)
Integrating Equation (7) yields Equation (8) from which k can be determined (See
Appendix B, Figure B-3 for further details about integration) [4].
0
= .
1
0
(8)
(9)
() =
() ,
() = ln
(10)
3. Results
The results obtained are presented here and include analytical assays, reaction conversion,
reaction rates, rate constants and the estimated activation energy.
Analytical assays
Determination of Response factors
From Equation (2) response factors of individual components were calculated. As an
example, determination of the response factor of ethanol is shown below. Response factor
results are given in Table 1.
159575
=
= 2.05
77793
Slope
Response factor
Cyclohexane
159575
1.00
Isoamylenes
146812
1.09
Ethanol
77793
2.05
TAEE
118434
1.35
As a calculation example for mole fractions, component mole fractions of feed sample are
calculated below (where MW represents molecular weight).
(
) (0.212 69.125)
=
=
= 0.318
46.07
(
)
(
)
= (0.150 69.125) = 0.148
=
70.13
(
)
(
) (0.000232 69.125)
=
=
= 0.000157
102.17
(
)
The full analytical results showing the composition of samples (mass and mole fractions) are
presented in Table 2.
Isoamylenes
TAEE
Cyclohexane
Temp. Time,
, C
h
Mass
fraction
Mole
Mass
fraction fraction
Mole
Mass
fraction fraction
Mole
fraction
Mass
fraction
Mole
fraction
39.9
0.00
0.2123
0.3186
0.1499
0.1477
0.00023
0.00016
0.609
0.50
0.25
0.1987
0.2982
0.1634
0.1611
0.00121
0.00082
0.609
0.50
0.54
0.1980
0.2971
0.1606
0.1583
0.00155
0.00105
0.609
0.50
0.75
0.1991
0.2988
0.1583
0.1560
0.00216
0.00146
0.609
0.50
1.22
0.1974
0.2962
0.1588
0.1566
0.00365
0.00247
0.609
0.50
1.42
0.1974
0.2961
0.1581
0.1559
0.00424
0.00287
0.609
0.50
0.00
0.2123
0.3186
0.1499
0.1477
0.00023
0.00016
0.609
0.50
0.28
0.1971
0.2958
0.1587
0.1564
0.00475
0.00321
0.609
0.50
0.50
0.1977
0.2966
0.1576
0.1553
0.00426
0.00288
0.609
0.50
0.75
0.1968
0.2953
0.1551
0.1528
0.00600
0.00406
0.609
0.50
1.02
0.1958
0.2937
0.1513
0.1491
0.00944
0.00639
0.609
0.50
1.40
0.1949
0.2924
0.1485
0.1464
0.01296
0.00877
0.609
0.50
0.00
0.2123
0.3186
0.1499
0.1477
0.00023
0.00016
0.609
0.50
0.26
0.1997
0.2997
0.1564
0.1542
0.00328
0.00222
0.609
0.50
0.50
0.1976
0.2965
0.1543
0.1521
0.00842
0.00570
0.609
0.50
0.82
0.1954
0.2932
0.1511
0.1489
0.01450
0.00981
0.609
0.50
1.00
0.1935
0.2903
0.1478
0.1457
0.01991
0.01347
0.609
0.50
1.26
0.1906
0.2860
0.1440
0.1420
0.02523
0.01707
0.609
0.50
0.00
0.2123
0.3186
0.1499
0.1477
0.00023
0.00016
0.609
0.50
0.26
0.1982
0.2973
0.1513
0.1492
0.01164
0.00788
0.609
0.50
0.50
0.1934
0.2902
0.1447
0.1426
0.01991
0.01347
0.609
0.50
0.93
0.1862
0.2793
0.1338
0.1319
0.03829
0.02591
0.609
0.50
1.25
0.1812
0.2719
0.1253
0.1235
0.05129
0.03470
0.609
0.50
1.42
0.1762
0.2644
0.1199
0.1182
0.05998
0.04058
0.609
0.50
50.4
60.7
70.9
(0 ) (0.3186 0.2644 )
=
= 0.170
0
0.3186
,
0,18
T=39.9C
T=50.4C
T=60.7C
T=70.9C
0,16
Conversion,-
0,14
0,12
0,10
0,08
0,06
0,04
0,02
0,00
0,0
0,2
0,4
0,6
0,8
t, h
1,0
1,2
1,4
1,6
Conversion rate in Equation (6)-(7) was calculated by finite difference using the three-point
differentiation formulas [4] (See Appendix B, Figure B-3). The calculation method is
demonstrated below using the data collected at 70.9 C, particularly for the feed sample (for
time =0), sample at 0.26 h and the last sample at 1.42 h (representing the three point
differentiation formulas respectively).
For time equal to zero (t=0) the derivative was solved as follows,
30 + 4 1 2 (3 0) + (4 0.0667) 0.0891
(
) =
=
=0
2 ()
2 (0.26 0) ()
= 0.3469 (1)
(0.0891 0)
1
(2 0 ) =
(
)
=
= 0.1856 (1)
=0.26 2
2 (0.5 0.26)
Considering the last sample in that particular series, at t = 1.42 h, conversion rate was
computed as shown below.
1
0.123 (4 0.1466) + (3 0.170)
(3 44 + 35 ) =
(
)
=
=1.42 2
2 (1.42 1.25)
1
= 0.140 ( )
Reaction rates were calculated from the conversion rate and initial concentration of ethanol.
Initial concentrations were estimated from the initial moles and volume of feed solutions (See
Appendix A, Tables A-3 & A-4 for detailed data). But in order to determine the volume,
density of the feed mixture was first estimated as illustrated in the Appendix B, Figure B-1.
Examples of calculated reaction rates for selected samples are given below.
)
=0
0 (
0 (
)
= 3.667 () 0.1856 (1) = 0.680 . 1 . 1
=0.26
Similary for the last sample, t = 1.42 h at 70.9 C, reaction rate was calculated as follows,
0 (
)
= 3.667 () 0.140 (1) = 0.5134 . 1 . 1
=1.42
Figure 2 shows the reaction rate results obtained. Conversion and reaction rates results are
summarized in Table 3.
1,6
1,4
T=39.9 C
1,2
T=50.4 C
1,0
T=60.7 C
0,8
T=70.9 C
0,6
0,4
0,2
0,0
-0,2
0,0
0,2
0,4
0,6
0,8
1,0
1,2
t, h
Figure 2. Reaction rate against residence time.
10
1,4
1,6
Time, h
0.00
Conversion
fraction
0.000
dXA/dt,
1/h
0.3763
Reaction
rate,
CA0*dXA/dt
(mol/L/h)
1.3798
0.25
0.54
0.75
1.22
1.42
0.064
0.067
0.062
0.070
0.070
0.1157
0.0044
0.0029
0.0205
0.0189
0.4242
0.0160
0.0108
0.0751
0.0693
50.4
0.00
0.28
0.50
0.75
1.02
1.40
0.000
0.071
0.069
0.073
0.078
0.082
0.3904
0.1533
-0.0029
0.0166
0.0121
0.0099
1.4316
0.5621
-0.0107
0.0610
0.0445
0.0363
60.7
0.00
0.000
0.3256
1.1940
0.26
0.50
0.82
1.00
1.26
0.059
0.069
0.080
0.089
0.102
0.1430
0.0322
0.0527
0.0442
0.0619
0.5242
0.1181
0.1931
0.1622
0.2269
0.00
0.26
0.50
0.93
1.25
1.42
0.000
0.067
0.089
0.123
0.147
0.170
0.3469
0.1823
0.0652
0.0907
0.1411
0.1414
1.2720
0.6686
0.2390
0.3325
0.5174
0.5186
Temp., C
39.9
70.9
11
below. The results of rate constants at different temperatures are presented in Table 4 (See
also Appendix A, Table A-6).
= 0.1286
0
3.667
= 0.1286
= 0.2572
0
1.833
.
T=39.9 C
0,08
y = 0,0066x + 0,0661
R = 0,5488
y = 0,0131x + 0,0704
R = 0,8656
0,09
XA/(1-XA)
0,075
XA/(1-XA)
T=50.4 C
0,1
0,07
0,065
0,06
0,08
0,07
0,06
t, h
t, h
T=60.7 C
T=70.9 C
0,25
y = 0,0495x + 0,049
R = 0,9885
0,1
y = 0,1286x + 0,021
R = 0,9632
0,2
XA/(1-XA)
XA/(1-XA)
0,12
0,08
0,06
0,15
0,1
0,05
0
0,04
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
t, h
t, h
Figure 3. Plots for determination of rate constants, k at different reaction temperatures based on
reaction conversion of ethanol.
39.9
0.01320
50.4
0.02620
60.7
0.09900
70.9
0.25720
12
1/T, (K-1)
-1
0,0029
-1,5
0,00295
0,003
0,00305
0,0031
0,00315
0,0032
0,00325
-2
ln(k)
-2,5
y = -10906x + 30,34
R = 0,9786
-3
-3,5
-4
-4,5
-5
Activation energy of 90.67 kJ/mol was obtained and a frequency factor (A), of 1.5e13. More
details are given in the Appendix A, Table A-6.
13
4. Discussion
In general, the rate of the reaction is slow. Appreciable conversion requires use of higher
temperature e.g. 70C. At this lower temperatures for instance <40C, the reaction is much
slower. This effect can also be observed in Figure 3 where it was relatively difficult to
estimate the rate constant. However, it is important to note that, initially (within the 15 min
time) the reaction rate was reasonably fast but after slowed down dramatically. This behavior
was more pronounced at lower temperatures studied (40-50C). The reasons for this kind of
phenomenon were not clearly understood. Among the speculated reasons would be due to
mass transfer constraints in the catalyst particles, slow chemical reaction and probably the
effect of reaction equilibrium.
According to the observed activation energy of 90.67 kJ/mol, it is relatively high which would
indicate a fairly slow reaction at lower temperatures even in the presence of the catalyst. In
literature, Linnekoski and Krause [5] reported activation energy for formation of TAEE from
2-methyl-1-butene and 2-methyl-2-butene to be equivalent to 90 kJ/mol and 108 kJ/mol
respectively. Gonzlez-Rugerio et al. [6], reported activation energies of 76.8 kJ/mol and
95.9 kJ/mol corresponding to use of 2-methyl-1-butene and 2-methyl-2-butene respectively.
Comparing the results in both cases, the observed activation energy in this work is within
range.
However, in the present work the reaction was taken as an elementary reaction but from
theory [5, 6] different steps may occur as shown in scheme I and thus affect the overall
estimation of kinetic parameters.
5. Conclusions
The observed activation energy of 90.67 kJ/mol was comparable to the literature values even
though, the reaction mechanism was simplified to an elementary reaction and the effects of
isomerization, equilibrium were not taken into account. Furthermore, the reaction
demonstrated fast initial reaction rates but overall exhibited low conversion especially at
temperatures of 39.9-50.4C.
14
7. References
1. European Fuel Oxygenates Association. Fuel Ethers improve Air Quality and reduce GHG
emissions, [online], Available: http://www.efoa.eu/en/fuel-ethers/fuel-ethers-improve-airquality-and-reduce-ghg-emissions.aspx [April 6, 2016]
2. The European Fuel Oxygenates Association. Fuel Ethers enable the Use of Biofuels, [online],
Available: http://www.efoa.eu/en/fuel-ethers/fuel-ethers-enable-the-use-of-biofuels.aspx
[April 06, 2016]
3. Hart Energy Consulting (2011) Relative CO2 Savings Comparing Ethanol and TAEE as a
Gasoline Component [online], Available:
http://www.efoa.eu/documents/document/20110328150906-2011-0323_relative_co2_savings_comparing_ethanol_and_taee_as_a_gasoline_component.pdf [April
6, 2016]
4. Fogler HS, Elements of Chemical Reaction Engineering, 4th edn, Pearson, Westford, 2005
5. Linnekoski JA, Krause,O.A and Rihko KL, Kinetics of the Heterogeneously Catalyzed
Formation of tert-Amyl Ethyl Ether. Industrial & Engineering Chemistry Research 36 (2):310316 (1997).
6. Gonzlez-Rugerio CA, Keller T, Pilarczyk J, Saacki W and Grak A, TAEE synthesis from
isoamylenes and ethanol by catalytic distillation: Pilot plant experiments and model validation.
Fuel Processing Technology, 102:1-10 (2012).
15
Cyclohexane
Time, h
T=39.9C
0.00
Isoamylenes
Ethanol
TAEE
103214.4
23377.5
17548.7
29.2
0.25
103211.3
25494.6
16426.7
152.2
0.54
105302.9
25552.5
16695.6
198.4
0.75
104300.7
24951.2
16632.3
274.2
1.22
104604.5
25110.5
16535.9
465.4
1.42
103846.8
24817.6
16413.3
537.3
Time, h
T=50.4C
0.00
103214.4
23377.5
17548.7
29.2
0.28
104768.5
25121.2
16539.8
606.9
0.50
104279.8
24832.1
16506.8
541.2
0.75
104876.2
24578.3
16531.2
767.8
1.02
103239.5
23603.3
16184.7
1188.3
1.40
105138.5
23603.3
16407.5
1661.0
Time, h
T=60.7C
0.00
103214.4
23377.5
17548.7
29.2
0.26
104409.2
24682.1
16698.5
417.4
0.50
104915.4
24460.9
16605.3
1077.3
0.82
103527.2
23639.7
16198.3
1830.1
1.00
103370.1
23094.6
16016.3
2508.7
1.26
104725.4
22797.5
15987.4
3221.0
Time, h
T=70.9C
0.00
103214.4
23377.5
17548.7
29.2
0.26
103547.7
23683.3
16432.6
1469.6
0.50
106286.5
23243.3
16460.1
2580.6
0.93
104730.4
21173.9
15614.6
4889.1
1.25
104907.7
19871.9
15222.0
6560.5
1.42
106323.2
19261.6
15001.8
7774.6
16
Cyclohexane
84.16
TAEE
102.17
Cyclohexane
0.7781
39.9
Reactor
feed
solution
49
0.709
0.354
0.236
0.118
0.5
0.333
0.167
50.4
47.4
0.686
0.343
0.229
0.114
0.5
0.333
0.167
60.7
52.47
0.759
0.380
0.253
0.127
0.5
0.333
0.167
70.9
53.73
0.777
0.389
0.259
0.130
0.5
0.333
0.167
Experiment
Temp. C
Total
moles
Moles of components
Cyclohexane
Ethanol
Isoamylenes
Mole fractions
Cyclohexane
Ethanol
Isoamylenes
Reactor feed
solution
Masses of Components
Mass fractions
Temp. C
39.9
50.4
mass, g
49
47.4
Cyclohexane
29.829
28.855
Ethanol
10.886
10.530
Isoamylenes
8.285
8.015
Cyclohexane
0.6088
0.6088
Ethanol
0.2222
0.2222
Isoamylenes
0.1691
0.1691
60.7
70.9
52.47
53.73
31.941
32.708
11.657
11.937
8.872
9.085
0.6088
0.6088
0.2222
0.2222
0.1691
0.1691
Reactor feed
solution, mL
64.4
62.3
69.0
Component moles
Cyclohexane Ethanol
0.354
0.236
0.343
0.229
0.380
0.253
Isoamylenes
0.118
0.114
0.127
Concentration, mol/L
Cyclohexane Ethanol
5.500
3.667
5.500
3.667
5.500
3.667
Isoamylenes
1.833
1.833
1.833
70.9
70.7
0.389
0.130
5.500
1.833
0.259
17
3.667
Table A-5. Calculated (plotted) data for determination of the rate constant
Experiment
t, h
XA/1-XA
1/t
0.2500
0.0683
4.000
0.5417
0.0724
1.846
0.7500
0.0662
1.333
1.2167
0.0755
0.822
1.4194
0.0757
0.705
0.2778
0.0770
3.600
0.5028
0.0741
1.989
0.7500
0.0786
1.333
1.0194
0.0845
0.981
1.4000
0.0895
0.714
0.2583
0.0631
3.871
0.5000
0.0742
2.000
0.8167
0.0867
1.224
1.0028
0.0973
0.997
1.2556
0.1137
0.796
0.2556
0.0714
3.913
0.5000
0.0979
2.000
0.9333
0.1404
1.071
1.2500
0.1718
0.800
1.4167
0.2050
0.706
Temp. C
39.9
50.4
60.7
70.9
Slope =
k*CB0/CA0
K
(L/mol/h)
313.05
0.00660
0.01320
-4.32754 0.003194
323.55
0.01310
0.02620
-3.642 0.003091
333.85
0.04950
0.09900
-2.31264 0.002995
343.05
0.12860
0.25720
-1.3579 0.002915
LN(k)
1/T, (1/K)
18
( ) = ( ) ( ) + (
)( ) + ( )( )
= (84.16 0.5) + (46.07 0.333) + (70.13 0.167) = 69.13 /
Density of the mixture calculation
( 3 ) = ( ) ( 3 ) + ( ) ( 3 ) +
( ) ( 3 )
19
20