A NOVEL TWO-STEP PROCESS FOR THE PRODUCTION OF RENEWABLE
AROMATIC HYDROCARBONS FROM TRIACYLGLYCERIDES
Swapnil Fegadea, Brian Tandea,*, Alena Kubátováb, Wayne Seamesa, Evguenii
Kozliakb
a
Department of Chemical Engineering, University of North Dakota, 241 Centennial
Drive, Stop 7101, Grand Forks, ND 58202-7101, USA
b
Department of Chemistry, University of North Dakota, P.O. Box 9024, Grand Forks, ND
58202, USA
* Corresponding author. Tel.: +1-701-777-3797; Fax: +1-701-777-3773. E-mail address:
[email protected]
1
Table S1. Details of GC-MS analysis used for reformate identification
Compound name
Formula
Benzene
Toluene
Ethylbenzene
p-Xylene
o-Xylene+m-xylene
o-Xylene 105
Naphthalene
Benzene C3z
Benzene, C3a
Benzene, C3b
Benzene, C3x
Benzene, C3y
Benzene, C4a
Benzene, C4b
Benzene, C4c
Indane
Benzene, C4y
Benzene, butylBenzene, C4d
Benzene, C4x
Benzene C4e
Benzene C4f
Benzene, C4z
Indane, C1a
Benzene C5y
Indane, C1
Benzene, C5a
Indane, C1x
Benzene, C5b
Benzene, C5z
Benzene, pentylBenzene, C5x
Indane, C2
Benzene, C6a
Benzene, C6y
Benzene, hexylBenzene, C6x
Naphthalene, C1y
Naphthalene, C1x
Benzene, heptylBenzene, C7x
Naphthalene, ethyl
Naphthalene, C2x
Naphthalene, C2y
Benzene, octylBenzene, C8x
Naphthalene, C3x
C6H6
C7H8
C8H10
C8H10
C8H10
C8H10
C10H8
C9H12
C9H12
C9H12
C9H12
C9H12
C10H14
C10H14
C10H14
C9H10
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C10H12
C11H16
C11H14
C11H14
C11H14
C11H16
C11H16
C11H16
C11H16
C11H14
C12H18
C12H18
C12H18
C12H18
C11H10
C11H10
C13H20
C13H20
C12H12
C12H12
C12H12
C14H22
C14H22
C13H14
Molecular
weight
78
92
106
106
106
106
128
120
120
120
120
120
134
134
134
118
134
134
134
134
134
134
134
132
148
132
148
132
148
148
148
148
146
162
162
162
162
142
142
176
176
156
156
156
190
190
170
Retention
time (min.)
4.6
7.1
9.1
9.3
9.7
9.7
13.7
10.2
10.8
10.9
11.1
11.3
11.5
11.6
11.7
11.9
12.0
12.1
12.2
12.28
12.37
12.4
12.47
12.52
13.06
13.13
13.17
13.27
13.48
13.61
13.31
13.41
13.73
14.19
14.27
14.36
14.44
14.83
15.01
15.34
15.41
15.75
15.85
16
16.25
16.30
16.71
Quantification
Ion
78
91
91
91
91
105
128
105
105
105
105
105
105
119
119
105
105
91
105
105
105
105
105
105
105
105
105
105
105
105
91
105
105
105
105
91
105
128
128
91
105
128
128
128
91
105
128
2
Naphthalene, C3y
Benzene, nonylBenzene, C9x
Benzene, decyl
Benzene, C10x
Benzene, C11a
Benzene, C11b
Benzene, undecenyl
Benzene, C11x
C13H14
C15H24
C15H24
C16H26
C16H26
C17H28
C17H28
C17H28
C17H28
170
204
204
218
218
232
232
232
232
16.82
17.10
17.16
17.91
17.96
18.11
18.18
18.67
18.73
128
91
105
91
105
105
105
91
105
Table S2. Summary composition of OLP obtained from non-catalytically cracked crop oil.
Reaction conditions
Temperature (oC)
435
435
435
Pressure (psig)
30
20
40
Concentrations, (w/w%)
Mean
StDev
Linear alkanes
9.3
10.3
9.5
9.7
0.53
Branched alkanes
0.1
0.1
0.1
0.1
0.0
Bicycloalkanes
0.1
0.1
0.1
0.1
0.0
Cycloalkanes
1.6
1.5
1.7
1.6
0.10
Alkenes with C=C bonds at the terminal position
4.5
4.5
4.4
4.5
0.058
Alkenes with a C=C bond at a non-terminal position
7.1
6.5
7
6.9
0.32
Alkadienes
0.2
0.1
0.2
0.17
0.058
Cycloalkenes
1.7
1.6
1.7
1.7
0.058
Ketones
BTEX
Monoaromatics (non-BTEX)
Indanes
Naphthalenes
Phenol
0.8
0.5
3.5
0.35
0.51
0.1
1
0.5
3.3
0.46
0.46
0.1
0.8
0.6
3.1
0.36
0.39
0.1
0.87
0.53
3.3
0.39
0.45
0.1
0.12
0.058
0.2
0.050
0.049
0.0
Saturated linear carboxylic acids
18
14
18
17
2.3
Saturated linear dicarboxylic acids
2
6.1
5.2
4.4
2.2
Identified compounds
51
51
53
55
2.1
Unidentified compounds, estimated by peak integration
8.2
9.9
12
10
1.9
Unresolved peaks, estimated by integration of a “hump”
21
39
44
35
12
Total
80
99.9
109
97
15
Table S3. Reformate concentrations for the catalytic (SiO2/Al2O3=23) conversion of OLP. Experiment
numbers correspond to the conditions in Table 1.
3
Expt
No.
1
2
3
4
5
6
7
8
9
10
11
12
Alkyl
benzenes
15
15
12
15
15
15
13
21
19
12
38
37
BTEX
1.8
1.9
1.5
1.7
1.9
2.0
2.5
3.8
2.2
2.0
8.7
8.7
Concentration in the reformate (w/w%)
Mono
Indanes
Naphthalenes
Aromatics
16
2.1
1.6
17
2.3
1.7
14
1.7
1.3
17
2.1
1.7
17
2.0
1.6
17
2.1
1.6
16
1.5
1.7
25
3.0
2.4
21
2.9
2.0
14
2.0
1.5
47
4.3
7.1
46
5.2
6.9
Total aromatics
20
21
17
21
20
21
19
30
26
18
58
58
4
Table S4. Composition of the gas fraction obtained by catalytic OLP*
reforming**
Sample 1
Sample 2
Concentration
Concentration
5
5
Coke yield (w/w%)
Liquid yield (w/w%)
80
81
Gas yield (w/w%)
15
14
Gas concentration
(vol %)
(vol %)
3.0
CO
2.8
6.3
Methane
6.4
1.3
CO2
1.5
0.39
Ethane
0.28
12
Ethylene
13
55
Propylene
54
16
Butane
16
2.4
Butane
2.1
0.62
Pentane
0.57
0.53
Hexane
0.58
3.1
Hydrogen
2.8
* OLP = Organic Liquid Product
** The reforming reaction conditions were: reaction temperature = 432
ºC, OLP to catalyst ratio = 4.5, reaction time = 12.5 minutes,
silica:alumina ratio = 23.
Table S5. The concentrations of aromatic hydrocarbons in replicate liquid reformate
samples
Aromatic
hydrocarbon
Benzene, C3a
Benzene, C3b
Benzene, C3x
Benzene, C3y
Benzene C3z**
Benzene, C4a
Benzene, C4b
Benzene, C4c
Benzene, C4d
Benzene C4e
Benzene C4f
Benzene C4x
Benzene C4y
Benzene, C4z
Benzene, C5a
Benzene, C5b
Benzene, C5x
Benzene C5y
Benzene C5z
Benzene, C6a
Benzene, C6x
Benzene C6y
Benzene, C7x
Formula
C9H12
C9H12
C9H12
C9H12
C9H12
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C11H16
C11H16
C11H16
C11H16
C11H16
C12H18
C12H18
C12H18
C13H20
Sample1*
(w/w%)
9.00
0.67
2.51
3.90
0.88
0.33
0.52
0.53
0.22
0.67
0.68
1.56
3.02
2.34
0.80
0.78
2.51
0.61
0.08
0.55
1.47
0.38
0.61
Sample2*
(w/w%)
9.69
0.76
2.76
4.23
0.95
0.38
0.55
0.59
0.25
0.66
0.66
1.71
3.33
2.60
1.43
0.86
2.80
0.68
0.10
0.63
1.66
0.41
0.67
Average
(w/w%)
9.34
0.72
2.64
4.06
0.92
0.36
0.53
0.56
0.23
0.66
0.67
1.64
3.17
2.47
1.12
0.82
2.66
0.64
0.09
0.59
1.56
0.40
0.64
StDev (+/-,
w/w%)
0.49
0.06
0.18
0.23
0.06
0.04
0.03
0.04
0.02
0.01
0.02
0.11
0.22
0.19
0.44
0.06
0.21
0.05
0.01
0.06
0.13
0.03
0.04
5
Benzene, C8x
Benzene, C9x
Benzene, C10x
Benzene, C11a
Benzene, C11b
Benzene, C11x
Benzene
Toluene
Ethylbenzene
p-Xylene
o-Xylene+mxylene
Indane
Indane, C1a
Indane, C1
Indane, C1x
Indane, C2
Benzene, butyl-***
Benzene, pentyl***
***
Benzene, hexylBenzene, heptyl-
C14H22
C15H24
C16H26
C17H28
C17H28
C17H28
C6H6
C7H8
C8H10
C8H10
0.34
0.16
0.05
0.40
0.37
0.07
0.86
2.68
1.34
2.66
0.33
0.19
0.06
0.43
0.42
0.09
0.93
2.88
1.49
2.85
0.33
0.17
0.06
0.41
0.39
0.08
0.89
2.78
1.42
2.76
0.00
0.02
0.01
0.03
0.04
0.01
0.05
0.14
0.10
0.13
C8H10
C9H10
C10H12
C10H12
C10H12
C11H14
C10H14
1.21
1.20
1.41
1.04
1.18
0.42
0.68
1.34
1.32
1.53
0.06
1.32
0.44
0.74
1.28
1.26
1.47
0.55
1.25
0.43
0.71
0.09
0.09
0.09
0.69
0.10
0.02
0.04
C11H16
C12H18
0.53
0.21
0.61
0.25
0.57
0.23
0.05
0.03
***
C13H20
0.23
0.26
0.24
0.02
Benzene, octylC14H22
0.07
0.09
0.08
0.01
Benzene, nonyl-***
C15H24
0.01
0.02
0.02
0.00
Naphthalene
C10H8
1.69
1.88
1.79
0.13
Naphthalene, C1x
C11H10
1.04
1.13
1.09
0.06
Naphthalene, C1y
C11H10
2.14
2.34
2.24
0.10
Naphthalene, ethyl
C12H12
0.44
0.49
0.47
0.04
Naphthalene, C2x
C12H12
0.66
0.71
0.68
0.04
Naphthalene, C2y
C12H12
0.41
0.46
0.43
0.04
Naphthalene, C3x
C13H14
0.42
0.49
0.45
0.05
Naphthalene, C3y
C13H14
0.14
0.09
0.11
0.04
* Samples 1 and 2 represent the reformate samples obtained from the replicates of
experiments with conditions of 432 ºC, OCR = 4.5 and reaction time of 12.5 minutes
under the silica:alumina ratio = 23.
** The number/character (e.g. C4a, C4b, C4x, C4y) represent the isomer profiles for the
given number of carbon atoms in the alkyl groups attached to the aromatic ring
obtained in the order of chromatographic elution.
*** These n-alkylbenzenes are listed separately and not included in the isomer profiles.
***
6