Supporting Information
Production of Linear Octenes from Oligomerization of 1-Butene over
Carbon Supported Cobalt Catalysts
Zhuoran Xu,† Joseph P. Chada,† Dongting Zhao,† Carlos A. Carrero, § Yong Tae Kim,† Devon C.
Rosenfeld,‡ Jessica L. Rogers,‡ Steven J. Rozeveld,‡ Ive Hermans,*,†,§ and George W. Huber*,†
†
‡
§
Department of Chemical and Biological Engineering, University of Wisconsin, Madison, Wisconsin 53706, United States
The Dow Chemical Company, 2301 N. Brazosport Blvd, Freeport, TX 77541-3257, United States
Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, United States
KEYWORDS : heterogeneous catalysis, selectivity, oligomerization, linear octene, pretreatment
temperature
Corresponding Author
*E-mail: [email protected].
*E-mail: [email protected].
Table S1. Mass and heat transfer evaluation
Formula
Interphase heat
Interparticle heat
Intraparticle heat
Interphase mass
Computed Values
|∆𝐻|𝑟 ′′′ 𝑟𝑝
𝑅𝑇𝑏
< 0.15
ℎ𝑇𝑏
𝐸
|∆𝐻|𝑟 ′′′ 𝑟𝑝2
𝑘𝑒 𝑇𝑤
< 0.4
𝑅𝑇𝑤 /𝐸
𝑟𝑝
[1 + 8 (𝑅 ) 𝐵𝑖𝑤 ]
0
|∆𝐻|𝑟 ′′′ 𝑟𝑝2
𝑅𝑇𝑠
< 0.75
𝜆𝑇𝑠
𝐸
𝑟𝑜𝑏𝑠 𝑅𝑝
𝐶𝐵 𝑘𝐷
𝑟𝑜𝑏𝑠 𝑅𝑝2
𝐶𝑠 𝐷𝑒𝑓𝑓
Intraparticle mass
Target
14.14 h-1 WHSV
0.71 h-1 WHSV
7.8×10-3
1.0×10-4
<1.1×10-2
1.4×10-2
1.8×10-4
<1.6×10-2
1.4×10-2
1.8×10-4
<3.1×10-2
1.1×10-5
1.4×10-7
<0.15
0.4
5.3×10-3
<0.6
NOMENCLATURE
∆𝐻 -heat of reaction
𝑟 ′′′ -rate per catalyst volume
𝑟𝑝 -radius of particles
𝑇𝑏 -bulk fluid temperature
ℎ-convective heat transfer coefficient
𝑘𝑒 -effective thermal conductivity
𝜆-effective thermal conductivity
𝐵𝑖-Biot number
𝐸-activation energy
𝑅𝑝 -radius of particles
𝐶𝐵 -concentration in bulk fluid
𝐶𝑆 -concentration at catalyst surface
𝑘𝐷 -mass transfer coefficient
𝐷𝑒𝑓𝑓 -effective diffusivity
Table S2. Experimental and Equilibrium linear octene distribution (Reaction condition: 80 oC, 450 psig)
2A-Co/C-230
WHSV(h-1)
Equilibrium
14.14
0.71
0.25
Conversion (%)
9.77
11.42
29
1-octene
0
0
0
0.83
cis-2-octene
14.61
9.16
8.81
8.49
trans-2-octene
21.02
25.42
25.29
35.25
cis/trans-3-octene
62.83
58.58
56.07
34.76
cis/trans-4-octene
1.54
6.84
9.83
20.67
cis-2-octene/trans2-octene
0.69
0.36
0.35
0.24
Table S3. Experimental and equilibrium methyl-heptene distribution (Reaction condition: 80 oC, 450 psig).
2A-Co/C-230
WHSV(hr-1)
Equilibrium
14.14
0.71
0.25
9.77
11.42
29
cis-5-methyl-3-heptene
10.9
9.8
8.3
3.4
trans- 5-methyl-3-heptene
12.2
11.1
12.5
14.4
trans-3-methyl-2-heptene
21.2
43.6
44.4
33.0
trans-5-methyl-2-heptene
16.7
17.8
19.9
29.4
cis-5-methyl-2-heptene
39.1
17.8
14.8
7.0
3-methyl-3-heptene
0
0
0
11.5
4-methyl-1-heptene
0
0
0
0.7
3-methyl-1-heptene
0
0
0
0.5
cis/trans -5-methyl-3-
0.89
0.88
0.67
0.24
cis/trans -5-methyl-2-
2.35
1.00
0.74
0.24
cis-5-methyl-3-heptene/cis-
1.85
0.41
0.33
0.21
trans-5-methyl-3heptene/trans-5-methyl-2heptene
0.73
0.63
0.63
0.49
Conversion (%)
heptene
heptene
5-methyl-2-heptene
Octene isomers distribution (%)
100
80
14.14 hr-1 WHSV
60
0.71 hr-1 WHSV
40
20
0
36
38
40
42
44
46
70
80
90
100
TOS (hr)
Figure S1. Octene isomers distribution with time on stream over 2A-13%Co/C-230, including: (▼) trans-3-octene, (▲) trans-2octene, (●) cis-2-octene, (■) cis-5-methyl-2-heptene, (►) 3-methyl-2-heptene, (◆) trans-4-octene, (◄) trans-5-methyl-3heptene, (○) cis-5-methyl-3-heptene and (★) trans-5-methyl-2-heptene at 80℃ and 450 psig.
Octene isomers distribution (%)
100
80
14.14 hr-1 WHSV
0.71 hr-1 WHSV
60
40
20
0
36
38
40
42
44
46
70
80
90
TOS (hr)
Figure S2. Octene isomers distribution with time on stream over 2NaOH-13%Co/C-230, including: (▼) trans-3-octene, (▲) trans2-octene, (●) cis-2-octene, (■) cis-5-methyl-2-heptene, (►) 3-methyl-2-heptene, (◆) trans-4-octene, (◄) trans-5-methyl-3heptene, (○) cis-5-methyl-3-heptene and (★) trans-5-methyl-2-heptene at 80℃ and 450 psig.
Octene isomers distribution (%)
100
80
0.71 hr-1 WHSV
14.14 hr-1 WHSV
60
40
20
0
36
38
40
42
44
60
70
80
TOS (hr)
Butene consumption rate (molbutene/molCo/h)
Figure S3. Octene isomers distribution with time on stream over 2A-13%Co/C-350, including: (▼) trans-3-octene, (▲) trans-2octene, (●) cis-2-octene, (■) cis-5-methyl-2-heptene, (►) 3-methyl-2-heptene, (◆) trans-4-octene, (◄) trans-5-methyl-3heptene, (○) cis-5-methyl-3-heptene and (★) trans-5-methyl-2-heptene at 80℃ and 450 psig.
10
1
-1
24 h WHSV
0.1
-1
0.25 h WHSV
0
10
20
30
40
50
60
70
80
90
TOS (hr)
Figure S4. Catalyst activity for (▼) 2A-Co/C-230 and (►) 2A-Co/C-270 vs TOS at 24 h-1 and 0.25 h-1 WHSV.


Intensity (a.u.)


Spent 2A-Co/C-550 oC






Spent 2A-Co/C-350 oC

Spent 2A-Co/C-270 oC
 

Spent 2A-Co/C-230 oC
 

5
10
15
20
25
30
35
40
45
Two Theta (deg)
Figure S5. Mo-XRD patterns of the spent catalysts, with characteristic peaks of △graphite, ●Co3O4, □CoO, ◆Cubic Co.
230oC
350oC
FWHM=20.7
FWHM=15.9
200
400
600
800
1000
1200
1400
1600
1800
2000
Raman shift (cm-1)
Figure S6. Comparison of CoOx signal at 690 cm-1 during pretreatment at 230oC and 350oC.
1.6
1.4
Normalized Absorption
1.2
1.0
2A-14% Co/C 270
Fit
CoO
Co3O4
Residual
0.8
0.6
0.4
0.2
0.0
-0.2
7700
7710
7720
7730
7740
7750
X-ray Energy (eV)
Figure S7. Fitted XANES spectra for 2A-14% Co/C-270 showing weighed spectra, linear combination fit, and residual difference
between the fit and data.