Supporting Information
Transiting from adipic acid to bio-adipic acid: Part I. Petroleum-based processes
Jan C. J. Bart and Stefano Cavallaro* Dipartimento di Ingegneria Elettronica, Chimica e Ingegneria Industriale dell’Università di Messina, Viale F. Stagno D’Alcontres, 31 – 98166 Sant’Agata di MESSINA (ITALY). *Corresponding Author E-Mail:
[email protected]
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Table S1. Desiderata for a green industrial adipic acid process.
· · · · · · · · · · · · · · · ·
Safety Inexpensive, renewable raw materials Minimal use of auxiliary (non-toxic) reagents Solvent- and metal-free route No generation of environmentally incompatible by-products Mono-step process Atom-efficient synthesis method High carbon efficiency High selectivity (> 70%) and yield High space-time yield Operational simplicity Mild reaction conditions Minimal energy requirements Easy recovery of pure adipic acid Straightforward recycling of the catalyst Low cost
Table S2. Oxygen-donor oxidants. Oxidant
Active oxygen (wt %)
By-product(s)
50-100
-
H2 O2
47.1
H2 O
t-BuOOH (t-BHP)
17.8
t-BuOH
HNO3
25.0
NOx, N2O, N2
N2 O
36.4
N2
Acetylperoxyborate (APB)
4.8
AcOH, H2O
Peracetic acid (PAA)
21.0
AcOH
O3
33.3
O2
O2
2
Table S3. Application of N2O abatement technology to adipic acid plantsa. N2O destruction factor (%)b 90-99+
Total plant capacity (kt/yr) 1393
Thermal destruction
98-99+
838
Recycle to nitric acid
98-99+
319
Rhodia (France)
Recycle to adipic acid
90-98
-
Ascend (USA)c
Unabated
-
356
Adarsh Chem (India), Bohui (China), Shandong (China), Rovno (Ukraine), Severodonetsk (Ukraine)
Unknown
-
81
Dushanzi Tianli (China), Sumitomo (Japan)
Abatement technology Catalytic destruction
a
Reflects 2010 status.
b c
Manufacturers Asahi Kasei(Japan), BASF (Germany), Invista (USA), Liaoyang (China), Radici (Italy, Germany), Shenma (China) Invista (Singapore), Lanxess (Germany), Rhodia (Brazil, S. Korea), Ascend (USA)
Destruction factor (representing the technology abatement efficiency) should be multiplied by an abatement system utility factor.
Pilot plant status.
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Table S4. Peroxidative oxidation of cyclohexane catalysed by redox molecular sievesa. Solvent (mL)
I/H2O2 mmol
Conversion I (%)
Ratio of III/II
H2 O2 consumed (%)
H2O2 eff.(%)
Turnoverb
Reference
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Acetone (6.3)
118.8/88.2
6.5
0.23
13
65
94
(238)
100
12
Acetone (15)
18.5/20.0
7.0
2.25
98
11
42
(239)
70
3
None
120/240
66.7
0.66
79
59
798c
(86)
Catalyst (wt% metal)
Catalyst (g)
T (°C)
t (h)
TS-1 (1.90) Ti-MCM-41 (1.48) NaGe-X
0.20
77
0.10 0.10
a
I, cyclohexane; II, cyclohexanol; III, cyclohexanone. Millimole of oxidised products per millimole of metal in the catalyst. c Millimole of oxidised products per gram of catalyst. b
Table S5. Aerobic oxidation of cyclohexane to adipic acid over N-hydroxy derivatives.
(%)
II
Selectivity (%) III
AcOH
90
-
2
76
(296)
-
n.g.
28
61
7
(300)
NHS/Co(II)a
AcOH
58
5
29
30
(299)
NHPI/Phen/Br2
CH3CN
48
-
22
75
(302)
Catalyst NHPI/metal salts 4-LauryloxycarbonylNHPI/Co(II), Mn(II)
Solvent
Conversion
Reference Adipic acid
NHPI, N-hydroxyphthalimide; NHS, N-hydroxysaccharin; Phen, o-phenanthroline; II, cyclohexanol; III, cyclohexanone. a
Data for cyclododecane.
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Table S6. Solventless aerobic oxidation of cyclohexane over lipophilic NHPIa. Catalyst
TONb
Product distribution (%) II
III
Adipic acid
Othersc
NHPI/Co(II)/Mn(II)
56
28
61
7
4
NHPI/Co(II)
41
25
65
7
3
NHPI/Mn(II)
7.7
35
57
4
4
NHPId/Co(II)/Mn(II)
33
20
53
26
1
NHPIe/Co(II)/Mn(II)
28
1
2
85
12
Abbreviations: II, cyclohexanol; III, cyclohexanone. a
Reaction conditions: 100°C, 10 atm (air) for 14 h using 37 mmol NHPI.
b c
Turnover number.
Mainly glutaric acid.
d
19 mmol NHPI.
e
9 mmol NHPI.
After ref. (302).
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