Acs Oprd 5b00359 PDF
Acs Oprd 5b00359 PDF
Acs Oprd 5b00359 PDF
pubs.acs.org/OPRD
Laboratoire de Genie des Procedes Catalytiques, UMR 5285, CPE Lyon, 43 bld du 11 nov. 1918, 69100 Villeurbanne, France
Conservatoire National des Arts et Metiers, CASER-SITI, 292 rue Saint Martin, 75003 Paris, France
S Supporting Information
*
INTRODUCTION
2-Ethylhexanoic acid 1 is an important chemical intermediate
used in the production of synthetic lubricants, lm plasticizers
for polyvinyl butyral, stabilizers for PVC as well as oil additives,
and functional uids like automotive coolants.1,2 Moreover,
metal salts of 2-ethylhexanoic acid are used in wood
preservatives, as catalyst for polyurethane synthesis, as metal
soaps in paint dryers, and in various other applications.3 This
product belongs to the C8 compounds family and is obtained
through the aldol condensation of butyraldehyde 2.4,5 An
overview of the industrial synthetic pathway to 1 is shown in
Scheme 1.
According to the patent literature, the oxidation of 2ethylhexanal 3 to 2-ethylhexanoic acid 1 is typically performed
in a gas sparged stirred tank or gas lift bubble column reactors
with air or enriched air as the gas phase using molecular oxygen
as the terminal oxidant and with the optional presence of a
catalyst.69 However, this oxidation is strongly exothermic
(rH = 287 kJ/mol, adiabatic temperature rise of 1065 K for
pure aldehyde) and proceeds via highly reactive free radical
species; thus an ecient temperature control is claimed to be
critical for the selectivity, the productivity, and the safety of the
process.69 This intrinsically fast reaction presents gasliquid
mass transfer limitation in most industrial reactors.611 As a
matter of fact, even at the lab scale, the productivities published
in recent articles on aerobic oxidation are aected by the gas to
liquid oxygen mass transfer rate.12,13 In order to reach the
chemical regime and improve the productivity, advanced
microreactors can be used. They are known to provide better
mass and heat transfers than classical vessels.1420 Thus,
continuous ow micro- and millimetric reactors were
2015 American Chemical Society
DOI: 10.1021/acs.oprd.5b00359
Org. Process Res. Dev. 2016, 20, 9094
Communication
Reaction type: (a) hydroformylation; (b) aldol condensation; (c) hydrogenation; (d) oxidation.
EXPERIMENTAL EQUIPMENT
Analytical grade heptane and tetradecane (Aldrich) was used. 2Ethylhexanal 3 (96%) (Aldrich or Acros) was used as obtained
from the supplier and stored at 4 C under N2 with protection
from light. Mn(II) 2-ethylhexanoate (40% in mineral spirits)
was provided by STREM and used as obtained. Pressurized
oxygen (99.995%) was provided by Messer.
Figure 1 shows the experimental setup. A PFA tubing
(Upchurch Scientic) (internal diameter of 1.65 mm with
DOI: 10.1021/acs.oprd.5b00359
Org. Process Res. Dev. 2016, 20, 9094
Communication
conditions, in the rst part of the tube, the initial transfer rate is
improved, and consequently so is the apparent reaction rate.
When high conversion is reached, the total ow rate decreases
(due to O2 volume decreasing), and this phenomenon possibly
aects the oxygen mass transfer coecient and thus the
apparent reaction rate. Thus, residence time could not be
precisely determined under these conditions, but it can be
visually estimated to be around 1 min. Nevertheless conversion,
selectivity, and volumetric reactor productivity could be
precisely determined. One important consequence of the new
conditions is a ca. 10-fold increase of the heat ux from the
reaction (vide supra). As a precaution and to enhance cooling
of the reaction mixture, the PFA tubing was immersed in a
water bath at 25 C, and the slower uncatalyzed neat oxidation
of 2-ethylhexanal 3 was attempted rst.
Under neat conditions, the uncatalyzed aerobic oxidation of
3 proceeds gently (Table 1, entry 1). A low conversion and a
entry
catalyst (ppm)
O2 (bar)
conv. (%)b
select. (%)b
1
2c
3d
4
5e
6f
0
10
200
10
10
5
6
6
6
7.5
7.5
7.5
9
95
69
>99.5
52
>99.5
95
95
56
94
94
97
a
General conditions: Inlet O2 ow: 200 NCCM, inlet aldehyde ow:
2.5 mL/min., neat 2-ethylhexanal 3 containing sodium 2-ethylhexanoate (2 wt %), tetradecane as internal standard (1 wt %), tube
length: 6.7 m, id: 1.65 mm, water bath at 25 C. bMean value of at
least three samples spaced 2 min. cSee movie No. 1. dVaporization of
the liquid phase was observed in the rst 10 cm, see movie No. 2.
e
Water bath at 5 C. fG and L ow rate divided by 2.
CONCLUSION
These experiments demonstrate the capability of simple tube
microreactor (total volume of 15 mL, overall footprint of half
the size of standard laboratory fume hood) to perform
continuous reactions under explosive conditions. A daily
production of 3.22 kg of 2-ethylhexanoic acid with a purity of
94% could be reached without further purication nor solvent
separation with simple, cheap, and readily available materials
and equipment. Such productivity could not be considered
using a classical 10 L lab-scale batch reactor for safety reasons
due to the explosive gas mixture,33,34 the adiabatic temperature
rise of 1065 K and the required heat removal capability of about
700 W. The use of PFA tubing allows the visual control of the
ow associate to a low permeability to liquids, gases, organic
vapors, and wide operating temperature range (240 C to
+260 C). However, the relatively low heat transfer coecient
of PFA (0.195 W/mK) does not allow ecient management of
the reaction heat ux. Thus, the catalyst amount had to be
decreased to maintain the high conversion and selectivity of the
process. Higher oxygen pressure and total ow velocity
associated with a better heat management integration would
help to improve the productivity by reaching a more favorable
process window.
DOI: 10.1021/acs.oprd.5b00359
Org. Process Res. Dev. 2016, 20, 9094
Communication
Figure 3. Top view of the PFA tubing layout and visualization of the segmented G/L ow during the aerobic oxidation of 2-ethylhexanal 3. Reaction
conditions: neat 2-ethylhexanal 3 + 2 wt % of sodium 2-ethylhexanoate, 6 bar of O2, PFA tube length: 6.7 m, i.d.: 1.65 mm, water bath at 25 C, 10
or 200 ppm, respectively, of Mn(II) for the upper and for the lower picture (images taken from the movies, see the Supporting Information).
AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected].
Notes
(1) Kohlpaintner, C.; Schulte, M.; Falbe, J.; Lappe, P.; Weber, J.
Aldehydes, Aliphatic and Araliphatic. In Ullmanns Encyclopedia of
Industrial Chemistry, 6th ed.; Wiley-VCH: 2003; Vol. 2, pp 6599.
(2) BASF and PETRONAS Chemicals Group have built a new
world-scale production plant for 2-ethylhexanoic acid with a total
annual capacity of 30 000 t in Kuantan, Malaysia. The plant is expected
to start production in the fourth quarter of 2016. https://www.basf.
com/en/company/news-and-media/news-releases/2015/02/p-15146.html (accessed Dec 15, 2015).
(3) Raju, R.; Prasad, K. Tetrahedron 2012, 68, 13411349.
(4) Riemenschneider, W. Carboxylic Acids, Aliphatic. In Ullmanns
Encyclopedia of Industrial Chemistry, 6th ed.; Wiley-VCH: 2003; Vol. 6,
pp 493508.
(5) Seki, T.; Grunwaldt, J.-D.; Baiker, A. Chem. Commun. 2007,
35623564.
(6) Litz, L. M.; Santalone, J. J. Improved gas-liquid mixer. Eur. Patent
No. 0 374 967, Dec. 23, 1988.
(7) Weise, M. K.; Adis, M. Enhanced gas-liquid reactions. Eur. Patent
No. 0 439 013, Jan 3, 1990.
(8) Kingsley, J. P.; Litz, L. M.; Lacopelli, F. S.; Weise, M. K. Process
for producing organic acids. Eur. Patent No. 0 792 865, Feb 27, 1996.
(9) Koch, H. F.; Reed, R. P. Oxidation process. Patent WO No. 01/
303 46111, June 28, 2001.
(10) Sajus, L.; Sere De Roch, I. The Liquid Phase Oxydation of
Aldehydes. In Liquid-Phase Oxidation, Boamford, C. H., Tipper, C. F.
H., Eds.; Elsevier: Amsterdam, 1980; Vol. 16, pp 89124.
(11) McNesby, J. R.; Heller, C. A. Chem. Rev. 1954, 54, 325346.
(12) Vanoye, L.; Favre-Reguillon, A.; Aloui, A.; Philippe, R.; de
Bellefon, C. RSC Adv. 2013, 3, 1893118937.
REFERENCES
ASSOCIATED CONTENT
S Supporting Information
*
DOI: 10.1021/acs.oprd.5b00359
Org. Process Res. Dev. 2016, 20, 9094
Communication
94
DOI: 10.1021/acs.oprd.5b00359
Org. Process Res. Dev. 2016, 20, 9094