United States Patent to 11, 4,018,831

Bowes et al. 45 Apr. 19, 1977

54 PRODUCTION OF 2-ETHYL HEXANAL Primary Examiner-Bernard Helfin
Assistant Examiner-W. B. Lone
75 inventors: Emmerson Bowes, Glassboro, N.J.; Attorney, Agent, or Firm-Carroll F. Palmer
Robert E. Chute, Erie, Pa.
(73) Assignee: Mallinckrodt, Inc., St. Louis, Mo.
22 Filed: Sept. 11, 1975 57 ABSTRACT
(21) Appl. No.: 612,679 2-Ethyl hexanal is produced by hydrogenation of 2
(52) U.S. C. ........................................... 260/601 R ethyl hexene-2-al-1 without substantial formation of
Int. Cl”......................................... C07C 47/02 by-product 2-ethyl hexanol by liquid phase upflow
(51) through a catalyst bed with controlled hydrogen con
(58 Field of Search ................................ 260/601 R centration at 90°-180° C and a pressure of 5-40
56 References Cited Kgm/cm.
UNITED STATES PATENTS
3,449,435 6/1969 Kudu et al. ........................ 260,593
3,903,171 9/1975 Toussaint et al. ............. 260/601 R 2 Claims, No Drawings
 4,018,831 2
1.
high selectivity for olefinic unsaturation hydrogena
PRODUCTION OF 2-ETHYL HEXANAL tion.
BACKGROUND OF THE INVENTION
3. Such methods that produce high yields of 2-ethyl
hexanal.
1. Field of the Invention Other objects and further scope of applicability of
This invention relates to the production of 2-ethyl the present invention will become apparent from the
hexanal by hydrogenation of 2-ethyl hexene-2-al-l. It detailed description given hereinafter; it should be
involves the discovery that the hydrogenation may be understood, however, that the detailed description,
accomplished without producing 2-ethyl hexanol as a while indicating preferred embodiments of the inven
byproduct by using liquid phase upflow through a cata 10 tion, is given by way of illustration only, since various
lyst bed under controlled hydrogen concentration and changes and modifications within the spirit and scope
reaction conditions. of the invention will become apparent to those skilled
2. Description of the Prior Art in the art from this detailed description.
Unsaturated carbonyl compounds can be produced 15 SUMMARY OF THE INVENTION
on an industrial scale by aldolization processes, e.g.,
see U.S. Pat. No. 3,248,428. Dimerization of butyralde These objects are accomplished according to the
hyde in this manner followed by dehydration of the present invention by a process for the production of
condensation product produces 2-ethyl hexene-2-al-l 2-ethylhexanal which comprises:
(TEH). The present invention utilizes TEH prepared in A. providing a bed of particulate hydrogenation cata
this or any other manner for the production of 2-ethyl 20 lyst,y; passing substantially anhydrous liquid comprising
hexanal.
When unsaturated carbonyl compounds, e.g., a-g 2-ethyl-hexene-2-al-1 (TEH) upwardly through said
unsaturated aldehydes, are hydrogenated either the bed at a liquid hourly space velocity (LHSV) from
olefinic unsaturation may be saturated, the carbonyl 25 about 0.5 to 3,
group may be reduced or both reactions may occur. C. providing hydrogen in said liquid in a concentra
For production of saturated carbonyl compound from tion of about 2 to 3 mols of hydrogen per mol of TEH
the unsaturated analog there has been employed either therein,
catalytic liquid phase hydrogenation process (see U.S. D. maintaining the temperature of the catalyst bed at
Pat. No. 3,272,873) or vapor phase hydrogenation 30 about 90°-180°C,
process that has strong activity for olefinic hydrogena E. maintaining the fluid in contact with said catalyst
tion (see U.S. Pat. No. 3,278,605). Palladium catalysts bedF. atrecovering
a pressure between about 7 to 35 Kgm/cm, and
2-ethyl hexanal from the over-head
are known to have a strong activity for hydrogenating
olefinic unsaturation (see U.S. Pat. No. 3,280,192). effluent stream from said catalyst bed.
It is also known that the hydrogenation of the unsatu Concentration of hydrogen in the process is con
rated carbonyl compounds may simultaneously pro 35 trolled by (a) control of the catalyst bed D/A ratio or
duce saturated carbonyl compounds and saturated (b) incremental introduction of hydrogen as will be
alcohol, e.g., 2-ethylhexanal and 2-ethylhexanol from explained below in more detail.
TEH (see U.S. Pat. No. 3,449,435). The liquid reaction mixture charged to the catalyst
Although anhydrous, or substantially anhydrous, 40 bed by liquid phase upflow is preferably a solution of
reaction systems are more generally employed in hy TEH in an inert solvent, e.g., a 10-30% solution in
drogenations as outlined above, aqueous systems have e.g., 2-ethylhexanol. Various known catalysts may be used,
also been disclosed as useful to saturate the olefinic palladium coated or suspended on a carrier, but
group without reduction of the carbonyl function (see producemetal
nickel combined with alumina has been found to
unique results.
U.S. Pat. No. 3,185,757). 45
Palladium catalysts and other having selected activity DESCRIPTION OF PREFERRED EMBODMENTS
for olefinic unsaturation hydrogenation are generally The following details of operations in accordance
expensive and often subject to poisoning by trace impu
rities. Furthermore, processes designed to saturate the with the invention and the reported data illustrate the
olefinic group in unsaturated carbonyl compounds 50 futher principles and practice of the invention. In these
without reduction of the carbonyl function frequently fication examples
specific
and
and throughout the remaining speci
claims, all parts and percentages are by
fail to produce high conversions to the desired product, weight unless otherwise specified.
even when selected activity catalysts are involved. Ac
cordingly, there is a need, notwithstanding the state of EXAMPLE 1
development of the art, for improvements in the selec 55 Catalyst Preparation
tive hydrogenation of unsaturated aldehydes to satu
rated aldehydes and, specifically, conversion of TEH to A solution of nickel nitrate containing 0.038 g.
2-ethylhexanal. Ni/ml. (3430 ml.) was mixed with good agitation with
OBJECTS
1500 ml. of aqueous solution containing 103 g. sodium
60 aluminate, 75.5 g NaOH and 1.82 g. NaCo at ambient
A principal object of this invention is the provision of temperature (20-15° C). At the completion of the
improvements in the production of 2-ethyl hexanal. precipitation, the supernatant liquor was removed by
Further objects include the provision of: filtration and the filter cake was washed six times, each
1. New methods for converting TEH to 2-ethylhexa with a liter of water. The washed filter cake was then
nal with high selectivity relative to by-product conver 65 dried at 110°C and calcined at 350° C. The final pow
sion to 2-ethylhexanol. der was blended with 3% ground graphite and formed
2. Hydrogenation procedures for converting TEH to into slugs in a tablet press. The slugs were granulated
2-ethyl hexanal which do not require catalysts having and tableted in a commerical tablet press to form 4.8 X
 4,018,831 4
3
4.8 mm. cylinders. The cylinders were heated to 375°C ration of the reaction mixture produced the following
in nitrogen and reduced in a flow of hydrogen gas at data:
435+ C. The reduced cylinders were then cooled to TEH converted - 89%
ambient temperature and stabilized by introduction of Product as 2-ethylhexanal - 0.1%
a steam of nitrogen containing 0.1% O, and then con 5 Product as 2-ethyl hexanol - 99.9%
tinuously increasing the oxygen concentration until no DISCUSSION OF DETAILS
further exotherm occurred, the rate of increase of oxy
gen concentration being controlled to limit the temper The success of the present invention is due, in part, to
ature ot a maximum of 65°C. The catalyst is designated the discovery that in hydrogenation of TEH to 2-ethyl
herein as "NiCalsicat'. O hexanal using liquid phase upflow through a catalyst
In another case, catalyst was prepared using the same bed under controlled hydrogen concentration and re
procedure except that the 3430 ml. of nickel nitrate action conditions as described herein, high yields of
solution contained 25.1 g of zinc acetate dihydrate 2-ethylhexanal without substantial by-product 2-ethyl
dissolved therein. The resulting catalyst is referred to hexanol can be obtained with a wide variety hydroge
herein as Ni Calsicat Special and is designed to be 15 nation catalysts, i.e., the new procedures are not de
resistant to poisoning by sulfur in contact with feed pendent on catalysts known to be specific for olefinic
streams that might contain minor amounts of sulfur unsaturation reduction as opposed to carbonyl function
compounds. reduction. Of course, such specific type catalysts may
be used, e.g., palladium metal catalysts, particularly
EXAMPLE 2 20 those using carbon or alumina as a carrier for Pd metal.
2-ethylhexanal Production Unique results have been obtained in the new methods
using nickel-alumina catalysts, particularly such cata
A circular bed of NiCaliscat catalyst of Ex. 1 having lysts formed by coprecipitation of Ni metal, oxide or
a depth to diameter ratio of 2.5 was prepared by load hydroxide and aluminum hydroxide followed by dehy
ing a cylindrical reactor, equipped with inlet and outlet 25 dration, calcination and oxidation to provide a Ni/Al
tubes, to the required depth. Os ratio of between 2:8 and 8.2. Other hydrogenation
A feed stream consisting of 14% 2-ethylhexen-2-al-l catalysts may be used, including cobalt, platinum, tung
and 86% 2-ethylhexanol was pumped into the reactor sten and molybdenum metal and oxides, salts, alloys
at a rate to provide a liquid hourly space velocity and complexes thereof.
(LHSV) of 1.1 through the reactor. The outlet tube 30 The catalysts should be in particulate form for use in
was throttled to create a pressure of aproximately 35 the new methods, e.g., pellets, rings, slugs, discs and
Kgm?cc. and the temperature was adjusted by external other molded shapes or irregular particles. They should
heating jacket to approximately 95 C. Hydrogen gas have an average particle size of between about 1 to 25
under sufficient pressure to enter the feed stream was mm., i.e., from a No. 18 to 1 inch U.S. standard sieve
injected through the reactor inlet tube to give a 2.7:1 35 series size. Preferred particle size is 4 to 12.7 mm., i.e.,
ratio of mols of hydrogen:mol of TEH in the feed No. 5 to 2 inch sieve series size.
stream. When the reactor has reached a steady state, In an embodiment of the invention, a catalyst is used
the effluent stream from the reactor was collected and which carries the active catalyst agent, e.g., Ni metal,
then separated into its components, i.e., TEH, 2-ethyl on the periphery of the catalyst particles so that the
hexanal and 2-ethylhexanol. This separation produced 40 slower carbonyl function reduction reaction will not
the following data: take place in the inner pores of the catalyst. Alterna
TEH converted - 74% tively, a catalyst having porosity large enough as not to
Product as 2-ethylhexanal -97.5% limit diffusion of reactants and products may be em
Product as 2-ethylhexanol - 2.5% ployed.
EXAMPLE 3
45 It is possible to use undiluted TEH as the reaction
liquid in the new methods. Preferably, however, a solu
Modifications of Example 2 tion of TEH in an inert, anhydrous solvent is used.
The procedure of Ex. 2 was repeated with the follow Although 2-ethyl hexanol is preferred as the solvent,
ing changes: others may be used, e.g., pentanol, cyclohexanol, hex
LHSV - 1.6 50 ahydrocumene, diamyl ether, 1.2 - dichlorobenzene,
Reactor temperature - 120 C etc. The concentration of TEH in such solution may be
Mols H/mol TEH - 2.9:1 about 5 - 95% and preferably 10-30%.
Separation of the effluent stream as in Ex. 2 pro The new hydrogenation processes may be conducted
duced the following data: TEH converted - 88% in any form of equipment in which a bed of the catalyst
Product as 2-ethylhexanal - 94% 55 particles may be formed for continuous liquid phase
Product as 2-ethylhexanol - 6% upward flow of reaction liquid through the catalyst bed
In another case the NiCalsicat Special catalyst of Ex. at a liquid hourly space velocity (LHSV) of between
1 was used instead of NiCalsicat. The results were not 0.5-3 and preferably 1.0-1.5. A cylinderical catalyst
appreciably different from those reported above. reactor is advantageously used, but a columnar reactor
60 of square, rectangular or other cross-sectional shape
EXAMPLE 4 may be employed. The equipment should include
Comparison Procedure valved inlets and outlets together with pump means to
provide a liquid pressure of between about 7 to 35 K
The reactor loaded as reported in Ex. 2 with catalyst gm./cm within the catalyst bed. The equipment may be
was operated in reverse, i.e., feed stream was fed down 65 structured so that the hydrogenation is conducted with
wardly so the reactor operated as a trickle bed with an the catalyst bed in a fluidized state.
LHSV of 1.5. Also the reactor was saturated with hy The temperature of the reaction liquid passing
drogen giving a mols H/mol TEH ratio of 160:1. Sepa through the catalyst bed should be about 90 - 180°C
 4,018,831 6
5
and preferably 90 - 120° C. The equipment should be gen concentration in the reaction liquid as it flows
provided with suitable heating means, e.g., external upwardly through the catalyst bed.
steam jacket, electrical resistance heaters, etc., to heat We claim:
the catalyst bed and maintain it at such temperature. 1. A process for the production of 2-ethylhexanal
The concentration of hydrogen in the liquid passing 5 without substantial simultaneous production of 2-ethyl
through the catalyst bed should be controlled to be hexanol which consists essentially of
slightly in excess of the stoichiometric requirement, A. providing a bed of particulate hydrogenation cata
preferably between about 2 to 3 mols of hydrogen per lyst consisting essentially of nickel coated on alu
mol of TEH present in the reaction liquid. In one em mina, the D/A ratio of said bed being between
10 about 1:1 and 6:1 wherein D is the depth of the bed
bodiment, this control is achieved by limiting the D/A in centimeters and A is the cross-sectional area in
ratio of the bed to between about 1:1 and 6:1, D being square centimeters,
the depth of the bed in centimeters and A being the B. passing 2-ethyl-hexene-2-al-1 (TEH) in the liquid
cross-sectional area in square centimeters and intro phase upwardly through said bed at a LHSV from
ducing hydrogen into the reaction liquid prior to 5 about 0.5 to 3,
contact with the catalyst bed to provide the aforesaid 2 C. injecting hydrogen into stream of TEH entering
- 3 mols Halper mol TEH ratio. In the case of a cylin said bed at the base thereof,
derical reactor and catalyst bed, the bed would have a D. maintaining the temperature of said bed at about
D/d ratio of 1:1 to 5:1, D being the depth of the bed and 90° - 180°C,
d the diameter, both measured in centimeters. 20 E. maintaining the fluid in contact with said bed at a
in another embodiment, the hydrogen concentration pressure between about 7 to 35 Kgm?cn”,
is controlled by incremental introduction of hydrogen F. removing a liquid stream overhead from said bed,
and
vertically along the catalyst bed. In such case, the bed G. recovering 2-ethyl hexanal from said overhead
can have a D/A ratio in excess of 6:1 and side entering 25 effluent stream.
inlets spaced vertically along the columnar reactor are 2. The process of claim 1 wherein said catalyst has an
used to introduce hydrogen gas under the reaction average particle size8 between about 1 to 25 mm.
pressure into the reactor to provide the stated hydro : k

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