US006121498A

United States Patent 19 11 Patent Number: 6,121,498

Tustin et al. (45) Date of Patent: Sep.19, 2000
54 METHOD FOR PRODUCING R. Pestman et al., “The formation of ketones and aldehydes
ACETALDEHYDE FROMACETIC ACID from carboxylic acids, Structure-activity relationship for
two competitive reactions”,Journal of Molecular Catalysis,
75 Inventors: Gerald C. Tustin; Leslie S. Depew, pp. 175-180, (1995).
both of Kingsport; Nick A. Collins, Fall Z.F. Pei et al., “On the intermediates of the acetic acid
Branch, all of Tenn.
reactions on oxides: an IR Study”, Applied Surface Science,
Assignee: Eastman Chemical Company, 103, pp. 171-182, (1996).
Kingsport, Tenn.
(List continued on next page.)
Appl. No.: 09/069,953
Filed: Apr. 30, 1998 Primary Examiner-Howard C. Lee
ASSistant Examiner Everett White
Int. Cl." ........................... C07C 47/00; CO7C 45/00; Attorney, Agent, or Firm-Harry J. Gwinell; Matthew W.
B01J 23/00; B01J 23/42 Smith
U.S. Cl. .......................... 568/420; 568/401; 502/300; 57 ABSTRACT
502/326; 502/339
Field of Search ..................................... 568/.420, 401; A method of producing acetaldehyde hydrogenates acetic
502/300, 325, 339 acid in the presence of an iron oxide catalyst containing
between 2.5 and 90 wt % Pd, more preferably 10 and 80 wt
References Cited % Pd and most preferably 20 and 60 wt % Pd. The catalyst
has a specific Surface area of less than 150 m/g. Hydrogen
U.S. PATENT DOCUMENTS and acetic acid are fed to a reactor in a hydrogen to acetic
4,237,073 12/1980 Steppich et al. ........................ 568/401
acid ratio of 2:1 to 25:1, more preferably in a hydrogen to
4,268.362 5/1981 Ogawa et al. ............................ 203/28 acetic acid ratio of 3:1 to 15:1 and most preferably in a
5,059,716 10/1991 Joentgen et al. ..... ... 568/426 hydrogen to acetic acid ratio of 4:1 to 12:1. The hydroge
5,306,845 4/1994 Yokohama et al. ...... ... 568/449 nation is performed at a temperature of about 250 C. to
5,336,810 8/1994 Van Geem et al. .................... 568/435 400° C., more preferably about 270° C. to 350° C. and most
preferably about 280° C. to 325° C. The hydrogenation of
FOREIGN PATENT DOCUMENTS acetic acid produces a partially gaseous product, and acetal
0539274A1 4/1993 European Pat. Off.. dehyde is absorbed from the partially gaseous product with
0700890A1 11/1996 European Pat. Off.. a Solvent containing acetic acid. The gas remaining after the
WO 96/18458 6/1996 WIPO. absorption Step contains hydrogen, and this gas is recycled
for the hydrogenation of acetic acid. The absorbed acetal
OTHER PUBLICATIONS dehyde is distilled to isolate Same. After acetaldehyde is
isolated from unreacted acetic acid and the other products
J. Kondo et al., “Infrared Study of Hydrogenation of Ben Via distillation, the unreacted acetic acid is separated from
zoic Acid to Benzaldehyde on ZrO Catalysts”, Bull. Chem. the other products using azeotropic distillation. Water is
Soc., Jpn, pp. 3085-3090, (1993). contained in the other products, and the azeotrope is an
R. Pestman et al., “Selective hydrogenation of acetic acid azeotrope of ethyl acetate and water. The unreacted acetic
towards acetaldehyde', Reel. Trav: Chim. Pays-Bas, 113, acid is separated in a column, and the column is controlled
pp. 426-430, (1994). to contain an ethyl acetate rich azeotrope of ethyl acetate and
E.J. Grootendorst et al., “Selective Reduction of Acetic Acid Water.
to Acetaldehyde on Iron Oxides”,Journal of Catalysis, 148,
pp. 261-269, (1994). 27 Claims, 2 Drawing Sheets

OFFGAS/18

PRODUCT
19

S. 23 TO HOAC
RECOVERY
30

C-SE
 6,121.498
Page 2

OTHER PUBLICATIONS Pavlova, et al., “Low-Temperature Co Oxidation on Iron

Oxide S ted Palladium”. React. Kinet. Catal. Lett
Pestman, et al., “Identification of the Active Sites in the N. yer p "No. edCl. Klilei. Udial. Lell, VO1.
Selective Hydorgenation of Acetic Acid to Acetaldehyde on
Iron Oxide Catalysts”, Journal of Catalysis, vol. 174, 1998, Abstract of Japanese Patent Publication No. 9-100254A,
pp. 142-152. Apr. 15, 1997.
Pestman, et al., “Reactions of Carboxylic Acids on Oxides”, Chemical Abstracts, vol. 113, No. 8, Aug. 20, 1990, p. 136,
Journal of Catalysis, vol. 168, 1997, pp. 255-264. Abstract No. 61684.
U.S. Patent Sep. 19, 2000 Sheet 1 of 2 6,121.498

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 6,121.498
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METHOD FOR PRODUCING reaction (I) (300–400° C.). The above discussed reactions
ACETALDEHYDE FROMACETIC ACID related to hydrogen and acetic acid in the vapor phase are
Summarized below:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates in general to producing (I) CH,CO.H + H, -> CHCHO + HO AGse . . = +0.8
acetaldehyde. More specifically, the present invention kcal/mole
relates to producing acetaldehyde by hydrogenating acetic AGoooo... = -0.04
kcal/mole
acid. (II) CHCHO + H, -> CHCH-OH AGse . . = -0.4
2. Description of the Related Art kcal/mole
Acetaldehyde is an important industrial chemical. It has AGooo c. = +2.5
kcal/mole
been used as a Starting material for the commercial manu (III) 2 CH,CO.H-> CHCOCH + CO + H.O.
facture of acetic acid, acetic anhydride, cellulose acetate,
other acetate esters, Vinyl acetate resins, Synthetic pyridine 15
derivatives, terephthalic acid, peracetic acid and pentaeryth The hydrogenation of acetic acid to acetaldehyde and
ritol. Historically, acetaldehyde has been used to produce water (reaction (I)) is a mildly endothermic reaction. So, the
acetic acid, but improvements in technology have resulted in thermodynamics of this reaction improve as the temperature
more economical acetic acid production from Synthesis gas is increased. The Subsequent reaction (II), the hydrogenation
(a mixture of carbon monoxide and hydrogen). This devel of acetaldehyde to ethanol, is exothermic, and this reaction
opment implies that it may be more economically attractive becomes less favorable as the temperature increases. Since
the equilibrium of the acetic acid hydrogenation is poor, the
to produce acetaldehyde from acetic acid rather than to reaction must be run with an excess of hydrogen to achieve
produce acetic acid from acetaldehyde if a technically viable appreciable acetic acid conversion. Thus, on a thermody
route existed. namic basis, ethanol formation will be favored at tempera
Acetaldehyde has been produced commercially by the 25 tures of 300–400° C. Reaction (III), the formation of
reaction of ethanol with air at 480 C. in the presence of a acetone, is essentially irreversible at all temperatures above
Silver catalyst. This process has been replaced by the current O C. and becomes very favorable thermodynamically as the
process, the Wacker oxidation of ethylene. Both of these temperature is increased. Increasing the temperature signifi
processes Start with ethylene, and the Wacker route is more cantly above 400° C. will not likely improve the selectivity
direct and efficient than the ethanol oxidation route. Acetal to the desired acetaldehyde product because of increasing
dehyde has also been produced by the hydration of acety acetone production. Other reactions, Such as the formation
lene. This process uses mercury Salts as a catalyst, and of methane, carbon oxides and C2 hydrocarbons also are
mercury handling can cause environmental and Safety prob relevant in acetic acid hydrogenation chemistry, but are of
lems. The use of acetylene causes Safety concerns, and the leSS importance than the three reactions described above
high cost of acetylene relative to ethylene has rendered this 35 unless excessively high temperatures are used. In Some
process obsolete. Acetaldehyde can also be produced by circumstances, the formation of ethyl acetate presumably
reacting Synthesis gas over a rhodium on Silica catalyst at through ethanol as an intermediate can also lower the
elevated temperature and preSSure, but the Selectivity to Selectivity to the desired acetaldehyde.
acetaldehyde is poor, and the proceSS has never been prac Thus, it appears that a major challenge in producing
ticed commercially. Acetaldehyde has also been produced 40 acetaldehyde Via acetic acid hydrogenation is catalyst
from the reaction of methanol with Synthesis gas at elevated design. The ideal catalyst should facilitate the initial hydro
temperature and pressure using a cobalt iodide catalyst with genation of acetic acid to acetaldehyde but have essentially
a group 15 promoter, but this process also has never been no activity for the Subsequent hydrogenation to ethanol nor
practiced commercially. Although the Wacker proceSS is the for the dimerization reaction producing acetone. If a catalyst
preferred commercial process at this time, it also has many 45 has even a Small activity for conversion of acetaldehyde to
undesirable aspects. These include the Special Safety and ethanol or for the conversion of acetic acid into acetone, then
handling problems associated with reacting ethylene with extreme losses in acetaldehyde Selectivity may occur if the
oxygen and the very corrosive nature of the aqueous acidic reaction is operated beyond the equilibrium conversion level
chloride-containing reaction mixtures which necessitates allowed for converting acetic acid and hydrogen into acetal
very expensive materials of construction. Thus a need exists 50 dehyde and water. A need exists for a catalyst that Selectively
for an acetaldehyde Synthesis that is an improvement over hydrogenates acetic acid to acetaldehyde.
the existing known processes. Catalyst Selectivity is only one requirement for a viable
A potentially attractive means to Synthesize acetaldehyde acetaldehyde Synthesis. The Synthesis must also be operated
is by the hydrogenation of acetic acid. See reaction (I) in a manner that will allow for the facile recovery of the very
below. However the carboxylic acid group is generally 55 Volatile acetaldehyde product, the recovery of byproducts
considered to be among the most difficult functional groups and the recycle of unconverted reactants. Generally pro
to reduce by catalytic hydrogenation. Aldehyde groups, ceSSes that hydrogenate carboxylic acids to aldehydes do So
conversely, are easily reduced by catalytic hydrogenation to under conditions of about 1 bar pressure (all pressures given
alcohols. See reaction (II) below. Thus, under the conditions herein are in terms of absolute pressures) and hydrogen to
required to reduce a carboxylic acid, the aldehyde is often 60 carboxylic acid ratioS approaching 50/1. Although these
not isolated in good yield because the aldehyde is further conditions may be sufficient for nonvolatile aldehydes, they
reduced to an alcohol. Furthermore, when the carboxylic are impractical for acetaldehyde which boils at 19-20 C.
acid contains an O-hydrogen, conversion to a ketone, water Thus, a need also exists for a process that converts acetic
and carbon dioxide can occur. See reaction (III) below. This acid into acetaldehyde in a manner that is Selective and
reaction becomes more prevalent as the number of 65 provides for the economical recovery of the acetaldehyde.
C-hydrogens increases. Thus, acetone can be readily formed In spite of the thermodynamic limitations Surrounding the
from acetic acid at the temperatures typically used for hydrogenation of carboxylic acids to aldehydes, Several
 6,121.498
3 4
examples of this reaction appear in the prior art. Generally that there is an optimum Pt level, and that increasing the Pt
these reactions are performed at about 1 bar pressure in the level above 1.25 atomic % actually decreases the selectivity.
Vapor phase in a large exceSS of hydrogen at temperatures Although the acetic acid hydrogenation proceSS Studied
ranging between 200 and 500 C., and the reaction is most by Ponec and coworkers is very Selective to acetaldehyde, it
Successful with aromatic carboxylic acids or aliphatic acids is impractical as a commercial way to produce acetaldehyde.
containing few C-hydrogens. Van Geem et al., in U.S. Pat. The impracticality Stems from the need to isolate and collect
No. 5,336,810, describe a Mn/Zn/Al oxide catalyst that acetaldehyde (normal boiling point=19-20° C.) from a
converts benzoic acid to benzaldehyde in the vapor phase at Vapor Stream where it is present in maximum concentrations
330 C. in a large excess of hydrogen in 88.3% selectivity of 2-3% (or less, depending on the conversion) at about 1
at 98.9% conversion. Joentgen et al., in U.S. Pat. No. bar pressure. Water and byproducts must be removed from
5,059,716, describe catalyst system based on titanium or the mixture, and hydrogen and unconverted acetic acid must
Vanadium oxides in conjunction with one or more metals be recycled to the reactor. These operations require that the
Selected from Cr, Mo, Co, Ni, Zn, Cd and Cu for the temperature be lowered considerably from the 300-400 C.
hydrogenation of aromatic and aliphatic carboxylic acids reaction temperature. A practical process requires much
containing not more than one O-hydrogen at 325-425 C. at 15 lower hydrogen/acetic acid ratioS and much higher reaction
1 bar in the presence of a large exceSS of hydrogen. preSSures than used by Ponec.
Yokoyama et al., in Stud. In Surf Sci. and Cat. 1994, 90,
47–58 and in Bull Chem. Soc. Jpn. 1993, 66, 3085-3090, SUMMARY OF THE INVENTION
describe the use of Zirconium oxide and modified Zirconium Accordingly, it is an object of the present invention to
oxide catalysts for the hydrogenation of aromatic carboxylic provide a method of producing acetaldehyde that avoids
acids to aldehydes under Similar reaction conditions. dangers associated with mercury and acetylene.
Yokoyama et al., in U.S. Pat. No. 5,306,845, also describe It is a further object of the present invention to provide a
the use of a purified chromium oxide catalyst for the method of producing acetaldehyde that avoids handling
hydrogenation of both aromatic and aliphatic carboxylic problems associated with reacting ethylene and oxygen.
acids under Similar reaction conditions. This patent gives 25
Several examples of the hydrogenation of high molecular It is a still further object of the present invention to
weight acids, Such as Stearic acid. Acetic acid is also Stated provide a method of producing acetaldehyde that avoids
to be as a Suitable acid, but no examples are given. corrosive aqueous acidic acid chloride-containing reaction
Yokoyama et al. StreSS that the reason for the high purity mixtures.
requirement in the chromium oxide is to prevent the ketone It is another object of the present invention to provide a
formation reaction. Welguny et al., in European Patent method for hydrogenating acetic acid with good Selectivity
Application EP 0 700 890 (1996), describe the use of for producing acetaldehyde.
oxide-Supported tin catalysts for hydrogenation of a wide It is still another object of the present invention to provide
variety of carboxylic acids to aldehydes under the typical a method for hydrogenating acetic acid that allows for easy
high-temperature, high-hydrogen, low-pressure conditions 35 recovery of Volatile acetaldehyde.
described previously. Although acetic acid is included in the These and other objects are accomplished by a method of
claims of this patent application, the only examples are for producing acetaldehyde that hydrogenates acetic acid in the
aromatic carboxylic acids and for pivalic acid. Ferrero et al., presence of an iron oxide catalyst containing between 2.5
in European Patent Application No. EP 539,274 (1993), and 90 wt % Pd, more preferably 10 and 80 wt % Pd and
describe Ru-Sn-B on alumina catalysts for hydrogena 40 most preferably 20 and 60 wt % Pd. The catalyst has a
tion of a wide variety of carboxylic acids to aldehydes under specific Surface area of less than 150 m/g. Hydrogen and
the typical high-temperature high-hydrogen low-pressure acetic acid are fed to a reactor in a hydrogen to acetic acid
conditions described previously. Although the Ferrero patent ratio of 2:1 to 25:1, more preferably in a hydrogen to acetic
application gives no examples for acetic acid hydrogenation, acid ratio of 3:1 to 15:1 and most preferably in a hydrogen
it is mentioned in the claims. Most of the Ferrero reference 45 to acetic acid ratio of 4:1 to 12:1. The hydrogenation is
concerns the reduction of Senecioic acid to prenal or the performed at a temperature of about 250 C. to 400 C.,
reduction of aromatic carboxylic acids to the corresponding more preferably about 270° C. to 350° C. and most prefer
aldehydes. ably about 280 C. to 325 C. The hydrogenation of acetic
The most definitive work on the acetic acid hydrogenation acid produces a partially gaseous product, and acetaldehyde
to acetaldehyde is described by Ponec and coworkers in 50 is absorbed from the partially gaseous product with a Solvent
Recl. Trav. Chim. Pays-Bas 1994, 426-430, in J. Catal. containing acetic acid. The gas remaining after the absorp
1994, 148, 261-269, in J. Molecular Catalysis A. Chemical tion Step contains hydrogen, and this gas is recycled for the
1995, 103, 175-180, in Applied Surface Science 1996, 103, hydrogenation of acetic acid. The absorbed acetaldehyde is
171-182, and in J. Catal. 1997, 168, 255-264. These distilled to isolate Same. After acetaldehyde is isolated from
workers have proposed a working mechanism for the reac 55 unreacted acetic acid and the other products via distillation,
tion and have reported Several examples of the conversion of the unreacted acetic acid is separated from the other prod
acetic acid to acetaldehyde in good Selectivity. The base ucts using azeotropic distillation. Water is contained in the
catalysts for these reductions are partially reduced metal other products, and the azeotrope is an azeotrope of ethyl
oxides having an intermediate metal-oxygen bond strength. acetate and water. The unreacted acetic acid is separated in
Partially reduced iron oxide is the most selective metal 60 a column, and the column is controlled to contain an ethyl
oxide, and acetaldehyde Selectivities almost as high as 80% acetate rich azeotrope of ethyl acetate and water.
could be obtained at 1.2 bar preSSure and using a hydrogen/ BRIEF DESCRIPTION OF THE DRAWINGS
acetic acid ratio=50/1 at 321° C. Addition of 5 wt.% Pt to
this catalyst further increases the Selectivity to acetaldehyde The invention will be readily understood by reference to
to over 80%. With tin oxide, the addition of the Pt about 65 the following description of the Specific embodiments
doubles the selectivity, increasing it from about 40% to described by way of example only, with reference to the
about 80%. Ponec mentions in J. Catal. 1997, 168, 255-264 accompanying drawings, wherein:
 6,121.498
S 6
FIG. 1 is a Schematic representation of components used AR, acetic acid is recovered from stream 33. This acetic acid
to produce acetaldehyde; and may be mixed with hydrogen and fed to reactor RX via
FIG. 2 is an Schematic representation of components used stream 3.
to recover acetic acid. The overhead from acetic acid column AC contains ethyl
acetate, water and other products. Because water is difficult
DETAILED DESCRIPTION OF THE to Separate from acetic acid as mentioned above, it is
PREFERRED EMBODIMENTS important that excess water not be Supplied via Stream 35.
For this purpose, Stream 32 is condensed in decanter cooler
The present invention will now be described with pre DC and then decanted in decanter DE. The aqueous phase
ferred embodiments and examples which are given by way leaves decanter DE in Stream 38, and the organic phase
of example only, not limitation. leaves in stream 37. A portion of stream 37 is supplied back
A specific embodiment of the process of the invention to the acetic acid column AC. Another portion of stream 37
consists of two main Sections: a reaction Section and a is fed to azeotrope column Zvia stream 39 to distill a “near”
recovery section shown schematically in FIGS. 1 and 2, ethyl acetate-water azeotrope. The mixture is a “near
respectively. Acetic acid is converted to acetaldehyde and 15 azeotrope because it does not contain the exact azeotropic
water with exceSS hydrogen in the reaction Section over a ratio of ethyl acetate to water. AS mentioned above, the
catalyst containing iron and palladium in a fixed-bed reactor azeotrope has a low boiling point and therefore can be
RX. The acetaldehyde product is recovered via distillation D removed as an overhead from azeotrope column Z. After
after absorption A using the acetic acid-rich distillation azeo column condenser ZC, the azeotrope is indirectly
bottoms as a Solvent after cooling S. recycled back to acetic acid column AC via Stream 43.
Referring to FIG. 1, stream 3 is a feed to the reactor RX From the bottom of azeotrope column Z, stream 42 is
containing acetic and hydrogen. Although a 1-to-1 molar Supplied to ethyl acetate column E after azeo column
ratio is Stoichiometrically Sufficient for producing reboiler ZR. AS mentioned above, exceSS hydrogenation of
acetaldehyde, an excess of hydrogen is Supplied in feed 3. acetic acid produces ethanol. The ethanol can react with the
The reactor RX contains an iron oxide/palladium catalyst. 25 acetic acid and produce ethyl acetate in an esterification
Before the feed is supplied to the reactor, it is heated with process. This reaction occurs throughout the apparatus,
furnace F and reactor preheater PH. The product of reactor whenever ethanol and acetic acid are present together. The
RX is fed to an absorber A. This product is hot and is cooled reaction may be especially prominent when both reactants
in feed effluent exchanger FE. Feed effluent exchanger FE are in the liquid phase. Ethyl acetate column E Separates
also serves to preheat the feed 3 to the reactor. The product ethyl acetate as an overhead. After ethyl acetate column
of reactor RX is Substantially gaseous. Absorber A is used to condenser EC, Stream 54 contains ethyl acetate which can be
liquify the acetaldehyde and other products. Cooled product sold as a finished product. From the bottom of ethyl acetate
4 Supplied to the absorber A and acetic acid feed 7 is also column E, a somewhat Small stream 55 of acetic acid is
Supplied. Acetic acid from feed 7 captures the products and produced after ethyl acetate column reboiler ER.
allows hydrogen to pass via Stream 6. A portion of the 35 AS mentioned above, decanter DE Separates aqueous
hydrogen is recycled via Stream 10, recycle compressor RC products from organic products. The aqueous Stream 38 is
and Stream 13. Another portion of the hydrogen is purged via Supplied to Steam Stripper SS. Steam Stripper SS is a
Stream 9, and this maintains the purity of hydrogen. Recycle distillation column heated by Steam 46. Lighter organics
compressor RC compresses the hydrogen. Reactor RX and come off the top of steam stripper SS in stream 45 and waste
absorber A operate under pressure. The pressure in absorber 40 water comes off the bottom as stream 47. The organics in
A is from pressurized product in Stream 4 and from pump Stream 45 are Supplied to waste acetone column W. Acetone
PU. has a very low boiling point, even lower than the azeotrope.
The liquid coming off of absorber A as stream 8 is sent to Thus, a waste acetone Stream 51 is produced after acetone
distillation column D to recover acetaldehyde. The overhead column condenser WC. From the bottom of the waste
from distillation column D is cooled via condenser C to 45 acetone column W, a near ethyl acetate-water azeotrope
condense Same. A portion of the condensed liquid is sent stream 50 is recycled after acetone column reboiler WR.
back to the distillation column D as a reflux. Offgas 18 is not The two azeotrope recycle streams 50 and 43 are not
condensed and leaves the system shown in FIGS. 1 and 2. Supplied directly back to the acetic acid column AC. Instead,
Acetaldehyde product comes from Stream 19, and this also they are fed to decanter cooler DC and decanter DE to
leaves apparatus shown in FIGS. 1 and 2. From the bottom 50 remove Water.
of the distillation column, a re-boiler RB is provided to The processes depicted in FIGS. 1 and 2 are designed for
Supply the more Volatile compounds back to the distillation optimum operation at the following conditions: 1) a 5/1
column D. Stream 23 is acetic acid rich and is partially molar ratio of hydrogen to acetic acid in the reactor RX feed
recycled to the absorber A. AS mentioned previously, the 3, 2) byproduct ethanol is converted to ethyl acetate as
absorption in absorber A works best at lower temperatures, 55 dictated by chemical equilibrium at of conditions present in
and Solvent cooler S is provided for this purpose. the bottom of the acetaldehyde recovery column D, and 3)
Stream 30 may contain ethyl acetate, water, acetic acid the reactor operates at 300 C., 17.2 bar, and 45% acetic acid
and acetone. To Separate these compounds, the recovery conversion with a selectivity of 89% to acetaldehyde, 5% to
apparatus shown Schematically in FIG. 2 is employed. First, ethanol, 4% to acetone (and CO), and 2% to methane and
acetic acid column AC is used to Separate out acetic acid. 60 C2 hydrocarbons (ethylene plus ethane). If the degree of
The boiling point of acetic acid is very close to that of water, ethyl acetate formation from ethanol and unconverted acetic
and it would normally be difficult to separate these two acid in the reactor RX is low, the reaction may be simply
components via distillation. To address this problem, ethyl catalyzed by adding sulfuric acid to the HOAc-rich solvent
acetate is fed to acetic acid column AC via stream 35. Ethyl before recovery. The recovery scheme shown in FIG. 2 is
acetate forms an azeotrope with water. The azeotrope has a 65 highly dependent on this conversion of byproduct ethanol to
boiling point Significantly lower than either water or ethyl ethyl acetate and is a significant part of the present inven
acetate. This enables Separation. After acetic acid reboiler tion.
 6,121.498
7 8
Mass-separating agents other than ethyl acetate are poS 90 wt % Pd with the balance of the weight calculated as
Sible. Such agents may be Selected from those organic FeO (the actual chemical nature of the iron may or may not
compounds that from a minimum-boiling azeotrope with be FeO depending on the Specific method of catalyst
water and Separate into water-rich and organic-rich liquid Synthesis used). More preferred catalysts contain between
phases upon condensation. Those skilled in the art of Sepa 10 and 80 wt % Pd based on FeO. The most preferred
rations may select Such an alternate to ethyl acetate and catalysts contain between 20 and 60 wt % Pd based on
modify the proceSS depicted in FIG. 2 appropriately. Fe2O. Catalysts containing low amounts of palladium per
However, as ethyl acetate is a coproduct of the process its form well under low-pressure high-hydrogen conditions, but
use as an azeotroping agent avoids introducing another may not perform well under the high-pressure low-hydrogen
compound to the process and as Such is used in the preferred conditions preferred in the invention. Catalysts containing
embodiment. low amounts of palladium may rapidly lose their activity and
In the preferred embodiment the azeotroping agent both Selectivity under the high-pressure low-hydrogen conditions
forms a minimum boiling azeotrope with water and forms preferred in the invention. Excessively high amounts of
two liquid phases upon condensation. Potential azeotroping 15 palladium are uneconomical and may produce excessive
agents include, but are not limited to, acrylonitrile, allyl amounts of hydrocarbons. The active components of the
acetate, allyl acetone, allyl cyanide, benzene, 1-butanol, catalyst of the invention can be Supported, but the Support
1-butenylethyl ether, 1-butoxy-2-propanol, butyl acetate, should be unreactive for the conversion of acetic acid to
butyl acetoacetate, butyl acrylate, n-butyl aniline, butyl acetone. The catalyst should have a surface area below 150
benzoate, butylbutyrate, butyl chloride, butyl ether, butyl m/g. Catalysts with excessively high Surface areas can
isoprope nyl ether, 2-butyl octanol, butyraldehyde, exhibit reduced selectivity to the desired acetaldehyde. The
butyronitrile, carbon disulfide, carbon tetrachloride, catalysts of the invention may be reduced in hydrogen prior
2-chloroethyl ether, chloroform, chloroisopropyl ether, to their use in the reaction of hydrogen and acetic acid by
crotonaldehyde, cyclohexane, cyclohexanone, 25 contacting the catalysts with hydrogen at about between 50
cyclopentanone, diallyl acetal, diallyl amine, dibutyl acetal, and 500 C. and at about 1-50 bar pressure. More preferred
dibutyl amine, dibutyl ethanolamine, 2,3-dichloropropanol, prereduction conditions are between 200 and 400° C. and
dicyclopentadiene, diethyl acetal, diethyl butyral, 1-20 bar preSSure, and the most preferred prereduction
disobutylene, diisobutyl ketone, dimethyl butyral, 2.5- conditions are between 250 and 350° C. and 1-5 bar
dimethyl furan, 2,6-dimethyl-4- he ptanol, preSSure.
dimethylisobutyral, dipropyl acetal, dipropyl ketone, It is rather important that the catalyst be in a correct
epichlorohydrin, ethyl acetate, ethyl acrylate, n-ethyl oxidation State, and the correct oxidation State should be
aniline, ethylbenzene, 2-ethylbutanol, 2-ethylbutyl acetate, readily regenerated under the reaction conditions. If the
2-ethylbutyl butyrate, ethylbutyl ether, ethylbutyl ketone, 35 catalyst is in an over oxidized State, then acetone becomes
2-ethylbutyraldehyde, ethylcrotonate, ethylene dichloride, the predominant product. The Selective catalysts contain a
ethyl formate, 2-ethylhexanol, 2-ethylhexyl acetate, mixture of Zero Valent metal and metal oxide phases. If the
2-ethylhexyl amine, 2-ethylhexyl chloride, 2-ethylhexyl catalyst is in an over reduced State, methane becomes the
crotonate, 2-ethylhexyl ether, ethylidene acetone, 40
predominant product. Addition of Pd to the catalyst facili
4-ethyloctanol, ethyl propionate, heptane, 2-heptyl acetate, tates the formation and maintenance of the desired oxidation
3-heptyl acetate, hexaldehyde, hexane, hexanol, 2-hexenal, State.
hexyl acetate, hexyl chloride, isobutyl alcohol, isophorone, The catalysts of the invention are reactive and Selective
isopropyl acetate, isopropylbenzene, isopropyl chloride, iso under a wide variety of conditions. Temperatures can range
propyl ether, mesityl oxide, methacrylaldehyde, 1-methoxy 45 from about 250 to 400° C. More preferred temperatures
1,3-butadiene, 3-methoxybutyl acetate, methylamylketone, range from 270 to 350° C., and the most preferred tempera
methylene chloride, 2-methyl-5-ethyl pyridine, 5-methyl-2- ture range is from 280 to 325 C. At low temperatures the
hexanone, methylisobutyl ketone, methylisopropenyl rate may be low and, if the mixture is low in hydrogen, the
ketone, n-methylmorpholine, 2-methyl pentanal, 2-methyl reaction can also be limited by the equilibrium restrictions
50
pentanol, 4-methyl-2-pentanol, 4-methyl-2-pentene, dictated by the thermodynamics of the reaction. Excessively
4-methyl-2-pentyl acetate, 2-methylpropyl acetate, methyl high temperature can lead to lower acetaldehyde Selectivity
propyl ketone, nonane, paraldehyde, pentane, 2,4- due to the formation of acetone and hydrocarbons. PreSSures
pentanedione, 3-pentanol, propionitrile, propyl chloride, can range from less than 1 bar to greater than 50 bars, and
propylene dichloride, Styrene, tetrachloroethylene, 1,4- 55 the catalysts will Still have excellent rates and acetaldehyde
thioxane, toluene, triallyl amine, 1,1,2-trichloroethane, 1,1, Selectivities provided the right temperatures and hydrogen to
2-trichloroethylene, Valeraldehyde, Valeric acid, Vinyl acetic acid ratios are used. At preSSures of about 1 bar at
acetate, Vinylallyl ether, Vinylbutyl ether, vinyl butyrate, 300 C. and at hydrogen to acetic acid ratio of about 40,
vinyl crotonate, vinylethyl ether, vinyl-2-ethylhexyl ether, excellent rates and conversion are Seen even with Fe2O
Vinylisobutyl ether, vinyl isobutyrate, Vinyl isopropyl ether, 60
containing no Pd. The rate and Selectivity under these
Vinyl-2-methyl pentanoate, vinyl propionate, vinylpropyl conditions are even higher if Pd is added to the FeO in the
ether, and m-Xylene. Among these, ethyl acetate is preferred levels preferred in the present invention. However the recov
Since, as mentioned above, it is a coproduct and its use does ery and recycle portions of the process of the invention
not introduce another component to the Separation. 65 become impractical at these low-pressure high-hydrogen
The catalyst (in reactor RX) of the invention contains iron conditions. Lowering the hydrogen to acetic acid ratio at low
and palladium. Catalysts can contain between about 2.5 and preSSure lowers the rate and conversion to impractical levels
 6,121.498
9 10
and places the catalyst in an unfavorable oxidation State than acetaldehyde (boiling point 19-20°C.) using a solvent
causing increased Selectivity to acetone. Generally an rich in acetic acid. The conditions used in absorber A will be
increase in hydrogen plus acetic acid pressure increases the largely dictated by the temperature, preSSure, and composi
rate and degree of acetic acid conversion if other conditions tion of the reactor effluent and the desired acetaldehyde
remain unchanged. Selectivity can also change as the pres recovery. Acetaldehyde recoveries over 50% are desired and
Sure is increased. Ethyl acetate, which normally is not a may be obtained by proper choice of conditions. Generally,
Significant product at low pressure, becomes a significant recovery improves with decreasing temperature, increasing
product as the preSSure increases. Acetone, which can be a preSSure, and increasing Solvent feed rate. This is why the
Significant product under low-pressure low-hydrogen temperature of the reactor effluent is decreased via a reactor
conditions, is not a significant product at high-pressure feed-effluent heat exchanger FE as depicted in FIG. 1.
low-hydrogen conditions provided the catalyst contains Preferably, the temperature of the effluent will be reduced
about 20 wt % Pd based on FeO. If the catalyst contains below 250 C. prior to absorption. More preferred are
significantly less than about 20 wt % Pd based on FeO, temperatures below 200 C. with temperatures below 150
then the activity and acetaldehyde Selectivity of the catalyst 15 C. most preferred.
rapidly deteriorate with time on Stream, and acetone and The pressure in absorber A is important to acetaldehyde
ethyl acetate Selectivity increase under high-pressure low recovery and should be as high as practically possible. This
hydrogen conditions. PreSSures from acetic acid and hydro preSSure should be close to that used in the reactor after
gen greater than 50 bars can cause increased Selectivity to taking into account pressure drops and placement of the
ethanol and ethyl acetate. However the use of diluents to gaseous recycle compressor RC. AS noted previously, cata
increase the pressure Significantly above 50 bars is within lyst selectivity to acetaldehyde suffers when the combined
the Spirit of the invention and can be done without harming partial pressure of hydrogen and acetic acid exceeds 50 bars
the selectivity. In view of the above-mentioned which effectively limits the absorber pressure to below 60
considerations, the preferred pressure of acetic acid plus 25
bar after accounting for diluents. So, a broad range of
hydrogen for the process of the invention is between about absorber pressure is 5 to 60 bar with pressures of 6 to 25 bars
5 and 50 bars. A more preferred pressure of hydrogen plus preferred.
acetic acid is between about 5 and 30 bars, and the most
preferred pressure is between about 6 and 20 bars. The composition of the absorber solvent in stream 7 will
depend on catalyst Selectivity and acetic acid conversion in
The catalysts of the invention are active under a wide the reactor. It should contain mostly unconverted acetic acid,
range of hydrogen to acetic acid ratioS. The rate of the however, with at least 50 wt % acetic acid ranging up to 95
reaction increases as the amount of hydrogen increases. The wt % at low conversion levels. Preferably the acetic acid
rate of reaction first increaseS as the amount of acetic acid
content of stream 7 will be between 60 and 85 wt %. Solvent
increases then decreases as the amount of acetic acid 35
increases further. AS mentioned above excessive amounts of
rates will be dictated by the desired acetaldehyde recovery
acetic acid at low pressure can place the catalyst in the in absorber Abut should range between a solvent to absorber
wrong oxidation State giving low rates and increased Selec feed (stream 4) ratio of 0.1 to 20 wit/wt and preferably
between 1 and 10 wit/wt.
tivity to acetone. Acetaldehyde can be produced at hydrogen
to acetic acid ratioS ranging from about 2:1 to 50:1 or higher. 40 The gaseous product of stream 6 from the absorber will
However, in view of the recovery and recycle portions of the contain mostly unconverted hydrogen and light gases
invention, the preferred hydrogen to acetic acid ratio ranges formed as reaction byproducts. This stream will be largely
from about 2:1 to 25:1. More preferred hydrogen to acetic recycled to the reactor with a purge rate Set to maintain a
acid ratio ranges from about 3:1 to 15:1, and the most 45
desired hydrogen purity. While none of these light gases
preferred ratio ranges from 4:1 to 12:1. have been shown to have a deleterious effect on catalyst
The gas hourly space velocity (GHSV, Volumes of reac performance, it is expected that the hydrogen content of the
tants contacting the catalyst per hour at reaction conditions) gaseous recycle 13 should exceed 50 mol % with purities
depends on the other parameters described previously. Gen between 60 and 95 mol % preferred.
erally the Space Velocity is chosen to provide the desired 50 The Second major separation Step is recovery of the
conversion. The Selectivity to acetaldehyde decreases as the acetaldehyde via distillation in distillation column D. Col
acetic acid conversion increases. This effect can be greater umn pressure is important for producing liquid Stream 19
at very low hydrogen levels because once the equilibrium from this relatively low-boiling acetaldehyde component
conversion level is reached any further reaction converts the 55
(19-20° C.) and should be as high as possible to minimize
acetaldehyde into ethanol and ethyl acetate. Under the most refrigeration requirements in the overhead condenser. Mini
preferred conditions of temperature, hydrogen to acetic acid mum column pressure is 1 bar with preferred preSSures from
5 to 20 bar.
ratio and hydrogen plus acetic acid pressure it is preferred to
keep the acetic acid conversion below 50% if acetaldehyde EXAMPLES
60
is the main product desired. If greater amounts of ethyl The examples that follow are intended to illustrate the
acetate are desired, then it is possible to operate the reaction process of the invention and are not intended to limit the
So that the acetic acid conversion approaches 100%. Scope of the invention.
Separation of the reactor effluent into product and uncon
verted reactant Streams requires a number of Steps. In the 65 General Experimental Methods
preferred embodiment, the first Step is the absorption in Acetic acid hydrogenations at one bar pressure were
absorber A of acetaldehyde and compounds boiling higher performed using a reactor System equipped with on-line gas
 6,121.498
11 12
chromatography. Metered gas flows were provided by Six In Some cases a higher temperature was used for the reduc
Tylan Model FC-260 mass flow controllers. Electric tem tion. When the reactor was idle between acetic acid hydro
perature control and monitoring were provided by a Dow genation experiments with the Same catalyst charge, hydro
Camile(R) control system interfaced with a Gateway Model gen flow (22.4 SCCM) was maintained at 300° C.
2000 486DX/33 computer. All gas delivery lines were teed High pressure acetic acid hydrogenation reactions were
into preSSure relief columns containing water to prevent performed in a reactor constructed from a 12 inch length of
accidental Over pressurization. Acetic acid was fed by meter Hastelloy C tubing having an outer diameter of 4 inch. All
ing hydrogen or nitrogen through a temperature-controlled gas flow, preSSure and temperature control devices were
Vaporizer containing the acetic acid. The temperature of the controlled by a Camile(R) Model 3300 process monitoring
Vaporizer was maintained by a circulating water/ethylene and control system interfaced with an IBM Model 750-P90
glycol bath. Product analysis was performed by on-line gas computer. Hydrogen flow was provided by a Brooks mass
chromatography utilizing a Hewlett-Packard Model 3790A flow controller, and acetic acid was fed using dual ISCO
gas chromatograph fitted with a 6 ft.x/s inch StainleSS Steel high pressure Syringe pumps. The device was fitted with a
15
column containing 80/120 Carbopack B/6.6% Carbowax(R) relief valve set for 35 bar. Pressure was controlled by a
20M. Products were analyzed by this on-line gas chromato modified Research Control Valve with a pressure transducer
graph with the column programmed for 80 C. for 0 minutes, located between the flow controller and the reactor. A
4° C./minute to 150° C. and 150° C. for 0 minute using a 2-micron filter was placed between the reactor and the
flame ionization detector. A 4-port Valco Industries Sampling Research Control Valve. The product exiting the Research
Valve was used to Send the feed mixture to the reactor or to Control Valve was fed to a Valco Industries 6-port gas
the gas chromatograph for analysis. Two six-port Valco chromatographic Sampling valve containing a 1 mL Sample
Industries gas chromatographic Sampling valves containing loop. The gas chromatographic Sampling valve was inter
1 mL Volume Sample loops were used to Sample the reactant faced to a Hewlett-Packard Model 3790A gas chromato
Stream or the product Stream. All tubing lines connecting the 25
graph fitted with a 6 ft.x/s inch StainleSS Steel column
exit of the acetic acid vaporizer, bypass valve, reactor, containing 80/120 Carbopack B/6.6% Carbowax(R) 20M.
six-port Sampling valves and the gas chromatograph were Products were analyzed by this on-line gas chromatograph
constructed of /s-inch StainleSS Steel and were heated with with the column programmed for 80 C. for 0 minutes, 4
temperature-controlled heating tapes to 150° C. The three C./minute to 150° C. and 150° C. for 0 minute using a flame
sampling valves were heated to 150 using valve ovens. The ionization detector. The transfer lines, filter and Research
reactor was constructed of main Section of 8-inch longx8 Control Valve connecting the reactor to the gas chromato
mm O.D. borosilicate glass fused to a lower Section con graphic Sampling valve were heated to 200 C. by a
sisting of 6-inch longx7.5 mm O.D.-3 mm I.D. capillary temperature-controlled heating tape. The gas chromato
tubing. The reactor had a 1-inch longx8 mm O.D. borosili 35 graphic Sampling valve and the transfer line connecting it to
cate side arm situated at 90 and 1 inch down from the top the gas chromatograph were maintained at 150 C. The
of the 8 mm O.D. glass portion of the main reactor Section. reactor tube was loaded to position the accurately weighed
The three openings to the reactor were fitted with 2-inch catalyst charge (typically 0.2 g) in the middle of the reactor.
long "4-inch O.D. kovar metal tubing sealed to the end of the 40 Quartz fines (1 inch layer), 12x20 mesh quartz chips (3.5
glass. Accurately weighed catalyst charges (typically 0.2 g) inches layer) and quartz or glass wool plugs were placed on
were loaded into the reactor by first inserting a glass or both sides of the catalyst charge. The entire length of the
quartz wool plug from the top of the reactor into the top part reactor was heated with a temperature-controlled heating
of the capillary Section and then placing the catalyst charge tape. The acetic acid was delivered to the reactor via a line
on top of the glass or quartz wool plug. Athermocouple was 45 passing concentrically through the reactor head and about an
inserted through the top of the reactor into the catalyst bed inch into the upper portion of the heated portion of the
and sealed to the kovar tube with SwagelokCR fittings. The reactor. The hydrogen delivery line and the relief valve were
reactant mixture was fed through the Side arm, and the also fitted to the reactor head. Thus the upper portion of the
product exited at the base of the reactor. The kovar portions 50 heated reactor acted as an acetic acid vaporization and vapor
of the reactor inlet and outlet were connected to the StainleSS mixing Zone. Catalysts were reduced in hydrogen (25
Steel transfer lines using SwagelokE fittings. The reactor SCCM) at 1.7 bar at 300° C. in the reactor over night or
was heated with a vertically-mounted Single element electric longer before feeding hydrogen and acetic acid. Reactions
furnace containing a 12-inch long heat Zone. The apparatus were started by Setting the hydrogen and acetic acid feeds to
allowed for additional hydrogen or inert gas to be metered 55 the desired rates at the 1.7 bar Setting and then Setting the
into the vapor Stream exiting the temperature-controlled pressure to the desired amount. When the reactor was idle
Vaporizer. The acetic acid partial pressure could be con between acetic acid hydrogenation experiments with the
trolled by altering the temperature of the vaporizer or by same catalyst charge, hydrogen flow (22.4SCCM) at 1.7 bar
adding hydrogen or inert gas to the vapor Stream exiting the was maintained at 300 C.
60
temperature-controlled vaporizer. The apparatus could also The following definitions apply to the Specific examples:
easily be configured to allow inert gas to be metered to the Space velocity (SV or GHSV)=volumes of gas per vol
temperature-controlled vaporizer. This flexibility in Setting ume of catalyst per hour under reaction conditions,
the feed composition facilitated the Study of the reaction Space time yield (STY)=grams of product produced per
kinetics. Normally catalysts were reduced in hydrogen (22.4 65 liter of catalyst per hour,
standard cubic centimeters per minute, SCCM) overnight at % acetic acid conversion=100(mmoles acetic acid
300 C. before feeding the acetic acid and hydrogen mixture. reacted)/(mmoles acetic acid fed),
 6,121.498
13 14
% acetic acid accountability=100(mmoles acetic acid Catalyst No. 8: Pd sponge. Pd sponge (20 mesh, Alfa lot
recovered--mmoles acetate equivalents in products)/ #00777) was used as received.
(mmoles acetic acid fed), Example 1
% normalized selectivity=100(mmoles product)/(total This example illustrates the effect of changing the weight
mmoles all products). percentage of Pd on Fe2O by large amounts under a
Catalysts
The catalysts used in the examples were obtained by the Standard Set of feed conditions at one bar pressure. The
methods that follow. example illustrates that acetic acid conversion is low when
Catalyst No. 1: Fe O. FeO3 (Aldrich, lot the catalyst contains 0 or 100% Pd and that the selectivity to
#DQ15808DQ, 99.98% purity) was used as received. methane is high. The example also illustrates that, of those
catalysts converting over 90% of the acetic acid, the catalyst
Catalyst No. 2: 2.5% Pd on FeO. A solution was containing 10 wt % Pd produces acetaldehyde at the highest
prepared from Pd(NO)xH2O (442 mg, Alfa lot rate and selectivity with the lowest methane selectivity. The
#120982, 39.9% Pd) and water (10 mL). This solution example further shows that although the catalyst containing
was added to 20x40 mesh Catalyst No. 1 (7.1607 g) 15 no Pd had the highest acetaldehyde selectivity, it also had the
contained in an evaporating dish. The mixture was lowest acetic acid conversion. The relationship between
dried on the Steam bath and calcined in a muffle furnace acetaldehyde Selectivity and conversion will become more
for 4 hours at 400° C. apparent in Subsequent examples. The data for Example 1
Catalyst No. 3: 5% Pd on FeO. A solution was prepared were collected at a point in time when the catalyst activity
from Pd(NO)xHO (127 mg, Alfa lot #120982, was high and are presented in Table 1.
39.9% Pd) and water (2 mL). This solution was added Example 2
to Catalyst No. 1 (1.0294 g) contained in an evaporat This example compares the performance of catalysts
ing dish. The mixture was dried on the Steam bath and containing 2.5 and 5 wt % Pd under conditions of compa
calcined in a muffle furnace for 5 hours at 400 C. 25
rable acetic acid conversion. The same feed conditions used
Catalyst No. 4: 10% Pd on FeO. A solution was pre in Example 2 were used as in Example 1, and the data were
pared from Pd(NO)xHO (251 mg, Alfa lot #120982, collected after the catalyst activity had moderated thus
39.9% Pd), Fe(NO).9H2O (5.06 g, Mallinckrodt lot allowing for the lower conversions. The example illustrates
#5032 KHTJ) and water (10 mL). To this solution was that the catalyst containing 5 wt % Pd is more selective than
added a separate Solution prepared from citric acid that containing 2.5 wt % Pd when run at the same level of
(2.59 g, Eastman Chemical Company plant material) acetic acid conversion. The example further illustrates that
and water (5 mL). The mixture was evaporated on the much higher acetaldehyde selectivity at much higher acetic
Steam bath to a Scaly mass and then calcined in a muffle acid conversion can be achieved with catalysts containing
furnace for 5 hours at 400° C. 35
Pd than the FeO catalyst of Example 1. The data for
Catalyst No. 5: 20% Pd on FeO. A solution was pre Example 2 are presented in Table 2.
pared from Pd(NO)xH2O (501 mg, Alfa lot #120982,
39.9% Pd), Fe(NO).9HO (5.06 g, Mallinckrodt lot Example 3
#5032 KHTJ) and water (10 mL). To this solution was This example compares the performance of catalysts
40
added a separate Solution prepared from citric acid containing 5 and 10 wt % Pd under conditions of comparable
(2.23 g, Eastman Chemical Company plant material) acetic acid conversion. The Same feed conditions used in
and water (5 mL). The mixture was evaporated on the Example 3 were used as in Example 1, and the data were
Steam bath to a Scaly mass and then calcined in a muffle collected while the catalyst activity was highest thus allow
furnace for 5 hours at 400° C. 45 ing for the higher conversions. The example illustrates that
Catalyst No. 6: 40% Pd on FeO. A solution was pre the catalyst containing 10 wt % Pd is more selective than
pared from Pd(NO)xHO (Alpha lot #120982, 39.9% that containing 5 wt % Pd when run at the same level of
Pd), Fe(NO)x9H2O (Mallinckrodt lot #5032 KHTJ) acetic acid conversion. The example further illustrates that,
and water (10 mL). To this solution was added a at one bar pressure, the optimum performance is achieved
50
Separate Solution prepared from citric acid (Eastman when the Pd level of 10 wt %. The data for Example 3 are
Chemical Company plant material) and water (5 mL). presented in Table 3.
The mixture was evaporated on the Steam bath to a Example 4
Scaly mass and then calcined in a muffle furnace for 5 This example illustrates the effects of changing the mole
hours at 400° C. The amount of Pd(NO)xHO used in 55
fraction of acetic acid in hydrogen (XA) at various Space
Catalyst No. 5 was approximately doubled to achieve velocities on the performance of the 5 wt % Pd on FeO at
40% Pol.
one bar pressure. The example illustrates that high acetal
Catalyst No. 7: 80% Pd on FeO. A solution was pre dehyde Selectivity can be achieved at high acetic acid mole
pared from Pd(NO)xHO (2005 g, Alfa lot #120982, 60 fraction, but that it is difficult to obtain higher conversions
39.9% Pd), Fe(NO).9HO (1.01 g, Mallinckrodt lot by lowering the Space Velocity when the acetic acid mole
#5032 KHTJ) and water (10 mL). To this solution was fraction is high at one bar pressure. The data for Example 4
added a separate Solution prepared from citric acid are presented in Table 4.
(1.93 g, Eastman Chemical Company plant material)
and water (5 mL). The mixture was evaporated on the 65
Example 5
Steam bath to a Scaly mass and then calcined in a muffle This example illustrates the performance of the 10 wt.%
furnace for 5 hours at 400° C. Pd on Fe2O at 250 psig pressure and at a 5/1 hydrogen/
 6,121.498
15 16
acetic acid ratio as a function of time on Stream. The
example illustrates that good rate and acetaldehyde Selec TABLE 1.
tivity can be achieved, but that the rate, conversion and
acetaldehyde Selectivity decrease after a certain time on Effect of 0 to 100 wt % Pd on the Performance of Fe O Catalysts
Stream. The example also illustrates that the Selectivity to Wt 9%, Pd O 1O 2O 40 8O 1OO
hydrocarbons is very low under the high-pressure low
hydrogen conditions. The example further illustrates that Catalyst No. 1. 4 5 6 7 8
ethyl acetate is a significant product under the high-pressure % HOAc Conv. 19 96 98 99 81 26
low-hydrogen conditions. The performance data for G/(1-hr) HAc 28O 499 157 79 45 1.
% HAc sel.* 8O 56 38 35 15 4
Example 5 are presented in Table 5. % acetone sel. O6 3.1 2.7 1.1 O.2 O.3
%. EtOH sel. 7 38 50 55 22 0.4
Example 6 % CH sel. 10.5 2.7 8.5 8.6 62.9 95.4
% C, H. C. sel.** 3.1 O.1 O.7 O.3 O O.1
This example illustrates the performance of the 40 wt % 15 % HOAc acct.*** 100 1OO 108 107 105 1OO
Pd on FeO at 17.2 bar gauge pressure at 7/1 and 5/1
hydrogen/acetic acid ratios with time on Stream. This Conditions: 90 SCCM H containing 2 mol % HOAc, 0.2 g catalyst, 300
C.
example also illustrates that the performance of this catalyst Selectivities are normalized.
does not deteriorate in the manner exhibited by the 10 wt % **C. Hydrocarbons = ethylene + ethane.
Pd catalyst of Example 5. The performance data for ***Acetic acid accountability.
Example 6 are presented in Table 6.

TABLE 2

Effect of % Pd on the Performance of Fe O Catalysts

Wt 9%, Pd 2.5 5

% HOAc Conv. 54 50 52 50 45 59 51 48 45
G/(1-hr) HAc 597 621 656 698 527 748 694 674 662
% HAc sel.* 78 79 77 8O 73 82 84 84 84
% acetone sel. O.8 O.8 O.9 O.8 1.6 O.7 O.7 O6 O.6
%. EtOH sel. 15 15 17 14 18 12 10 9 9
% CH sel. 4.6 4.1 4.4 3.8 6.1 5.2 5.7 5.9 5.9
% C, H. C. sel.** 1.0 0.9 0.9 0.8 1.6 0.7 0.7 0.6 0.6
% HOAc acct.*** 91 107 103 103 101 97 101 102 105

Conditions: 90 SCCM H2 containing 2 mol % HOAc, 0.2 g catalyst, 300° C.

*Selectivities are normalized.
**C. Hydrocarbons = ethylene + ethane.
***Acetic acid accountability.

Example 7
This example illustrates the integrated process of the TABLE 3
invention. The processing Steps of the invention are depicted Effect of 26 Pod on the Performance of Fe2O. Catalwsts:
in FIGS. 1 and 2. The reactor (a) is loaded with a Pd/FeO. Comparison at the 5 and 10 Wt. %2\/3
Levels ysts:
catalyst of the invention and operated at 300° C. with a 5/1
molar hydrogen to acetic acid ratio at 17.2 bar pressure, and so Wt 9%, Pd 5 1O
the reaction is 89% selective to acetaldehyde, 5% selective
to ethanol /ethyl acetate, 4% selective to acetone and CO2, % HOAc Conv. 98 92 97 91
and 2% selective to hydrocarbons at 45% acetic acid con- G/(1-hr) HAc 642 779 773 994
version. Ethanol is converted to ethyl acetate as dictated by % HAc sel.* 36 47 52 68
the chemical equilibrium conditions in the bottom of the 55 % acetone sel. 1.1 O.9 1.O 1.O
acetaldehyde recovery column (I). Optional Sulfuric acid %. EtOH sel. 44 39 40 27
catalyst can be used to facilitate the attainment of the % CH sel. 14 11 5.4 3.4
ethanol-acetic acid-water-ethyl acetate equilibrium. The % C, H.C. sel.** 3.7 2.6 1.O O6
heat and material balances for the process of the invention 60 % HOAc acct.*** 98 103 98 103
operating in this mode are provided in Tables 7 and 8.
While the invention has been described in connection Conditions: 90 SCCM H2 containing 2 mol % HOAc, 0.2 g catalyst, 300
with the preferred embodiments and examples, it will be C.
Selectivities are normalized.
understood that modifications within the principle outlined
above will be evident to those skilled in the art. Thus, the 65 **C. Hydrocarbons = ethylene + ethane.
invention is not limited to the preferred embodiments and ***Acetic acid accountability.
examples, but is intended to encompass Such modifications.
 6,121.498
17 18
TABLE 4
Effect of Changing the Mole Fraction of Acetic Acid in Hydrogen
on the Performance of 5 wt.% Pd(Fe2O3
at Different Space Velocities.
TTOS, min.* 5350 7033 7141 8134 8886 9291 9328 9396
SCCMH2 90 3O 90 90 90 90 25 25
GHSV, hr 73OOO 24OOO 73OOO 73OOO 73OOO 73OOO 2OOOO 2OOOO
XHOAc 0.057 O.O95 O.095 O.O26 O.2O O.2O O.2O O.2O
% HOAc conv. 38 31 16 66 23 16 17 26
G/(1-hr) HAc 1003 283 497 740 523 899 338 4O7
% HAc sel.** 87 87 89 79 87 90 89 89
% Acetone sel. 1.1 1.1 O.9 O.9 2.5 1.8 3.9 3.0
%. EtOH sel. 8.0 6.8 5.3 15.8 7.5 5.8 4.6 5.4
% CH sel. 3.2 4.8 3.9 3.7 2.7 1.8 1.9 2.2
% C, H. C. sel.*** O.6 O.8 0.5 O.7 O.2 0.4 O.3 O.6
% HOAc acct.**** 86 82 91 92 81 95 96 89

Conditions: 0.2 g catalyst, 300° C.

*TTOS = total time on stream under hydrogen and acetic acid feed.
**Selectivities are normalized.
***C. Hydrocarbons = ethylene + ethane.
****Acetic acid accountability.

TABLE 5 TABLE 6
25
Effect of Time on Stream on the Perfomance of 10 wt % Pd/FeOs Effects of Hydrogen/Acetic Acid Ratio and Time on Stream on the
at 250 psig and 5/1 Hydrogen/Acetic Acid Ratio. Performance of 40 wt % Pd/Fe2O at 250 psig.

TTOS, mini 512 534 2318

TTOS, mini 1739 2089 3O
H/HOAc 7 5 5
% HOAc Conv. 22 1O GHSV, hr-1 353O 26OO 26OO
G/(1-hr) HAc 3350 970 % HOAc Conv. 46 42 38
% HAc sel.** 77.9 62.7 G/(1-hr) HAc 1530 2125 2175
% acetone sel. 1.5 4.6 35 % HAc sel.** 86.4 77.1. 77.0
%. EtOH sel. 15.O 16.2 % acetone sel. 1.7 1.3 1.5
%. EtOAc sel. 4.6 15.5 %. EtOH sel. 9.6 15.9 15.2
% CH sel. O.7 O.7 %. EtOAc sel. 2.1 5.6 6.3
% C, H.C. sel.*** O.2 O.1 40 % CH sel. O.1 <0.1 <0.1
% C.H. C. sel.*** O <0.1 <0.1
Conditions: GHSV = 12200, 300° C. Conditions: 300° C.
*TTOS = total time on stream under hydrogen and acetic acid feed. *TTOS = total time on stream under hydrogen and acetic acid feed.
**Selectivities are normalized. 45 **Selectivities are normalized.
***C. Hydrocarbons = ethylene + ethane. ***C. Hydrocarbons = ethylene + ethane.

TABLE 7
HOAe Hydrogenation Reaction Section Balance
Stream 11 13 18 19 23 3O 31 33 36

Temperature C 67.3 77.6 37.8 37.8 167.8 167.8 167.8 37.8 66.7
Pressure BAR 19.O 19.0 6.9 6.9 6.6 6.6 6.6 2.8 19.O
Vapor Fraction O848 1.OOO 1.OOO O.OOO O.O1O O.O1O O.O1O O.OOO O847
Mole Flow KGMOL/HR 4982 3845 22 318 4466 737 3729 3729 4982
Mass Flow KG/HR 63O88 18807 510 13455 183638 3O312 153325 153325 63O86
Volume Flow M3/HR 6348 5914 84 18 465 77 389 155 6333
Enthalpy MJ/HR -388.810 -57092 -2148 -61647 -1624722 -268188 -1356535 -1397118 -3.88610
Mole Flow KGMOL/HR
HOAC 742.54 15.63 O.OO O.OO 2265.66 373.98 1891.67 1891.67 748.43
H2 3742.14 3332.30 5.28 O.05 O.OO O.OO O.OO O.OO 3742.14
HAC 33.21 33.21 S.94 293.39 O.30 O.05 O.25 0.25 33.21
METHANE 358.78 356.76 8.40 2.95 O.OO O.OO O.OO O.OO 358.76
ACETONE 2.59 2.59 O.OO O.O6 26.65 4.40 22.25 22.25 2.59
ETHANOL O.23 O.23 O.OO O.OO 6.11 1.01 5.10 5.10 6.12
 6,121.498
19 20
TABLE 7-continued
HOAe Hydrogenation Reaction Section Balance
Stream 11 13 18 19 23 3O 31 33 36

ETHENE 28.43 28.43 1.28 2.18 O.OO O.OO O.OO O.OO 28.43
H2O 28.98 28.98 O.11 16.85 2O71.76 341.98 1729.78 1729.78 23.09
CO2 39.37 39.37 1.49 2.61 O.OO O.OO O.OO O.OO 39.37
ETOAC 5.89 5.89 O.OO O.OO 95.49 15.76 79.73 79.73 O.OO
Mass Fraction

HOAC O.7070 O.OSOO OOOOO O.OOOO O.7410 O.7410 O.7410 O.741O O.712O
H2 O.12OO O.3610 O.O210 O.OOOO O.OOOO OOOOO O.OOOO OOOOO O.12OO
HAC O.O230 O.O790 O.5.130 O.961O O.OOO1 O.OOO1 O.OOO1 O.OOO1 O.O230
METHANE O.O910 O.3090 O.2840 O.OO40 O.OOOO OOOOO O.OOOO OOOOO O.O910
ACETONE O.OO2O O.OO8O OOOOO O.OOO3 O.OO8O O.OO8O O.OO8O O.OO8O O.OO2O
ETHANOL O.OOO2 O.OOO8 OOOOO O.OOOO O.OO2O O.OO2O O.OO2O O.OO2O O.OO40
ETHENE O.O130 O.0430 O.O7OO O.OOSO O.OOOO OOOOO O.OOOO OOOOO O.O130
H2O O.OO8O O.O28O OOO40 O.O230 O.2O3O O.2O3O O.2O3O O.2O3O O.OOFO
CO2 O.O270 O.O930 O.1280 O.OO90 O.OOOO OOOOO O.OOOO OOOOO O.O270
ETOAC O.OO8O O.O28O OOOOO O.OOOO O.O460 O.O460 O.O460 O.O46O O.OOOO

TABLE 8
HOAe Hydrogenation Recovery Section Balance
Stream 1. 2 3 5 7 8 9 12

Temperature C 167.8 96.8 141.5 43.3 43.3 43.3 43.3 102.2

Pressure BAR 8.8 2.1 2. 2.1 2.1 2.1 2.1 2.1
Vapor Fraction O.OO6 1.OOO O.OOO O.OOO O.OOO O.OOO O.OOO O.OOO
Mole Flow KGMOL/HR 737.5 1490.7 382.8 1136.1 1198.6 353.3 62.6 16.9
Mass Flow KG/HR 3O323 8762O 22466 79762 84156 7270 4394 1445
Volume Flow M3/HR 61.4 22170.6 24.8 89.5 94.4 7.6 4.9 1.8
Enthalpy MJ/HR -268378 -515645 -169455 -473168 -499232 -102244 -26065 -7813
Mole Flow KGMOL/HR
HOAC 374.10 28.74 370.36 25.00 26.38 2.41 1.38 1.36
ACETONE 4.40 87.36 O.OO 82.96 87.53 4.96 4.57 O.09
ETHANOL 1.01 10.92 O.OO 9.91 1046 1.60 0.55 O.O1
H2O 342.15 587.71 12.47 238.03 251.14 336.28 13.11 O.O1
ETOAC 15.77 795.05 O.OO 779.28 822.21 7.98 42.93 15.41
HAC O.OS O.92 O.OO 0.87 O.92 O.05 O.OS O.OO
Mass Fraction

HOAC O.7410 O.O2OO O.99OO O.O190 O.O190 O.O2OO O.O190 0.0570

ACETONE O.OO8O O.O58O O.OOOO O.06OO O.O6OO O.O4OO O.O6OO OOO40
ETHANOL O.OO2O O.OO60 O.OOOO O.OO60 O.OO60 O.O1OO O.OO60 OOOO4
H2O O.2O3O O.117O O.O1OO O.O540 O.O540 O.833O O.O540 O.OOO1
ETOAC O.O460 O.7990 O.OOOO O861O O861O O.O970 O861O O.9390
HAC O.OOO1 O.OOOS O.OOOO O.OOOS O.OOOS O.OOO3 O.OOOS OOOOO

What is claimed is: 50 6. The method according to claim 1, further comprising

1. A method of producing acetaldehyde, comprising the the Step of Supplying hydrogen and acetic acid to a reactor
Steps of: in a hydrogen to acetic acid ratio of 4:1 to 12:1.
(a) hydrogenating acetic acid at a pressure between about 7. The method according to claim 1, wherein the iron
5 and 50 bars in the presence of an iron oxide catalyst oxide is Fe2O.
containing between 20 and 90 wt % palladium to 55 8. The method according to claim 1, wherein the hydro
produce a gaseous product; and genation is performed at a temperature of about 250 C. to
(b) absorbing acetaldehyde from the gaseous product with 400° C.
a Solvent containing acetic acid. 9. The method according to claim 1, wherein the hydro
2. The method according to claim 1, wherein the catalyst genation is performed at a temperature of about 270° C. to
contains between 20 and 80 wt % palladium. 60
350° C.
3. The method according to claim 1, wherein the catalyst 10. The method according to claim 1, wherein the hydro
contains between 20 and 60 wt % palladium. genation is performed at a temperature of about 280 C. to
4. The method according to claim 1, further comprising 325° C.
the Step of Supplying hydrogen and acetic acid to a reactor 11. The method according to claim 1, wherein the catalyst
in a hydrogen to acetic acid ratio of 2:1 to 25:1. has a specific Surface area of less than 150 m/g.
5. The method according to claim 1, further comprising 65 12. The method according to claim 1, wherein the Step of
the Step of Supplying hydrogen and acetic acid to a reactor absorbing acetaldehyde is run at a temperature below 250
in a hydrogen to acetic acid ratio of 3:1 to 15:1. C.
 6,121.498
21 22
13. The method according to claim 1, wherein the step of from the mixture of ethyl acetate, water, acetic acid and
absorbing acetaldehyde is run at a temperature below 200 acetone using decantation, Steam Stripping and distillation.
C. 25. The method according to claim 16, wherein step (c)
14. The method according to claim 1, wherein the step of produces acetaldehyde product and a mixture containing
absorbing acetaldehyde is run at a temperature below 150 acetic acid, a portion of the mixture containing acetic acid
C. being used in step (b) as the Solvent for absorbing acetal
15. The method according to claim 1, wherein step (b) dehyde.
produces a gaseous remainder containing hydrogen, the 26. A process for the preparation and recovery of acetal
gaseous remainder being recycled to step (a) for the hydro dehyde comprising the Steps of:
genation of acetic acid.
16. The method according to claim 1, further comprising (a) contacting within a reactor Zone hydrogen and acetic
the step of (c) distilling the absorbed acetaldehyde from the acid with a hydrogen to acetic acid molar ratio of less
Solvent containing acetic acid. than 25 in the presence of an iron oxide catalyst
17. The method according to claim 16, wherein step (c) is containing between 20 and 90 wt. % palladium at
performed at a pressure of 1 bar or greater. 15 temperatures between 250 and 400° C. and pressures
18. The method according to claim 16, wherein step (c) is between 5 and 50 bar;
performed at a pressure from 5 to 20 bar. (b) absorbing the reaction product in acetic acid-rich
19. The method according to claim 16, wherein step (c) Solvent and returning a major portion of the uncon
produces acetaldehyde product and a mixture of ethyl densed gases to the reactor Zone;
acetate, water, acetic acid and acetone, the method further (c) distilling the acetaldehyde from the acetic acid-rich
comprising the Step of (d) recovering the acetic acid from the Solvent;
mixture of ethyl acetate, water, acetic acid and acetone using (d) recovering unconverted acetic acid by azeotropic
an azeotropic distillation. distillation;
20. The method according to claim 19, wherein a hetero (e) returning the recovered acetic acid to the reactor Zone;
geneous water azeotrope is used for the azeotropic distilla 25
and
tion.
21. The method according to claim 19, wherein an azeo (f) recovering the coproducts water, acetone and ethyl
trope of ethyl acetate and water is used for the azeotropic acetate by decantation, Steam Stripping and distillation.
distillation. 27. A method of producing acetaldehyde, comprising the
22. The method according to claim 21, wherein the Steps of
unreacted acetic acid is separated in a column, and the (a) Supplying hydrogen and acetic acid to a reactor in a
column is controlled to contain an ethyl acetate rich azeo hydrogen to acetic acid ratio of 2:1 to 25:1, and
trope of ethyl acetate and water. (b) hydrogenating acetic acid in the reactor at a preSSure
23. The method according to claim 19, wherein step (a) is between about 5 and 50 bars and a temperature of about
conducted in a reactor Zone, the method further comprising 35 250 C. to 400 C., the hydrogenation being conducted
the Step of returning acetic acid recovered in step (d) to the in the presence of an iron oxide catalyst containing
reactOr ZOne. between 20 and 60 wt.% palladium.
24. The method according to claim 19, further comprising
the step of (e) recovering ethyl acetate, water and acetone k k k k k