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Method, Catalyst and Apparatus for Producing Acetaldehyde from Acetic Acid

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Method, Catalyst and Apparatus for Producing Acetaldehyde from Acetic Acid Patentamt Europaisches ||| || 1 1| || || || ||| || || || ||| ||| || (19) J European Patent Office Office europeen des brevets (11) EP 0 953 560 A1 (12) EUROPEAN PATENT APPLICATION Date of (43) publication: (51) |nt. CI.6: C07C 45/41 , C07C 47/06, 03.11.1999 Bulletin 1999/44 B01J 23/74, B01J 23/76 (21) Application number: 98115520.3 (22) Date of filing: 18.08.1998 (84) Designated Contracting States: • Depew, Leslie S. AT BE CH CY DE DK ES Fl FR GB GR IE IT LI LU Kingsport, TN 37662-5072 (US) MC NL PT SE • Collins, Nick A. Designated Extension States: Kingsport, TN 37662-5072 (US) AL LT LV MK RO SI (74) Representative: (30) Priority: 30.04.1998 US 69953 Winter, Brandl, Furniss, Hubner, Ross, Kaiser, Polte, Kindermann (71) Applicant: Partnerschaft EASTMAN CHEMICAL COMPANY Patent- und Rechtsanwaltskanzlei Kingsport, Tennessee 37662-5075 (US) Alois-Steinecker-Strasse 22 85354 Freising (DE) (72) Inventors: • Tustin, Gerald C. Kingsport, TN 37662-5072 (US) (54) Method, catalyst and apparatus for producing acetaldehyde from acetic acid (57) A method of producing acetaldehyde hydro- genates acetic acid in the presence of an iron oxide cat- alyst containing between 2.5 and 90 wt % Pd, more "p'J. " f3^ preferably 10 and 80 wt % Pd and most preferably 20 ^ i 'V""^ .. ' and 60 wt % Pd. The catalyst has a specific surface XX area of less than 150 m2/g. Hydrogen and acetic acid n * are fed to a reactor in a hydrogen to acetic acid ratio of M£p 2:1 to 25:1 , more preferably in a hydrogen to acetic acid > Mvx, [=3 ratio of 3:1 to 15:1 and most preferably in a hydrogen to eTF acetic acid ratio of 4:1 to 12:1. The hydrogenation is Vj9 TT ' ' performed at a temperature of about 250°C to 400°C, ' ' — more preferably about 270°C to 350°C and most prefer- ably about 280°C to 325°C. The hydrogenation of acetic acid produces a partially gaseous product, and acetal- dehyde is absorbed from the partially gaseous product FIGFIG. 1 with a solvent containing acetic acid. The gas remaining after the absorption step contains hydrogen, and this gas is recycled for the hydrogenation of acetic acid. The absorbed acetaldehyde is distilled to isolate same. After acetaldehyde is isolated from unreacted acetic acid and the other products via distillation, the unreacted acetic acid is separated from the other products using azeo- tropic distillation. Water is contained in the other prod- o CO ucts, and the azeotrope is an azeotrope of ethyl acetate LO and water. The unreacted acetic acid is separated in a CO column, and the column is controlled to contain an ethyl LO acetate rich azeotrope of ethyl acetate and water. <7> O Q_ LU Printed by Xerox (UK) Business Services 2.16.7/3.6 EP 0 953 560 A1 Description BACKGROUND OF THE INVENTION 5 1. Field of the Invention [0001] The present invention relates in general to producing acetaldehyde. More specifically, the present invention relates to producing acetaldehyde by hydrogenating acetic acid. 10 2. Description of the Related Art [0002] Acetaldehyde is an important industrial chemical. It has been used as a starting material for the commercial manufacture of acetic acid, acetic anhydride, cellulose acetate, other acetate esters, vinyl acetate resins, synthetic pyri- dine derivatives, terephthalic acid, peracetic acid and pentaerythritol. Historically, acetaldehyde has been used to pro- 15 duce acetic acid, but improvements in technology have resulted in more economical acetic acid production from synthesis gas (a mixture of carbon monoxide and hydrogen). This development implies that it may be more economi- cally attractive to produce acetaldehyde from acetic acid rather than to produce acetic acid from acetaldehyde if a tech- nically viable route existed. [0003] Acetaldehyde has been produced commercially by the reaction of ethanol with air at 480°C in the presence of 20 a silver catalyst. This process has been replaced by the current process the Wacker oxidation of ethylene. Both of these processes start with ethylene, and the Wacker route is more direct and efficient than the ethanol oxidation route. Acetal- dehyde has also been produced by the hydration of acetylene. This process uses mercury salts as a catalyst, and mer- cury handling can cause environmental and safety problems. The use of acetylene causes safety concerns, and the high cost of acetylene relative to ethylene has rendered this process obsolete. Acetaldehyde can also be produced by 25 reacting synthesis gas over a rhodium on silica catalyst at elevated temperature and pressure, but the selectivity to acetaldehyde is poor, and the process has never been practiced commercially. Acetaldehyde has also been produced from the reaction of methanol with synthesis gas at elevated temperature and pressure using a cobalt iodide catalyst with a group 15 promoter, but this process also has never been practiced commercially. Although the Wacker process is the preferred commercial process at this time, it also has may undesirable aspects. These include the special safety 30 and handling problems associated with reacting ethylene with oxygen and the very corrosive nature of the aqueous acidic chloride-containing reaction mixtures which necessitates very expensive materials of construction. Thus a need exists for an acetaldehyde synthesis that is an improvement over the existing known processes. [0004] A potentially attractive means to synthesize acetaldehyde is by the hydrogenation of acetic acid. See reaction (I) below. However the carboxylic acid group is generally considered to be among the most difficult functional groups to 35 reduce by catalytic hydrogenation. Aldehyde groups, conversely, are easily reduced by catalytic hydrogenation to alco- hols. See reaction (II) below. Thus, under the conditions required to reduce a carboxylic acid, the aldehyde is often not isolated in good yield because the aldehyde is further reduced to an alcohol. Furthermore, when the carboxylic acid contains an a-hydrogen, conversion to a ketone, water and carbon dioxide can occur. See reaction (III) below. This reaction becomes more prevalent as the number of a-hydrogens increases. Thus, acetone can be readily formed from 40 acetic acid at the temperatures typically used for reaction (I) (300-400°C). The above discussed reactions related to hydrogen and acetic acid in the vapor phase are summarized below: (I) CH3C02H + H2 - CH3CHO + H20 AGsoo-c = +0.8 kcal/mole AG^.c = -0.04 kcal/mole 45 (II) CH3CHO + H2 - CH3CH2OH AG3oo-c = -0.4 kcal/mole ACoq.c = +2.5 kcal/mole 50 (III) 2 CH3C02H -» CH3COCH3 + C02 + H20. [0005] The hydrogenation of acetic acid to acetaldehyde and water (reaction (I)) is a mildly endothermic reaction. So, 55 the thermodynamics of this reaction improve as the temperature is increased. The subsequent reaction (II), the hydro- genation of acetaldehyde to ethanol, is exothermic, and this reaction becomes less favorable as the temperature increases. Since the equilibrium of the acetic acid hydrogenation is poor, the reaction must be run with an excess of hydrogen to achieve appreciable acetic acid conversion. Thus, on a thermodynamic basis, ethanol formation will be 2 EP 0 953 560 A1 favored at temperatures of 300-400°C. Reaction (III), the formation of acetone, is essentially irreversible at all temper- atures above 0°C and becomes very favorable thermodynamically as the temperature is increased. Increasing the tem- perature significantly above 400°C will not likely improve the selectivity to the desired acetaldehyde product because of increasing acetone production. Other reactions, such as the formation of methane, carbon oxides and C2 hydrocarbons 5 also are relevant in acetic acid hydrogenation chemistry, but are of less importance than the three reactions described above unless excessively high temperatures are used. In some circumstances, the formation of ethyl acetate presum- ably through ethanol as an intermediate can also lower the selectivity to the desired acetaldehyde. [0006] Thus, it appears that a major challenge in producing acetaldehyde via acetic acid hydrogenation is catalyst design. The ideal catalyst should facilitate the initial hydrogenation of acetic acid to acetaldehyde but have essentially 10 no activity for the subsequent hydrogenation to ethanol nor for the dimerization reaction producing acetone. If a catalyst has even a small activity for conversion of acetaldehyde to ethanol or for the conversion of acetic acid into acetone, then extreme losses in acetaldehyde selectivity may occur if the reaction is operated beyond the equilibrium conversion level allowed for converting acetic acid and hydrogen into acetaldehyde and water. A need exists for a catalyst that selec- tively hydrogenates acetic acid to acetaldehyde. 15 [0007] Catalyst selectivity is only one requirement for a viable acetaldehyde synthesis. The synthesis must also be operated in a manner that will allow for the facile recovery of the very volatile acetaldehyde product, the recovery of byproducts and the recycle of unconverted reactants. Generally processes that hydrogenate carboxylic acids to alde- hydes do so under conditions of about 1 bar pressure (all pressures given herein are in terms of absolute pressures) and hydrogen to carboxylic acid ratios approaching 50/1 . Although these conditions may be sufficient for nonvolatile 20 aldehydes, they are impractical for acetaldehyde which boils at 1 9-20°C. Thus, a need also exists for a process that con- verts acetic acid into acetaldehyde in a manner that is selective and provides for the economical recovery of the acetal- dehyde. [0008] In spite of the thermodynamic limitations surrounding the hydrogenation of carboxylic acids to aldehydes, sev- eral examples of this reaction appear in the prior art. Generally these reactions are performed at about 1 bar pressure 25 in the vapor phase in a large excess of hydrogen at temperatures ranging between 200 and 500°C, and the reaction is most successful with aromatic carboxylic acids or aliphatic acids containing few a-hydrogens.
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