Acetato de Etilo GPS

This article was downloaded by: [Stanford University Libraries]
On: 14 June 2012, At: 18:42

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Catalysis Reviews: Science and

Engineering
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/lctr20
The Catalytic Hydrogenolysis of Esters to

Alcohols
a a b
T. Turek , D. L. Trimm & N. W. Cant
a
School of Chemical Engineering and Industrial Chemistry University
of New South Wales Kensington, NSW, 2033, Australia
b
School of Chemistry Macquarie University Macquarie, NSW, 2109,
Australia
Available online: 23 Sep 2006
To cite this article: T. Turek, D. L. Trimm & N. W. Cant (1994): The Catalytic Hydrogenolysis of Esters
to Alcohols, Catalysis Reviews: Science and Engineering, 36:4, 645-683
To link to this article: http://dx.doi.org/10.1080/01614949408013931
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation
that the contents will be complete or accurate or up to date. The accuracy of any
instructions, formulae, and drug doses should be independently verified with primary
sources. The publisher shall not be liable for any loss, actions, claims, proceedings,
demand, or costs or damages whatsoever or howsoever caused arising directly or
indirectly in connection with or arising out of the use of this material.
CATAL. REV.-SCI. ENG., 36(4), 645-683 (1994)
The Catalytic
Hydrogenolysis of
Esters to Alcohols
Downloaded by [Stanford University Libraries] at 18:42 14 June 2012
T. TUREK and D. L. TRIMM*
School of Chemical Engineering and Industrial Chemistry

University of New South Wales
Kensington, NSW 2033, Australia
N. W. CANT
School of Chemistry
Macquarie University
Macquarie, NSW 2109, Australia
I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . 646
11. HYDROGENOLYSIS OF FORMATES . . . . . . . . . . . . . . . . . , . . . . . 647
A. Methyl Formate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . 647
B. Higher Formates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . 653
111. HYDROGENOLYSIS O F MONOESTERS . . . . . . . . . . . . . . . . . . . . 655
A. Kinetic Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655
B. Reaction Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
C. Manufacture of Ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
IV. HYDROGENOLYSIS OF FATTY ACID ESTERS . . . , . . . . . . . . . 660
A. Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
B. Kinetic Studies and Reaction Mechanism . . . . . . . . . . . . . . . . . . . 663
C. New Developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
"To whom correspondence should be sent.

645
Copyright 0 1994 by Marcel Dekker, Inc.

646 TUREK, TRIMM, AND CANT
V. PRODUCTION OF DIOLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666

A . Ethylene Glycol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
B. Butanediol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
C. Other Diols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 673
V1. CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
ACKNOWLEDGMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
REFERENCES ............................................. 675
Key Words: Alcohols; Copper catalysts; Esters; Hydrogenolysis.

The hydrogenolysis of esters to alcohols is a reaction between esters

and hydrogen which selectively splits a C - 0 bond adjacent to a carbonyl
group (1).
0
I1
R-C--O-R’ + 2H2+ RCH2OH + R’OH
A well-known large-scale industrial process based on this reaction-
the production of fatty alcohols from natural fatty acid esters-has been
operated commercially for more than 50 years. Several processes which
include the hydrogenolysis of an ester have been proposed for the manu-
facture of basic chemicals such as methanol and ethanol. Furthermore, there
has been continuous interest over the past two decades in replacing the
existing, energy-intensive processes for the production of ethylene glycol
and 1,4-butanedioI by more cost-effective routes involving ester hydrogen-
olysis.
While particular aspects of the literature on hydrogenolysis of esters
have been reviewed already [l-31, the objective of the present work is to
give a more general summary with special emphasis on the present or
possible industrial applications of ester hydrogenolysis.
I. INTRODUCTION
The reaction of esters with hydrogen may give different products such
as alcohols [I], acids and hydrocarbons [4-71, and ethers [8]. The product
composition depends on the reaction conditions, the structure of the sub-
strate, and the catalyst used. While the C - 0 bond in an ester
0
II
R-C-SR’
HYDROGENOLYSIS OF ESTERS TO ALCOHOLS 647
is split to obtain alcohols, acids and hydrocarbons are produced if the R’-
0 bond undergoes cleavage.
RCOOR’ + H Z + RCOOH + R’H (2)
Rylander [9] has pointed out that the formation of acids is expected
when the R ’ - 0 bond is weakened by R’ being a benzyl, vinyl, or ally1
group. However, even simple aliphatic esters can be converted to the cor-
responding acids and hydrocarbons over a rhodium catalyst, as shown by
Zdrazil [5, 61. Precious metals are normally not suitable for selectively
producing alcohols from esters. On the other hand, if rhodium is modified
with tin, catalyst properties drastically change and the competing hydro-
carbon formation is strongly suppressed [ 101.
The number of catalyst systems allowing the production of alcohols is
very limited. Adkins [I] used Raney nickel for the low-temperature hydro-
genolysis of amino esters. Zinc chromium oxide was found to have a very
low activity, but it made possible the hydrogenation of an unsaturated ester
to an unsaturated alcohol [I].
The catalysts of choice, which allow the highly selective conversion of
esters to alcohols, are usually based on copper. Since the first example of
ester hydrogenolysis to alcohols, the reaction of methyl formate to methanol
described by Christiansen [ll],copper catalysts have been employed in the
vast majority of cases. In particular, much of the study of ester hydrogen-
olysis has been based on the use of “copper chromite.” These catalysts
were initially developed in 1930 by Adkins et al. [12] for acetaldehyde
condensation. During the following decade, a number of hydrogenolysis
reactions, mainly in the field of fatty alcohol production, were established.
These processes have in common the use of copper chromite catalysts [13].
The copper chromite catalyst consists of an approximately equimolar
mixture of cupric oxide CuO and cupric chromite CuCr,O, [14]. However,
the cupric chromite phase is not essential for hydrogenolysis catalysts. If
the cupric oxide is removed with acid, the remaining material is inactive
for ester hydrogenation [l]. In consequence, there are many examples in
which copper catalysts other than copper chromite have been used. Ac-
cording to Kurc and Cerveny [15], ZnO as a carrier can replace the tra-
ditionally used cupric chromite. Furthermore, Evans et al. [16] showed that
copper on silica, or even pure Raney copper, can be as effective as copper
chromite for the hydrogenolysis of esters. Thus finely divided metallic cop-
per seems to be the catalytically active component in such systems.
11. HYDROGENOLYSIS OF FORMATES
A. Methyl Formate
The hydrogenolysis of methyl formate is of particular interest as it has

been proposed as part of an alternative route for methanol production.
While the common industrial manufacture of methanol via CO hydroge-

nation over Cu/Zn catalysts at around 100 bar and 250°C is a mature process,
there has been continuous interest in processes which use less severe re-
action conditions [17].
The concept of the methyl formate process to methanol was first de-
scribed by Christiansen in 1919 [ l l ] . The first step is the carbonylation of
methanol to methyl formate:
CH,OH + CO + CH,OCHO (3)
This reaction is carried out in the liquid phase using homogeneous
alcoholate catalysts formed by dissolving an alkali metal (e.g., sodium) in
methanol. The formate so formed can then be converted to 2 moles of
methanol in either the liquid or the gas phase using copper-based catalysts:
CH,OCHO + 2H2 .+ 2 CH,OH (4)

Overall, methanol is produced from synthesis gas, but at much lower
temperatures and pressures than employed during the conventional CO
hydrogenation route [18, 191. The methyl formate process can be carried
out as a two-stage route [20, 211, but both reactions (3) and (4) can also
be conducted in a single reactor. For that case Brendlein [22, 231 reported
the use of 100" to 160°C and 30 to 60 atm with copper chromite to catalyze
the hydrogenolysis step. A French report [24] stated that continuous op-
eration in a bubble column reactor at 110°C and 5 bar was possible. In
several other studies, a concurrent, continuous process was suggested as
the basis for developing an alternative route to methanol using methyl
formate as an intermediate [25-311. In all investigations, copper-based
catalysts were used for hydrogenation, the only exception being bimetallic
catalysts comprising rhodium together with Sn, Ge, o r Pb [32].
1. Thermodynamics
Methyl formate hydrogenolysis is an exothermic reaction ( A H {298 K,
1 atm} = -47.5 kJ/mol [33])and is favored at low temperatures. The
equilibrium between methyl formate and methanol was first examined by
Christiansen [34]. The temperature dependence of the equilibrium constant
was found to be:

3016
log(K,/(mol/L)) = -__
T/K
+ 3.61
Lacy et al. [35] later confirmed this value. Sorum and Onsager [25]
carried out a detailed thermodynamic analysis for the concurrent process
[reactions (3) and (4)] and recommended a total pressure of more than 60
bar and a reaction temperature below 170°C. Kim et al. [36] studied the
thermodynamics of the gas-phase hydrogenolysis of methyl formate taking
into account the competing decarbonylation reaction [reverse of reaction
(3~:
CH,OCHO + CH30H + CO (7)
To prevent C O formation, hydrogenolysis should be carried out at
temperatures below 500 K. High conversions of methyl formate to methanol
can be achieved in this temperature region even at atmospheric pressure.
2. Kinetics of the Gas-Phase Reaction

The kinetics of the gas-phase hydrogenolysis of methyl formate over
copper-based catalysts have been studied in some detail. Evans et al. [21,
371 mainly used a commercial copper chromite catalyst (Harshaw, type
1808) at atmospheric pressure in the temperature range 373 to 503 K. The
results showed that the selectivity to methanol SCHTOH
1 1 C - H 3 0 H produced
S C H ~ O-
H
-
; [n,] = mol
nCH30CHOconvcrtcd
was higher than 90% at methyl formate conversions below 90%. Selectivity
was not influenced by temperature or the ratio of hydrogen to methyl
formate. The main byproduct was CO, which originated from the parallel
decarbonylation reaction (7). When attention was focused on catalyst life-
time, both copper chromite and Raney copper deactivated with time o n
line. At 473 K , methyl formate conversion was found to decrease from an
initial value of 40% to a stable value of about 10% after 60 min reaction
time. The original activity could be restored by reduction with hydrogen at
temperatures higher than 473 K. Deactivation was attributed to methyl
formate chemisorption on the copper sites of the catalyst.
Monti et al. [38] studied the gas-phase hydrogenolysis over an ion-
exchanged copper on silica catalyst. In contrast to the copper catalysts used
earlier, copper on silica showed constant performance at a temperature of
460 K even over a period of 7 h. The kinetics of hydrogenolysis [reaction
(4)] and decarbonylation [reaction (7)] were determined in a recycle reactor
at ambient pressure and temperatures from 120" to 190°C. Mass transfer
resistances were found to be absent in each case. The kinetic data were
fitted using a power law expression,
r, = k,, exp { s}fi i= I

Psi (9)
where r, is the rate related to the specific copper surface area of the catalyst
([r,] = mol/{min m$,}), ko is the preexponential factor ( [ k O ]= mol/{min
m$, barx"(}),E, is the activation energy ([E,] = kJ/mol), Pi is the pressure
of the component i ([P,] = bar), and a,is t h e reaction order with respect
to component i.
Table 1 shows the results obtained for three copper-on-silica catalysts
with different copper surface areas. Furthermore, reaction rates were zero-
order with respect to hydrogen and methanol for both reactions. Figure 1
shows an Arrhenius plot for the hydrogenolysis reaction.
Carbon monoxide, when present in concentrations exceeding 1 mol%,
caused long-term decrease of the catalytic activity. However, in each case
the initial activity could be restored by purging the catalyst with hydrogen
for several hours at reaction temperature.
Kim et al. [36] investigated the influence of catalyst composition on
the selectivity of methanol formation during the gas-phase hydrogenolysis.
TABLE 1
Kinetic Data for Methyl Formate Hydrogenolysis and Decarbonylation Over
Copper on Silica [38]
H y drogenol ysis 3.6.10" 117 0.39 -0.17

Decarbonylation 2.2.109 112 1 0
Note. Temperature range: 120" to 190°C; methyl formate mole fraction: 0.1 to 0.33;
CO mole fraction: 0.01 to 0.05.
- 14
2.1 2.2 2.3 2.4 2.5 5
1000/T I K1 I
FIG. 1. Arrhenius plot of rate constants for the hydrogenolysis of methyl

formate with the influence of CO on reaction rate included (CuOX 50: copper
surface area = 1.4 m'/g, Cu 200: 6.6 m'ig, Cu 300: 8.2 m2/g) [38].
HYDROGENOLYSIS OF ESTERS TO ALCOHOLS 65 I
For the optimal copper chromite catalyst with 50-70 mol% copper, calcined
at 623 K , methanol selectivities of more than 98% were obtained even at
high conversions in the temperature range between 408 and 468 K.
3. Kinetics of the Liquid-Phase Reaction

Due to the potential possibility for conducting the carbonylation [re-
action (3)] and the hydrogenolysis simultaneously in a single reactor, the
liquid-phase reaction at elevated pressures has been studied by several
authors. Sorum and Onsager [2S] used a commercial copper chromite
catalyst (Girdler G-89) at a constant hydrogen pressure of 71 bar and at
temperatures from 428 to 458 K. The rate of reaction was found to be first-
order with respect to methyl formate concentration. The apparent activation
energy over the temperature range studied was 53 kJ/mol.
Monti et al. [39] used the same catalyst and additionally determined
the influence of hydrogen and CO pressure on the rate of reaction. The
results obtained at temperatures from 408 to 473 K and pressures between
17 and 45 bar could be described using the following equation
with an activation energy of EA = 62 kJ/mol. The effect of carbon monoxide

addition was studied by carrying out a series of experiments at a temperature
of 446 K. An apparent reaction order of -0.32 with respect to CO was
determined but, in contrast to the gas-phase studies, no progressive catalyst
poisoning was observed in any case. Surprisingly, an order of magnitude
less activity was obtained compared to Sorum and Onsager (251, though
the same catalyst was used. This was attributed to a different catalyst pre-
treatment.
Liu et al. [27] reported results very similar to Monti et al. [39]. They
also used copper chromite (Girdler G-89) and achieved comparable rates
as well as a detrimental effect of carbon monoxide. In an extension, the
influence of CO, on the rate of the liquid-phase hydrogenolysis reaction
was investigated. A decrease in reaction rate of 62% was caused by addition
of only 3 mol% CO,. This catalyst deactivation increased with time on
stream and was only partly reversible after removal of CO,. Liu et al. [28]
and Palekar et al. [29-311 also carried out both carbonylation and hydro-
genolysis in one reactor using alkali methoxidekopper chromite catalysts.
Surprisingly, higher methanol production rates than predicted from the
kinetics of the single reactions were found. A synergistic effect between the
two constituents of the catalyst system apparently enhanced both the car-
bonylation and the hydrogenolysis reaction. The overall methanol produc-
tion rates under mild conditions (100" to 180°C and 50 to 65 bar) were
comparable to those in the direct gas-phase synthesis over Cu/ZnO catalysts
Gormley et al. [40] showed that Raney copper and Raney copper zinc
catalysts exhibited activities comparable to copper chromite during the liq-
uid-phase hydrogenolysis of methyl formate. They studied in detail the
effect of carbon monoxide over Girdler (3-89 copper chromite as a function
of reaction temperature. While the apparent reaction order with respect to
CO at 388 K was -0.29, a value of only -0.10 was determined at a
temperature of 433 K.
4. Reaction Mechanism
A mechanism for the hydrogenolysis of methyl formate was first pro-
posed by Sorum and Onsager [25]. They suggested the formation of a
hemiacetal intermediate (1 1) followed by dissociation into formaldehyde
and methanol (12). The aldehyde is then instantly hydrogenated to methanol

(13).
0 OH
II I
CH3-WC-H i-
H2 -+ CH3--O-C-H
I
H
OH 0
I I1
CH,--O-C-H + CH3OH + H-C-H
I
H
0
II (13)
H-C-H + HZ+ CH3OH
A detailed investigation by Monti et al. including in situ infrared spec-
troscopy [41] and the use of labeled compounds [42] confirmed that the
mechanism proceeds via the hemiacetal and formaldehyde. Competitive
adsorption of carbon monoxide and hydrogen on the active sites causes the
reversible inhibition of the reaction by CO. Friedrich et al. [43] also showed
that carbon monoxide is adsorbed more strongly than hydrogen on copper.
The cause of the irreversible catalyst poisoning at sufficiently high C O
concentrations is the deposition of a residue originating from polymerization
of the formaldehyde intermediate.
In conclusion, it is obvious that methanol synthesis via methyl formate
still has some potential. New results for the gas-phase hydrogenolysis [36]
show that methanol can be obtained with very high selectivity over an
optimized copper chromite catalyst. For the simultaneous carbonylation
and hydrogenolysis, when a high level of C O is present in the reaction
mixture, inhibition by carbon monoxide is of highest importance. Gormley
et al. 1401 reported that inhibition by CO decreases with increasing tem-

perature. Furthermore, Liu et al. 1281 and Palekar et al. 129-311, when
carrying out the concurrent reaction in one reactor, found a much higher
rate of methanol formation than calculated from the rates of the carbon-
ylation and hydrogenolysis reactions taken separately. Thus, there seems
to be realistic chances of conducting the two reactions in one reactor with
reasonable methanol production rates.
B. Higher Formates
Christiansen I l l ] also proposed a more general preparation method

for methanol using alkyl formates by carbonylation of an alcohol
ROH + C O + ROCHO
(14)
followed by subsequent hydrogenation to methanol and the parent alcohol,
which is recycled.
ROCHO + 2 H 2 4 CH,OH + R OH (15)
Christiansen [ 11) carried o u t no hydrogenolysis experiments with any
formate other than methyl. Until recently, these reactions have been very
little studied. A patent [44] states that hydrogenolysis of butyl formates,
originating from hydroformylation, gave butanols and butyraldehydes. The
reaction was promoted by a Fe,O,-Cr,O, catalyst.
An extensive investigation of the hydrogenolysis of several alkyl for-
mates over copper catalysts was conducted by Evans et al. 116, 37, 451.The
reaction system was found to be complicated by the formation of methyl
CH30H + ROCHO -
formate originating from a transesterification reaction.
ROH + C H3C H0
The methyl formate produced can then further react according to Eq.
(16)
(4). Over a commercial copper chromite catalyst (Harshaw, type 1808) the
transesterifieation reaction was found to be in equilibrium. The equilibrium
constants
were determined experimentally and found to be constant in the temper-

ature range between 373 and 433 K. Using these equilibrium constants, the
rates of the hydrogenolysis reaction (15) could be calculated from the ap-
parent reaction rates based on alkyl formate conversion. The results for the
range of forrnates are summarized in Table 2. Using these values, the
methanol selectivity was calculated. Figure 2 shows a comparison between
calculated and measured selectivities as a function of conversion.
From the data summarized in Table 2 it can be seen that the rate of
hydrogenolysis decreases with the sizc of the alkyl group, and that branching
TABLE 2
Data for Alkyl Formate Conversion Over Copper Chromite [37]
Apparent reaction Hydrogenolysis
Kc EA 3 rate, rate,
Formate [Eq. (17)] kJ/mol lop6 mol g-I s-I mol g - ' s - '
Ethyl 1.82 47.7 9.2 4.9
n-Propyl 1.84 46.7 7.3 3.9
Isopropyl 4.00 - 5 .0 2.6
n-Butyl 1.92 46.0 (7.0 3.2
Isobutyl 2.40 44.4 6.5 3.4
sec- B ut yl 6.60 34.3 4.9 2.5
Note. Rates measured at 403 K and molar hydrogen-to-ester ratio of 9; apparent
activation energy determined in the temperature range 403 to 443 K .
FORMATE
90- AElhyI
0 Propyl
o Bulyl
- A ~sO.Bulyl
s ser-Butyl
70 -
60-
>-
+
- 50-
2
I-
u
W
LO-
cn
J
30-
a
C 0 NV E R 510 N ( %I
FIG. 2. Methanol selectivity as a function of formate conversion (condi-

tions: 1-5 g copper chrornite catalyst, 403-443 K, H,:CH,OCHO ratio = 9; the
solid lines represent calculated selectivities €or three different transesterification
equilibrium constants) [37].
on the alkyl group decreases the rate further. Similar observations have
been made by Naves [46] during the hydrogenolysis of a series of benzyl
esters over nickel.
The kinetics of ethyl formate hydrogenolysis over a copper-on-silica
catalyst were studied by Agarwal et al. [47]. The reaction order with respect
to ester concentration increased from 0.12 at 404 K to 0.52 at 459 K, while
the reaction order in hydrogen was found to be 0.26.
The industrial significance of the reaction of higher formates to meth-
anol seems to be limited. Due to the decreasing hydrogenolysis rate with
increasing molecular weight of the formed ester and due to side reactions,
it was concluded that methanol is the preferred parent alcohol for the
formate process to manufacture methanol [17].
111. HYDROGENOLYSIS OF MONOESTERS
This section deals with the hydrogenolysis of monoesters other than

formates and fatty acid esters. Due to the particular industrial importance,
the reaction of the latter esters is described in the next section. In 1937 two
patents were published dealing with the production of alcohols from the
hydrogenation of carboxylic acid esters. The first, by Lazier [48], proposed
a copper oxide/zinc oxide based catalyst to prepare, for example, butanol
from butyl butyrate.
CH,-(CH2)~-COO-(CH2)~-CH, + 2Hz -+2CH,-(CH,),-OH
(18)
High selectivities to the corresponding alcohols were obtained at tem-
peratures between 200" and 400°C and 50 to 250 atm pressure. The second
patent, by Schmidt [49], recommended atmospheric pressure and temper-
atures in the range of 200" to 400°C to effect these reactions. Among the
catalysts used were nickel, copper, and cobalt, usually supported on a finely
divided substrate.
A. Kinetic Studies
Yan et al. [50]studied, besides a series of fluorinated esters, the liquid-

phase hydrogenolysis of butyl acetate over a barium-promoted copper chromite
catalyst at 50 to 200 atm pressure and temperatures between 175" and 250°C.
Transesterification reactions were found to take place. Interestingly, ad-
ditives such as calcium hydride increased the reaction rate. This was at-
tributed to the removal of water, which acted as a catalyst poison.
The production of benzyl alcohol via hydrogenolysis of methyl ben-
zoate was described by Kato et al. [51]. The reaction was carried out over
copper chromite in a bubble column reactor at 140°C and 250 atm using a
methanol/toluene mixture as solvent.
Grey et al. [52, 531 developed an anionic ruthenium hydride complex

for hydrogenolysis of carboxylic acid esters to produce the corresponding
alcohols. In contrast to most other investigations, mild reaction conditions
( T = 90"C, P = 620 kPa) were recommended. Decarbonylation and
transesterification reactions were found to decrease the achievable selec-
tivity to the desired alcohol.
Several studies [ 17, 54-60] characterizing bimetallic rhodium-based
catalysts used the hydrogenolysis of ethyl acetate as a test reaction, with
two patents claiming that ethanol yields up to 90% could be obtained at
200" to 250°C and 10 to 50 bar [54, 601.
Evans et al. [61] studied the structural and reactivity effects in the
hydrogenolysis of a series of aliphatic esters. The studies were conducted
over Raney copper at atmospheric pressure and in the temperature range
210" to 280°C. The hydrogenolysis of ethyl acetate (19) was complicated by

the subsequent formation of acetaldehyde (20).
CH3COOC2Hs + 2H2 3 2C2HsOH (19)
C2H,0H -+ CH,CHO + H2 (20)
The latter reaction was found to be in equilibrium under the given reaction
conditions. The rate of ethyl acetate hydrogenolysis could be described
using a power law expression
with an apparent activation energy E, of 88 kJ/mol.

The hydrogenolysis of a series of acetates as well as of methyl pro-
panoate and methyl butanoate was studied at 220°C. Transesterification
reactions were found to take place, but in contrast to the reaction of for-
mates [37],equilibrium was not achieved. Table 3 shows the reaction rates
TABLE 3
Ester Hydrogenolysis Rates at 220°C over Raney Copper [61]
Total rate, Hydrogenolysis rate,
Ester lo3 mol/(cm' h) 10' mol/(cm' h)
Methyl acetate 7.9 6.0
Ethyl acetate 6.7 6.7
n-Propyl acetate 11.6 9.9
Isopropyl acetate 6.2 5.6
rt-Butyl acetate 12.6 11.2
lsobutyl acetate 15.7 13.6
Methyl propanoate 4.1 3.2
Methyl butanoate 7.1 5.0
Note. Hydrogen-to-ester ratio = 20.
obtained at a molar ester to hydrogen ratio of 20 during hydrogenolysis at

differential conditions. The hydrogenolysis rates were estimated from the
total rates taking into account the transesterification reactions. For the series
of n-alkyl acetates, the rate of hydrogenolysis increases with increasing alkyl
group size. The addition of a methyl group on the alkoxyl carbon (isopropyl
acetate) decreases the rate while branching on the second alkoxyl carbon
(isobutyl acetate) enhances the hydrogenolysis rate.
The rate data for the acetates, and the formates previously investigated
[37], were fitted to the Taft equation [62]:
log R = p" (T" + hAn + K
R is the rate of the respective acetate or formate relative to the methyl
compound, C u" is the sum of the inductive constants of R' and R groups
in the ester R'COOR, and An = 6 - C n , with n the number of a hydrogens
on alkoxyl and acyl carbons. Table 4 shows the parameter values and the
correlation coefficient r achieved.
Agarwal et al. [47] studied the hydrogenolysis of simple formates and
acetates at atmospheric pressure over a copper on silica catalyst. The re-
action rates of formates were found to be 3 orders of magnitude greater
than the rates of acetates. In contrast to the findings of Evans et al. [61],
the hydrogenolysis rate of the acetates at 493 K was about zero-order in
ester, and close to 0.5-order with respect to hydrogen concentration. The
apparent activation energies in the temperature range 483 to 523 K were 99
kJ/mol for methyl acetate and 107 kJ/mol for ethyl acetate hydrogenolysis.
Ferretti et al. [63] investigated the hydrogenolysis of ethyl acetate over
bimetallic Sn/Rh catalysts. With increasing Sn/Rh ratio, the rate of hydro-
genolysis to ethanol was enhanced, while the rate of the competing for-
mation of hydrocarbons was unaffected. The rate of hydrogenolysis in the
temperature range 521 to 543 K could be described using a Langmuir-
Hinshelwood-type rate equation.
Recently, Claus et al. [64] investigated the hydrogenolysis of methyl
and ethyl acetate over copper and group VIII metal catalysts. The hydro-
genolysis of methyl acetate over copper-based catalysts at a pressure of 4
MPa and temperatures below 523 K could be described with a reaction
network consisting of hydrogenolysis [equation ( 2 3 ) ] , subsequent transes-
TABLE 4
Parameters Based on the Taft Equation (22) for Formate and Acetate
Hydrogenolysis [61]
P* h K H
Formates 10.9 0.50 - 4.38 0.96
Acetates - 22.4 - 2.2 0.025 0.96
terification to yield ethyl acetate (24), and finally, hydrogenolysis of ethyl

acetate to produce ethanol (19).
CH3COOCH3 + 2H2 -+ CH,OH + CH3CH20H (23)
CHJCOOCH3 + CH3CH20H-+ CH3COOCH2CH, + CH30H
(24)
CH3COOC2H, + 2H, -+2CH3CH,0H (19)
No acetaldehyde was detected. This was explained by the much higher
pressure (4 MPa compared to 0.1 MPa employed during the studies of
Evans et al. [61]), strongly favoring ethanol according to Eq. (20). The
kinetics of the proposed reaction network over a copper/manganese oxide
catalyst could be described using exponential rate expressions.
Table 5 summarizes the calculated rate constants k, at the actual tem-

peratures, the preexponetial factors k,,,([k]= mol gg' ht' M P c 2 ) , and
the activation energies ([E,,] = kJ/mol) for each of the three individual
reactions. kcthy,/kmethy,
is the quotient of the rate constants of ethyl and
methyl acetate hydrogenolysis. Figure 3 shows a comparison between ex-
perimental and calculated ethyl acetate conversion as a function of space
time and temperature.
Van der Grift et al. [65] used the hydrogenolysis of methyl acetate as
a test reaction to explore the effect of different oxidation-reduction treat-
ments on the structure and reactivity of copper particles deposited on silica.
It could be shown that the catalyst activity was reversibly changed by trans-
forming the surface structure of the copper particles. The more densely
packed copper surfaces had a lower methyl acetate hydrogenolysis activity.
TABLE 5
Kinetic Parameters [Eq. (25)] for Acetate Hydrogenolysis [64]
Ethyl acetate
Methyl acetate Transesteri- hydro-
TIK hydrogenolysis fication genolysis kcthy, lk,,,'.lhYl
503 6.2 174.2 14.4 2.34

513 10.0 240.2 24.3 2.43
523 14.4 289.4 44.9 3.12
533 35.9 379.5 65.6 1.82
E A , kJ/mol 125.6 56.2 118.5

k,,. mol/(g h 10I I ) . 7') 10' 11') 1()"'4h
MPa*)
533K
1Q
'.OO
u 0.75
X
z
050
025
15 30 fS 60 75 90
FIG. 3 . Comparison between experimental (points) and calculated (curves)

conversions of ethyl acetate (XktoAc)versus space time ( W/(F&Ac) at various
temperatures (catalyst: copper/manganese oxide, P = 4MPa, molar hydrogedester
ratio = 12.2) [64].
B. Reaction Mechanism
A mechanism for acetate hydrogenolysis was proposed by Yan et al.

1501 and Evans et al. [61]. In contrast to the reaction of formates, which
involves the presence of undissociated formate species on the catalyst sur-
face, the acetate is adsorbed dissociatively
RCOOR' + 2" + RCO" + R'O" (26)
where * indicates a catalytic site on the surface. Isotopic labeling studies
[47] showed that the alkoxy fragment R'O" reacts quickly to form R'OH,
while the acyl group RCO" is adsorbed longer. Thus the hydrogenation of
the acyl fragment is believed to be the rate-determining step during acetate
hydrogenolysis. The acyl group can be hydrogenated either to the desired
alcohol or to the corresponding aldehyde, which is subsequently hydroge-
nated 150, 641. Agarwal et al. [66] have shown, using Cu/SiO, catalysts,
that acetaldehyde is hydrogenated more than 3 orders of magnitude faster
than ethyl acetate. Thus the amount of aldehyde in the product is deter-
mined by the thermodynamics of reaction (20). An in situ infrared spec-
troscopy investigation [67] during ethyl acetate hydrogenolysis gained fur-
ther evidence for the proposed mechanism via dissociatively adsorbed
fragments. Furthermore, Kenvin and White [68] could explain their results
on the hydrogenolysis of ethyl acetate over several copper-on-silica catalysts
based on the mechanism proposed by Evans et al. [61]. As a result, the
mechanism based on dissociative adsorption would seem to be established.
C. Manufacture of Ethanol
Some interesting new routes to ethanol including a hydrogenolysis step
have been proposed recently. Kiff and Schreck [69] started with acetic acid,
which was esterified using an alkene.
C H, CH,
I
CH,COOI-I + CH,-CH=C-CH, 4 CH,-COO-C-CH,-CH,
I (27)
C H,
The obtained ester could then be hydrogenated over a Cu/ZnO catalyst to

yield ethanol and a higher alcohol.
C H, CH,
I I
CH,--COQ-C---CH,-CH, -+ 2H, -+ CH,CH,OH + CH,-CH~-CC-CH,
The latter was then dehydrated back to the alkene.

c H3 c H,
I I
CH3-CH2-C-CH, + CH,-CH=C-CH, + 2H20 (29)
I
OH
Both Davy-McKee [70,71] and Halcon [72,73] have proposed similar
processes with esterification of acetic acid as the first step. In contrast to
Kiff and Schreck, lower alcohols such as methanol were used to produce
the ester (30).
CH,COOH + CH,OH-+ CH,COOCH, + H,O (30)
CH3COOCH, + 2H,+ CH,OH + CH,CH,OH (23)
The .methyl acetate produced was then hydrogenolyzed to the desired
product ethanol (19), while the by-product methanol was recycled for use
in the esterification.
IV. HYDROGENOLYSIS OF FATTY ACID ESTERS
The high-pressure hydrogenolysis of fatty acid esters is a widely used

process for the manufacture of fatty alcohols. Fatty alcohols, which are
aliphatic alcohols in the C6 to C22region:
CH,(CH2),0H n = 5 to 21
HYDROGENOLYSIS OF ESTERS TO ALCOHOLS 66 1
are mainly used as intermediates for the production of synthetic detergents

and emulsifying agents.
The development of catalytic hydrogenation for producing fatty al-
cohols dates back to the early 1930s. Processes were developed almost
simultaneously by Normann [74], Schmidt [75], and Schrauth et al. [76, 771
in Germany; and by Adkins and Folkers [78], Lazier [48,79], and Calingaert
and Edgar [go] in the USA. Fatty acids, fatty acid esters, and triglycerides
may be used as starting material according to the following equations:
RCOOH + 2H2+ RCH20H + H 2 0
RCOOR'+ 2H2 -+ RCH20H + R'OH
In most cases, hydrogenation is carried out using copper-containing
catalysts at temperatures in the range of 200" to 300°C and pressures be-
tween 20 and 30 MPa. Unsaturated alcohols can be obtained using mild

hydrogenation catalysts such as zinc chromite or copper cadmium chromite
[ X l ] . The use of these catalysts has been extensively reviewed by Bertsch
et al. [82].
Liquid-phase hydrogenation of free fatty acids is used industrially,
although catalysts and equipment have to meet higher demands due to
corrosion and poisoning which may be caused by the acids [83]. Hydro-
genation of triglycerides is also possible but has not yet been carried out
industrially. This is because, under the required conditions, the glycerol is
subsequently converted to propylene glycol and propanol, which have not
been considered as useful by-products [81]. The major raw materials for
the manufacture of fatty alcohols via hydrogenation arc fatty acid esters.
These esters are produced either by esterification of fatty acids (32) or by
RCOOH
C H2COOR
+ R'OH -
transesterification of triglycerides using methanol (33).
RCOOR' +
C H,OH
H20 (32)
I I
CH,COOR + 3CH30H -+ CHOH + 3RCOOCH, (33)
C H2COOR C H20H
The hydrogenolysis of the fatty acid esters obtained is carried out using
three different commercial processes. Suspension hydrogenation is a con-
tinuous liquid-phase process at a hydr-ogen-to-ester ratio of typically 50 in
the presence of a finely powdered catalyst. Gas-phase hydrogenation uses
a fixed bed of catalyst either at a large excess of hydrogen (ca. 500 mol of
H2 per mol of ester) or a mixture of hydrogen and inert gas. Trickle bed
hydrogenation combines the features of both liquid- and gas-phase processes
and offers a fixed bed operation, without the necessity of catalyst-product
separation. It is also usable for nonvaporizable starting materials. Details
of these processes have been reviewed [2, 81, 841.
A. Thermodynamics
Mutzall and van den Berg [85] determined the equilibrium constants
for the liquid-phase hydrogenolysis of coconut oil (containing C, to CI8
esters) and tallow oil (with esters in the range C,* to CIX).Equilibrium of
reaction (1) was reached using alcohol and ester as the starting material
(Fig. 4). The temperature dependence of the equilibrium constant K ( [ K ]
= atrnp2) in the liquid phase was found to be
K = 9.65.10-x.exp {s} for coconut oil
{z]
and
K = 16.8.10--8-exp for tallow oil
Equilibrium constants for the hydrogenolysis of pure C, to Clxfatty

acid esters were slightly higher than the values obtained for the mixtures.
A more general discussion of the thermodynamics of fatty alcohol
production can be found in a paper by Coenen [86]. He pointed out that
one has to consider three important individual reactions. Reaction (1) is
the desired reaction for the hydrogenolysis of both saturated and unsatu-
Y
L
II
.$ 0.6
3 I
0 1 2 3 4
- Reaction time (h)
FIG. 4. Course of hydrogenation of coconut ester and alcohol (temperature
302"C, hydrogen pressure 165 atm, 3% catalyst; 0 starting from ester, V starting
from fatty alcohol) [85].
TABLE 6
Equilibrium Constants for Reactions during Fatty Alcohol Production [86]
Reaction Kp (25°C) K , (300°C)
Hydrogenolysis (1) 1.9.10' a t m p l 3.5.10-' atm-'
Hydrocarbon formation (34) 2.1 .lo16 4.3.108
Saturation (35) 4.9. atm l.0-104atm-'
rated fatty acid esters. The formation of hydrocarbons according to (34) is

undesired in both cases. Reaction (3.5) is also undesired, if unsaturated
alcohols have to be produced.
+ H2-+ RCH, + H 2 0
RCH 2 0 H (34)
RCH=CHR' + H2 + RCH,CH2R' (35)
All reactions are exothermic and Table 6 shows calculated equilibrium
constants K , for the three reactions. While reactions (34) and (3.5) are
limited only by reaction kinetics, the equilibrium conversion of the hydro-
genolysis reaction at 300°C is only 2% at atmospheric pressure but can be
increased to 96% at a pressure of 200 atmospheres. Operation at lower
temperatures would be desired from a thermodynamic point of view, but
the activity of the usual copper-based catalysts necessitates a certain min-
imum temperature. Thus the hydrogenolysis of esters to fatty alcohols is
conducted at pressures between 200 and 300 atm, and at a temperature of
about 300°C. Higher temperatures are not used because hydrocarbon for-
mation then becomes more important [86].
B. Kinetic Studies and Reuction Mechanism
Church and Abdul-Gelil [87] conducted a series of experiments at

different temperatures and found that the optimum temperature for methyl
laurate hydrogenolysis with respect to reaction rate and yield is about 300°C.
By using different copper chromite catalysts it was shown that barium had
no positive effect on the catalyst performance. This was in contrast to
findings reported by Folkers and Adkins [88]. On the other hand, and in
agreement with results by Riener [89], careful control of the reaction con-
ditions during catalyst preparation was found to be necessary.
Miya et al. [90] studied the hydrogenolysis of rape seed fatty acid
methyl esters over copper chromite. They found that water, which is formed
during the reduction of the CuO component of the catalyst, acted as a
catalyst poison. Surprisingly, if C O was added to the reaction mixture, the
reaction rate increased. This was attributed to the removal of water by the
water-gas shift reaction (36):
CO + HZO + C02 + H2 (36)
and to the beneficial effect of the carbon dioxide formed on the rate of the
reaction.
The kinetics of liquid-phase fatty acid ester hydrogenolysis over copper
chromite have been determined by Mutzall and van den Berg [85].Coconut
oil and tallow oil esters were used in the temperature range 270" to 320°C
and at pressures between 47 and 165 atm. The rate of the net reaction could
be described by the following equation
r = klCc\rcr(PHJ2 - k 2 ( C h h < d 2 (37)
taking into account both hydrogenolysis and the reverse reaction. r is the
reaction rate ([r] = h-l), c, the concentration of the reactant i ([c,]= wt%),
PHLthe hydrogen pressure ( [ P H 2 ] = atm), k , the rate constant of hydro-
genolysis ( [ k , ]= h ' atm - 2 ) , and k2the rate constant of the reverse reaction
([k,] = h-I).
At a temperature of 28S"C, the influence of the water concentration
cHZO([cHZ0]= wt%) on the two rate constants was found to be
k 20
k2 =
1 + 14c,,, (39)
with k,, the rate constants for cHZO= 0 wt%. The equilibrium constant K
([K] = atm-2) calculated from the rate constants
K = klO/kzo= 6.1 10 + atm
was in good agreement with the value determined earlier [85].Mean values
for the temperature dependence of the rate constants for the hydrogenation
of coconut and tallow oil esters could be described by [85, 861:
klO/h-I atmP2 = lo3. exp {%}
Coenen [86] used data reported by Haidegger and Hodossy [91] to

estimate the activation energy of the hydrocarbon formation (reaction 34).
He determined a value of about 110 kJ/mol compared to 70 kJ/mol for
alcohol formation via hydrogenolysis.
The kinetics of hydrogenolysis of unsaturated fatty acid esters have
been studied to some extent by Bertsch and co-workers [92-941. They found
that the most suitable catalysts for that purpose are copper-cadmium ca-
talysts with a copper-to-cadmium mole ratio of about 3. Optimal reaction
conditions were 280" to 300°C and high hydrogen pressures (between 250
and 300 atm). Coenen [86] determined an activation energy of 103 kJ/mol
for the formation of unsaturated fatty alcohols using the data reported by
Bertsch et al. [92-941.
Very little attention has been paid to the mechanism of fatty acid ester
hydrogenolysis. Normann [74] postulated the formation of a hemiacetal
intermediate on the catalyst surface
OH
I
RCOOR' + H2 -+ R-C-0-R'
I
H
which was suggested then to be converted to 2 alcohol molecules. Yan
et al. [50] also proposed this mechanism and gained evidence by the oc-
currence of hemiacetals in the case of the hydrogenolysis of fluorinated

esters. On the other hand, Mutzall and van den Berg [85]could not detect
any intermediates over the whole range of reaction conditions of interest
and therefore concluded that there is no need to assume the formation of
intermediate products.
C. N e w Developments
Further research effort has been directed at both the development of

more active catalyst systems and alternative process schemes. While the
original copper chromite has been used almost exclusively for the production
of saturated fatty alcohols over several decades, the activity of this catalyst
has been shown to be significantly increased by the addition of zinc [95,
961 or iron [97-1001. Precious metal/zinc oxide catalysts have also been
used for the manufacture of C,, fatty alcohols with high yields [loll. Fur-
thermore, the use of ruthenium-tin catalysts with high activity has been
claimed as a means of allowing the hydrogenolysis of fatty acid esters to
be carried out at lower temperatures [54].
The proven zinc chromite catalyst system for producing unsaturated
fatty alcohols has also been improved by the addition of alumina [102, 1031.
The only precious metal based heterogeneous catalyst for obtaining unsat-
urated alcohols so far has been ruthenium- tin boride, as described by
Narasimhan and co-workers [104-1061. On the other hand, homogeneous
catalysts such as nickel Ziegler-type catalysts [ 1071 and ruthenium chloride
complexes [lo81 have been shown to be effective for the highly seiective
formation of unsaturated alcohols.
Some interesting modifications of the existing processes have been
suggested recently. Mugishima [109] claimed that the manufacture of fatty
alcohols was possible at very low hydrogen pressures. Hydrogenation of
methyl caprylate was carried out at 250" to 300°C and pressures below 5
atm. However, high fatty alcohol yields cannot be expected, taking the
thermodynamic constraints into account (cf. Sec. 1V.A.).
A reduction of the hydrogen excess during the gas-phase hydrogen-

olysis was achieved by the admixture of an inert gas such as nitrogen to the
reaction mixture [110]. In contrast to the findings on the inhibiting effect
of water, the addition of water was shown to maintain the long-term catalyst
activity in the hydrogenolysis of methyl C,2.,8fatty acid esters [ I l l ] .
If methyl esters can be used as starting material without prior esteri-
fication of fatty acids, a new process by Dupont et al. [112] might be used.
111 this case, the by-product methanol formed during hydrogenolysis is sub-
sequently subjected to methanol steam reforming (43). The hydrogen pro-
duced can be utilized in the initial reaction step.
CH30H + H 2 0 + C 0 2 + 3H2 (43)
The use of glycerides as starting materials for hydrogenolysis has also been
reconsidered [113]. Liquid glycerides were converted at 160" to 250°C and
50 to 300 bar hydrogen pressure using multitube reactors. The achieved
product consisted of fatty alcohols and 1,2-propanedioI. The latter com-
ponent is a valuable product, given the growing demand €or diols.
V. PRODUCTION OF DIOLS
Early work by Adkins and co-workers, reviewed in Ref. 1, showed

that esters of dibasic acids can be transformed to the corresponding diols.
ROOC-(CH,),,-COOR + 4H2 --+ HO-(CH,)n+,-OH + 2ROH
(44)
Liquid-phase hydrogenolysis over copper chromite at hydrogen pres-
sures between 170 and 270 atm gave diols in yields above 95%, when esters
of dibasic acids with more than 2 carbon atoms separating the carbalkoxy
groups ( n > 2) were used. The yield from succinates ( n = 2) was found to
be 80-90%, while only less than 40% 1,3-propanediol was obtained from
malonic ( n = 1) esters. According to Adkins, ethylene glycol ( n = 0) could
only be obtained at pressures higher than 270 atm [l].
Since the early 1970s, there has been a much expanded interest in
developing hydrogenolysis-based alternative routes for the production of
ethylene glycol and 1,4-butanediol. Ethylene glycol is a valuable commercial
chemical and finds application in antifreeze and hydraulic fluids as well as
in the manufacture of alkyd resins and polyester fibers. 1,4-Butanediol is
used in the production of solvents such as tetrahydrofuran and y-butyro-
Iactone and as a starting material for producing polybutylene terephthalate
(PBT), a thermoplastic polyester. Both ethylene glycol and 1,4-butanediol
are currently manufactured via costly routes involving ethylene oxide and
acetylene-based butynediol, respectively.
A. Ethylene Glycol
1. Processes
There have been few patents claiming the manufacture of ethylene
glycol via the liquid-phase hydrogenolysis of carboxylic acid esters.
ROOC-COOR + 4H2+ HO-(CHJZ-OH + 2ROH (45)
Chevron Research [114, 11.51 produced ethylene glycol over Cu/ZnO-
based catalysts at 250°C and at a hydrogen pressure of about 200 bar. Ube
Industries described the use of Cu-Cr-Mn [116] or copper-on-silica cata-
lysts [ 1171 for dimethyl oxalate hydrogenolysis in methanol at around 200°C
and between 20 and 120 atm hydrogen pressure.
However, higher ethylene glycol yields under mild reaction conditions

have been achieved by gas-phase hydrogenolysis. The first process for the
manufacture of ethylene glycol in the gas phase was described by Zehner
and Lenton [118]. The diol was obtained by the gas-phase reaction of several
dialkyl oxalates at 200" to 230°C and at relatively low pressures of 10 to 32
atm. The authors suggested a hydrogen to ester ratio of 4:l to 30:l and the
use of copper chromite catalysts. Poppelsdorf [ 1191 converted methyl or
ethyl oxalate at 180 to 240°C and pressures between atmospheric and 66
bar. Over copper chromite or copper-zinc chromite, ethylene glycol was
obtained with selectivities higher than 90%. Special attention was paid to
the extent of formation of by-product 1,2-butanediol (which might nega-
tively affect the use of the ethylene glycol for polyester fiber manufacture).
Kippax et al. [120] used comparable reaction conditions with a Cu/ZnO
catalyst, the activity of which was enhanced by addition of CO, to the
reaction mixture. Ube Industries [121, 1221 proposed a chromium-free cop-
per-on-silica catalyst, which gave rise to ethylene glycol in yields as high as
97%. Bartley [ 123, 1241 improved copper-on-silica catalysts by removing
impurities such as sulfate, iron, and alkali metals from the silica carrier.
2. Kinetics and Mechanism

A detailed study of the gas-phase hydrogenolysis of diethyl oxalate
over several copper-based catalysts has been published by Thomas et al.
[125, 1261. Thermodynamic analysis of the reaction system showed that high
conversions of diethyl oxalate to ethylene glycol were possible at pressures
below 600 kPa. At 513 K , 600 kPa, and a molar hydrogen to oxalate ratio
of 30:1, copper catalysts including Raney copper and copper deposited on
carriers such as silica, titania, or alumina were tested. All catalysts showed
initial deactivation with time on stream. Deactivation was lowest for the
catalyst with the highest copper dispersion, a copper-on-silica catalyst pre-
pared by the ion-exchange method. The product composition during diethyl
oxalate hydrogenolysis showed evidencc for sequential steps in the overall
reaction. In the first step (46), diethyl oxalate (DEO) was hydrogenolyzed
to ethanol and ethyl glycolate (EGT), which was subsequently converted

to the desired product, ethylene glycol (47).
C2Hy-OOC-C00-C2H, + 2H2
-+ C2HS-OOC-CH20H + C2HyOH (46)
C2H,-OOC-CH,OH + 2H2
-+ HOH2C-CH2OH + C2HSOI-I (47)
By-products included the formation of “gas” products containing CO,
C02, and C2H4in approximately equimolar proportions over Raney copper
and copper on silica. The product composition is shown in Fig. 5 . Copper
on acidic (A1,03) or basic (MgO) supports exhibited low overall selectivities
with respect to ethylene glycol, the by-products being mainly 1,4-dioxane

and diethyl ether.
The most suitable catalyst in terms of stability and selectivity (copper
on silica prepared by ion exchange) was subjected to a kinetic study. In the
temperature range 483 to 543 K, the rates of the two subsequent reactions
(46) and (47) could be described with the following equations, which were
derived using a Langmuir-Hinshelwood model.
C
.Q
.r
8 0.1
f
8
20.2
0
2
a
0
0 20 LO 60 80 100
Conversion of DEO (%I
FIG. 5 . Product composition for diethyloxalate hydrogenolysis over Raney
copper ( T = 513 K , P = 500 kPa, H,/ester = 9:1, (0)“gas”, ( 0 ) EtOH, (A)
EGL, (0)EGT, (v) DEO) [126].
TABLE 7
Values of Constants for Diethyl Oxalate Hydrogenolysis [126]
T, k, 7 k2 7 K,,,, KEoT, K,, Correlation
K mmol kg-'s-' mmol k g - k ' kPa-' kPa-' kPa-' coefficient
483 21.2 8.97 9.3 5.1 0.0027 0.999
513 89.6 54.5 3.96 1.04 0.0019 0.998
543 270 345 1.11 0.069 0.0012 0.998
The values obtained for the constants in these rate equations and the
corresponding correlation coefficients are given in Table 7. The Langmuir-
Hinshelwood model chosen involves the dissociative adsorption of both
diethyl oxalate and ethyl glycolate, which are expected to yield the following
fragments:
C2HS-OOC-COO-CzHS + 2*
-+C2Hs-OOC-CO" + C2HsO* (50)
C2HS-OOC-CH2OH + 2* + HOHZC-CO" + C2H50" (51)
Thus the proposed mechanism is similar to that previously established
for acetates and higher esters [41, 42, 671.
B. Butanediol
Several processes which utilize a hydrogenolysis step to obtain 1,4-

butanediol have been described in the patent literature. Maleic anhydride,
y-butyrolactone, or alkyl esters of maleic or succinic acid are possible start-
ing materials.
1. Hydrogenation of Maleic Anhydride

The hydrogenation of maleic anhydride is covered here because se-
quential hydrogenolysis steps have been observed in the overall reaction.
Mitsubishi Petrochemical has developed a process for the manufacture of
tetrahydrofuran from maleic anhydride [127- 1291. The liquid-phase reac-
tion was carried out at 60 to 120 bar and around 200" to 250°C over a nickel-
based catalyst. Maleic anhydride was rapidly converted into succinic an-
hydride, then into y-butyrolactonc, and finally into tetrahydrofuran. Bu-
tanediol was found to be an intermediate, forming a polyester with succinic
acid which reacted further to tetrahydrofuran.
Miya et al. [130] used a bifunctional catalyst containing Cu-Cr-Zn
and an alumina-silica component for the same reaction. At 25 atm and
270"C, a similar reaction sequence was found, but butanediol was also
formed from y-butyrolactone over the copper catalyst. Butanediol was then
dehydrated to tetrahydrofuran over the acidic catalyst. Loktev et al. [131,
670 TUREK,TRIMM, AND CANT
1321 studied the hydrogenation of maleic anhydride in dioxane over nickel

and cobalt catalysts at 200" to 250°C and a pressure of 100 atmospheres. In
the first step, maleic anhydride (MA) was hydrogenated to succinic anhy-
dride (SA), which underwent hydrogenolysis to form 1,4-butanediol (BDL)
via the intermediate y-butyrolactone (GBL). Butanediol then reacted fur-
ther to form tetrahydrofuran (THF), the side products being propanol and
butanol. The rate of maleic anhydride hydrogenation was found to be 1
order of magnitude higher than the rate of succinic anhydride conversion.
CH-€O, CH2<0, C H,<HZ, c H*--CH*,
II 0 4 I 0-t I 0 + H&(CHZ),-OH + I 0
CH--CO/ CH2<O/ CH2<0' C HZ-CH2'
MA SA GBL BDL THF
(52)
Fischer et al. [133] prepared butanediol from a maleic anhydride/l-

butanol mixture at 200 to 250 atm hydrogen pressure and a temperature of
220°C over a coppericobalt catalyst. Budge et al. [134, 1351 used a com-
mercial copper/zinc oxide catalyst to produce tetrahydrofuran in yields higher
than 90% from maleic anhydride at 40 atm and 230" to 270°C. However,
by adjusting the reaction conditions, e.g., by decreasing the temperature,
the intermediate y-butyrolactone could be obtained in yields of up to 50%.
Interestingly, the y-butyrolactone yield at fixed reaction conditions in-
creased with decreasing catalyst particle size [ 1351, thus indicating some
influence of pore diffusion on the selectivity. Mabry et al. [136, 1371started
with maleic acid to produce mixtures of tetrahydrofuran and butanediol
over a Pd/Re/carbon catalyst. At 175" to 215°C and around 200 atm pressure,
y-butyrolactone was again observed as an intermediate.
Castiglioni et al. [ 1381 prepared y-butyrolactone via gas-phase hydro-
genation of maleic anhydride over copper-based catalysts. In contrast to
the high-pressure processes, the reaction was carried out at atmospheric
pressure. While y-butyrolactone could react to tetrahydrofuran and butanol,
no butanediol was formed.
2. Hydrogenation of y-Butyrolactone
The cyclic ester y-butyrolactone was also utilized as a starting material
for producing butanediol. From the previous section it is obvious that high-
pressure operation is needed to obtain the diol in sufficiently high yields.
Nissan and Mitsubishi Chemical Industries [ 139, 1401 converted the lactone
to 1,4-butanediol batchwise at 200" to 250°C and 100 to 120 atm over nickell
cobalt or copper chromite catalysts. Butanediol could be obtained with
yields higher than 90%. Bradley et al. [141] described the gas-phase hy-
drogenolysis of y-butyrolactone at 200" to 230°C and pressures between 15
and 30 atm over a copper-zinc oxide catalyst. Butanediol, together with
n-butanol and tetrahydrofuran, were among the formed products. Cawse
et al. [142] used similar reaction conditions (40 atm and 210°C) to obtain
butanediol over a barium-stabilized copper chromite catalyst, while Weyer

et al. [143] recommended a hydrogen pressure of 60 atm and the use of a
copper/cobalt catalyst. Johnson et al. [144] improved the process by addition
of water vapor to the y-butyrolactonelhydrogen mixture.
3. Hydrogenolysis of Dicarboxylic Acid Esters

Many processes for the preparation of butanediol from esters of C,
dicarboxylic acids have been suggested in the patent literature. Blanshtein
et al. [145] converted esters to the corresponding diols via liquid-phase
hydrogenolysis a t 280" to 300°C and 300 atm in the presence of a copper
chromite catalyst. Bashkirov et al. [ 1461 obtained butanediol from dialkyl
succinates in the liquid phase over copper chromite at 553 K and 200 atm,
with butanediol yields of up to 80% reported. Couteau et al. [147] described

a two-stage route to manufacture 1,4-butanediol from maleic acid. In the
first step, maleic acid was esterified with a C,-balkanol to the corresponding
dialkyl ester. The dialkyl maleate produced was then hydrogenolyzed over
copper chromite to give butanediol and the alkanol, which was recycled to
the first stage. Kouba and Zletz [148] converted diethyl succinate to bu-
tanediol at 135 atm and 200°C over a copper-aluminum borate catalyst,
while Irick et al. [149] obtained a mixture of tetrahydrofuran, y-butyrolac-
tone, and butanediol over copperhitania at the same pressure but a higher
temperature of 300°C. Deshpande et al. [ 105,1061 hydrogenolyzed dimethyl
succinate in the liquid phase over Ru-Sn boride catalysts at 200°C and 88
bar, and obtained butanediol in high yield together with tetrahydrofuran
and methyl-y-hydroxybutyrate as by-products.
Davy-McKee have recently commercialized a new, cost-effective, bu-
tane-based route to butanediol and its derivatives which contains the gas-
phase hydrogenolysis of a dialkyl ester as one step [141, lSO-154]. The
process has three basic processing steps, the preparation of maleic anhydride
from n-butane via oxidation over vanadia catalysts (53), the esterification
of maleic anhydride using ethanol (54), and the hydrogenolysis of the re-
sulting diethyl maleate (55).
C,Hlo + 3.502 -+C,H20, + 4 H 2 0 (53)
C4H302+ 2C2HsOH -+C2HsOOC-CH=CH-COOC2H5 + H20
(54)
C,H500C-CH=CH-COOCzHs + 5HtI,
-+ HO-(CHJ,-OH + 2CZHsOH (55)
The hydrogenolysis step is carried out over copper-based catalysts at
170" to 190"C, 30 to 45 bar, and very high hydrogen-to-ester mole ratios of
150 to 800. The reaction is believed to proceed via diethyl succinate and y-
butyrolactone, while butanediol itself can further react to form tetrahydro-
furan. The relative amounts of y-butyrolactone and butanediol can be con-
trolled by choice of reaction conditions, with high pressures and low tem-
peratures favoring butanediol.
Thomas et al. [125, 155, 1561 studied the gas-phase hydrogenolysis of
dimethyl succinate over Raney copper. Thermodynamic analysis showed
that both y-butyrolactone and butanediol can be formed from dimethyl
succinate. y-Butyrolactone can then react to butanediol ( 5 6 ) , the formation
of butanediol being favored at high pressures and low temperatures.
C HZ-CHZ\
I 0 + 2H2+ HO-(CHZ),-OH
C H2-CO”
The product composition for dimethyl succinate hydrogenolysis at 5 13
K, a moderate pressure of 500 kPa, and a molar ester to hydrogen ratio of
9:l is shown in Fig. 6. y-Butyrolactone (GBL) was formed in the first step
(57). Tetrahydrofuran (THF) and water occurred as secondary products at
elevated dimethyl succinate (DMS) conversions (58).
CH,OOC-(CHZ),-COOCHJ + 2H2
C HZ-CH,\
- 1 0 + 2CH30H (57)
C H2-CO”
C H,--CH,\ C Hl-CH?\
I 0 +2H,-+ I 0 + H,O (58)
C HZ-CO” C fl2-CH2”
No traces of butanediol were found. Thomas [125] showed that bu-
tanediol, if formed as a n intermediate, would dehydrogenate to form y-
butyrolactone [reverse of reaction (56)] under the given reaction conditions
A methane
methanol
4.-
0
3 0 THF
U GBL
0
L
Q 0 DMS
.-c 0.6 A water
c
0
.-
c
u
c
F? 0.4
0.2
0.0
0.0 0.2 0.4 0.6 0.8
Conversion of DMS
FIG. 6. Product composition as a function of DMS conversion (reactor

pressure = 500 kPa, temperature = 513 K , hydrogeniDMS ratio = 9.1) [lSS].
at a rate much higher than the rate of dimethyl succinate hydrogenolysis.

Reppe [157] and Bartok et al. [158] had earlier also obtained y-butyrolac-
tone from butanediol over copper catalysts.
The rate of dimethyl succinate (DMS) hydrogenolysis at differential
conditions was described using a power law equation [156]:
where P, ( [ P J = kPa) is the partial pressure of species i and Y ( [ r ] = mmol

kg-' s-') is the reaction rate. Water drastically inhibited the reaction, but
since water is not known to be strongly adsorbed on copper, the formation
of succinic acid, which adsorbs on the copper surface and blocks active sites,
was postulated.
+ 2H20
CH,OOC-(CH2)2--COOCH,
-+ HOOC-(CH,)2-COOH + 2CH30H (60)
Zhang and Wu [159] studied the hydrogenolysis of diethyl succinate
over coprecipitated copper catalysts at temperatures between 200" and 230"C,
pressures in the range 20 to 40 bar and a molar hydrogen to ester ratio of
100. Diethyl succinate could react to both y-butyrolactone and butanediol,
which further formed tetrahydrofuran and water. At 200°C and 40 bar, the
main product was butanediol and, by altering the reaction conditions, it
was clearly shown that low temperatures and high pressures favor butanediol
formation. The experimental data could be described by power law expres-
sions.
In a recent investigation, Turek et al. [160] studied the hydrogenolysis
of dimethyl succinate at 513 K and 500 kPa over several copper-based
catalysts. Coprecipitated copper/zinc oxide was shown to have 1 order of
magnitude higher activity per unit copper surface area than other coppcr
catalysts such as copper chromite or copper on silica.
C. Other Diols
Although Adkins [1] showed that dicarboxylic acid esters with higher
molecular weight can also be converted to diols with high selectivity, there
have been few examples of commercial application of these reactions. East-
man Kodak [161] prepared cis- and truns-l,4-dimethylolcyclohexane, a start-
ing material for polyesters, polyurethanes, and polycarbonates, from di-
methyl terephthalate (DMT). Initially, DMT was hydrogenated using
palladium catalyst at 160" to 180°C and 300 to 400 atm to yield the dimethyl
ester of 1,4-cyclohexane dicarboxylic acid. In the second step, the ester was
subjected to hydrogenolysis over a copper chromite catalyst. The desired
product could be achieved in 96-98% selectivity and, by choice of the
reaction conditions and the catalyst composition, the cidtrans ratio in the
product could be controlled.
VI. CONCLUSIONS
The production of alcohols via ester hydrogenolysis is a versatile re-

action applicable for a wide range of substrates. Competing undesired re-
actions-the formation of hydrocarbons and acids-are possible; thus the
reaction usually has to be carried out at low temperatures over mild hy-
drogenation catalysts. Copper-based catalysts are still used in the majority
of applications. From the summarized material it is obvious that finely
divided copper is the active component in these catalyst systems. A variety
of carriers have been used successfully, and even pure (Raney) copper has
proven to be as active as other copper catalysts for the hydrogenolysis of
several esters. However, in the case of esters with higher molecular weight
such as fatty acid esters and dialkyl succinates, copper seems to be signif-
icantly promoted by zinc oxide.

Recently, modified rhodium catalysts have attracted much interest.
The preliminary results suggest that the selectivity with respect to the desired
alcohols can be strongly increased by the addition of tin to the precious
metal. These systems also remain more active than copper, thus enabling
operation at milder reaction conditions.
The most promising reaction of formates is the hydrogenolysis of methyl
formate as part of a two-stage route to methanol. In particular, the con-
current carbonylation and hydrogenolysis in one reactor seems to have great
potential. Methanol production rates comparable to those in the conven-
tional gas-phase route were recently achieved, reaction conditions being
much milder than during the direct CO hydrogenation. The hydrogenolysis
of acetates could be part of new, acetic acid based routes to ethanol. In
contrast to alternative processes, high overall ethanol yields have been
claimed. The production of fatty alcohols from fatty acid esters is a mature
process. After 50 years of successful industrial operation, research effort is
mainly directed at optimization of catalysts and process conditions.
One of the most promising fields in ester hydrogenolysis is the rnan-
ufacture of diols from esters of dicarboxylic acids. The esterification of
maleic anhydride, followed by hydrogenolysis of the ester obtained, allows
the production of 1,4-butanediol at lower temperatures and pressures than
employed in the conventional acetylene-based route. This alternative pro-
cess has recently been commercialized. It appears possible that a broad
range of diols could be produced in similar ways with high selectivities.
Given the growing demand for diols, these reactions might attract more
interest for future research.
ACKNOWLEDGMENT
One of the authors (T.T.) gratefully acknowledges a grant by the

Alexander von Humboldt Foundation under the Feodor Lynen program,
which provided the time for writing this review. We also thank the Aus-
tralian Research Council for financial support.
REFERENCES
1. H. Adkins, Catalytic hydrogenation of esters to alcohols, Org. Reactions,

8, 1-27 (1984).
2. U. Kreutzer, Manufacture of fatty alcohols based on natural fats and oils,
J . A m . Oil Chem. Soc., 61, 343-348 (1984).
3. L. Cerveny and V. Havlicek, Heterogenne katalyzovane redukce esteru
karboxylovych kyselin, Sb. Vys. Sk. Chem. -Technol. Praze, C: Org. Chem.
Technol., C30, 125-141 (1988).
4. P. E. Peterson and C. Casey, Solvents of low nucleophility. V. Platinum-
catalyzed hydrogenation of ketones, tertiary alcohols and esters, and tosy-

lates in acidic solvents including trifluoroacetic acid, J . Org. Chem., 29,
2325-2329 (1964).
M. Zdrazil, A kinetics of hydrogenolysis of aliphatic esters on rhodium,
Collect. Czech. Chem. Commun., 39, 1488-1493 (1974).
M. Zdrazil, Structure-reactivity dependence in hydrogenolysis of esters on
rhodium, Collect, Czech. Chem. Commun., 39, 3515-3521 (1974).
A. P. G. Kieboom, J. F. de Kreuk, and A. van Bekkum, Substituent effects
in the hydrogenolysis of benzyl alcohol derivatives over palladium, J . Catal. ,
20, 58-66 (1971).
8. J . D. Chanley and T. Mezzetti, The hydrogenation of dihydrolanosteryn and
dihydroagnosteryl acetates, J . Org. Chem., 29, 228-229 (1964).
9. P. N. Rylander, Hydrogenation methods, Academic Press, London, 1985,
p. 80.
10. J. P. Candy, 0. A. Ferretti, G. Mabilon, J . P. Bournonville, A. El Mansour,
J. M. Basset, and G. Martino, Surface organometallic chemistry on metals.
XI. Characterization of new bimetallic catalysts generated by reaction of Sn(n-
C,H,), with silica-supported rhodium, J . Catal., 112, 210-220 (1988).
11. J . A. Christiansen, Methyl alcohol from alkyl formates, US Patent 1,302,011
(April 29, 1919).
12. H. Adkins, M. E. Kinsey, and K. Folkers, Condensation reactions of acet-
aldehyde over certain oxide catalysts at pressures from 1 to 500 atmospheres
of hydrogen, Ind. Eng. Chem., 22, 1046-1048 (1930).
13. A. E. Bailey, Industrial oil and fat products, Interscience, New York, 1951,
p. 762.
14. 3. D. Stroupe, An X-ray diffraction study of the copper chromites and of
the “copper chromium oxide” catalyst, 1. A m . Chem. Soc., 71, 569-572
(1949).
15. L, Kurc and L. Cerveny, Activity of copper-chromite catalysts for hydro-
genolysis of the C - 0 bond in esters, Sb. Vys. Sk. Chem. -Technol. Praze,
C: Org. Chem. Technol., C30, 5-18 (1988).
16. J. W. Evans, N. W. Cant, D. L. Trimm, and M. S. Wainwright, Hydro-
genolysis of ethyl formate over copper-based catalysts, Appl. Catal., 6 , 355-
362 (1983).
17. D. L. Trimm and M. S. Wainwright, Steam reforming and methanol syn-

thesis, Catul. Today, 6, 261-278 (1990).
18. M. Roeper, Oxygenated base chemicals from synthesis gas. Methyl formate
as a versatile intermediate, Erdoel, Kohle, Erdgas, Petrochem., 37, 506-51 1
(1984).
19. J. S. Lee, J . C. Kim, and Y . G. Kim, Methyl formate as a new building
block in C, chemistry, Appl. Catal., 57, 1-30 (1990).
20. N. S. Imyanitov, B. E. Kuvaev, and D . M. Rudkovskii, Synthesis of meth-
anol at low pressures, Gidroformilirovanie, 1972, pp. 152-161 ( C A , 77,
163952r).
21. J. W. Evans, S. P. Tonner, M. S. Wainwright, and D. L. Trimm, Evaluation
of a two-stage route to methanol, 11th Aust. Conf. on Chem. Eng., Chem.
Eng. Today, 1983, pp. 509-516.
22. H. Brendlein, Methanol, Ger. Patent 809,803 (August 2, 1951).

23. H. Brendlein, Methanol, Ger. Patent 902,375 (January 21, 1954).
24. Petrole Informationy, May 13, 1982, p. 34.
25. P. A. Stirurn and 0. T. Onsager, Hydrogenolysis of methyl formate to
methanol, Proc. Int. Congr. Cutal., 8 , 233-244 (1984).
26. 0 .T. Onsager, Methyl formate and methanol in a liquid phase, World Patent
84 00,360 (July 6, 1982).
27. Z. Liu, J. W. Tierney, Y . T . Shah, and I. Wender, Kinetics of two-step
methanol synthesis in the slurry phase, Fuel Proc. Technol., 18, 185-199
(1988).
28 Z . Liu, J . W. Tierney, Y. T. Shah, and 1 . Wender, Methanol synthesis via
I
methyl formate in a slurry reactor, Fuel Proc. Technol., 23, 149-167 (1989).
29. V. M. Palekar, J . W. Tierney, and I. Wender, A novel synthesis of methanol,
Proc. Annu. Int. Pittsburgh Coal Conf., 7 , 622-631 (1990).
30. V. M. Palekar, H . Jung, J . W. Tierney, and I. Wender, Slurry phase synthesis
of methanol with a potassium methoxide/copper chromite catalytic system,
Appl. Catal. A : General, 102, 13-34 (1993).
31. V. M. Palekar, J. W. Tierney, and I. Wender, Alkali compounds and copper
chromite as low-temperature slurry phase methanol catalysts, Appl. Catul.
A: General, 103, 105-122 (1993).
32. C. Travers, R. Snappe, T. D. Chan, and J.-P. Bournonville, Methanol
produced by hydrogenolysis of methyl formate in the presence of a supported
metal catalyst, Fr. Patent 2,543,946 (October 12, 1984).
33. CRC Handbook of Chemistry and Physics, CRC Press, 73rd ed., Boca Raton,
FL, 1992.
34. J. A. Christiansen, The equilibrium between methyl formate and methyl
alcohol, and some related equilibria, J . Chem. Soc., 1926, pp. 413-421.
35. B. S. Lacy, R. G . Dunning, and H. H. Storch, Equilibrium in the synthesis
and decomposition of methanol, J . Am. Chem. Soc., 52, 926-938 (1930).
36. K. M. Kim, H. C . Woo, M. Cheong, J. C . Kim, K. H. Lee, J. S. Lee, and
Y . G. Kim, Chemical equilibria and catalytic reaction of gas-phase methanol
synthesis from methyl formate, Appl. Cutal. A : General, 83, 15-30 (1992).
31. J. W. Evans, P. S. Casey, M. S. Wainwright, D. L. Trimm, and N. W. Cant,
Hydrogenolysis of alkyl formates over a copper chromite catalyst, Appl.
Catal., 7, 31-41 (1983).
38. D. M. Monti, M. S. Wainwright, D. L. Trimm, and N. W. Cant, Kinetics

of vapor-phase hydrogenolysis of methyl formate over copper on silica
catalysts, Ind. Eng. Chem. Prod. Res. Dev., 24, 397-401 (1985).
39. D. M. Monti, M. A. Kohler, M. S. Wainwright, D . L. Trimm, and N . W.
Cant, Liquid phase hydrogenolysis of methyl formate in a semibatch reactor,
Appl. Catal., 22, 123-136 (1986).
40. R. J . Gormley, V. U. S. Rao, Y. Soong, and E. Micheli, Methyl formate
hydrogenolysis for low-temperature methanol synthesis, Appl. Catal. A :
General, 87, 81-101 (1992).
41. D. M. Monti, N. W. Cant, D. L. Trimm, and M. S. Wainwright, Hydro-
genolysis of methyl formate over copper on silica. I. Study of surface species
by in situ infrared spectroscopy, J . Catal., 100, 17-27 (1986).
42. D. M. Monti, N. W. Cant, D. L. Trimm, and M. S. Wainwright, Hydro-
genolysis of methyl formate over copper on silica. 11. Study of the mechanism
using labeled compounds, J . Catal., 100, 28-38 (1986).

43. J. B. Friedrich, M. S. Wainwright, and D. J. Young, Methanol synthesis
over Raney copper-zinc catalysts. I. Activities and surface properties of
fully extracted catalysts, J . Catal., 80, 1-13 (1983).
44. H. Baltz, R. Daute, S. Poredda, H . Raue, R. Schmuck, K. A . Alekseeva,
M. P. Vysotzkii, N. Y . Gordina, L. S. Kusmina, and G. P. Prokopenko,
Catalytic cracking of formic acid esters mixed with alcohols, Ger. (East)
Patent 122,180 (September 20, 1976).
45. J. W. Evans, Studies of copper catalysed hydrogenolysis of alkyl esters, Ph.D.
Thesis, University of New South Wales (1983).
46. Y. R. Naves, Hydrogenolyse des esters benzyliques au contact des cata-
lyseurs au nickel, Helv. Chim. Acta, 27, 261-268 (1944).
47. A. K. Agarwal, N. W. Cant, M. S. Wainwright, a n d D . L. Trimm, Catalytic
hydrogenolysis of esters: A comparative study of the reactions of simple
formates and acetates over copper on silica, 1. Mot. Catal., 43,79-92 (1987).
48. W. A. Lazier, Alcohols from esters of nonaromatic carboxylic acids, US
Patent 2,079,414 (May 4, 1937).
49. 0. Schmidt, Hydrogenation of esters of aliphatic carboxylic acids, US Patent
2,093,159 (September 14, 1937).
50. T. Y. Yan, L. F. Albright, and L. C. Case, Hydrogenolysis of esters, par-
ticularly perfluorinated esters, Ind. Eng. Chem. Prod. Res. Dev., 4 , 101
(1965).
51. K. Kato, K. Namikawa, and M. Watanabe, Optimal design of a benzyl
alcohol process, Bull. Jpn. Petrol. Inst., 14, 206-216 (1972).
52. R. A. Grey and G . P. Pez, Process for homogeneous hydrogenation of esters,
US Patent 4,232,170 (January 31, 1979).
53. R. A. Grey, G. P. Pez, A . Wallo, and J. Corsi, Homogeneous catalytic
hydrogenation of carboxylic acid esters to alcohols, J . Chem. Soc. Chem.
Commun., 1980, pp. 783-784.
54. C. Travers, D. C. Trinh, R . Snappe, and J.-P. Bournonville, Catalytic pro-
duction of alcohols by hydrogenolysis of carboxylic acid esters, Eur. Patent.
Appl. 95,508 (November 30, 1983).
55. C. Travers, Study of ethyl acetate hydrogenation catalyzed by rhodium on
a support, Energy Res. Abstr., 8, Abstr. No. 46974 (1983).
56. C. Travers, J.-P. Bournonville, and G . Martino, Supported rhodium cata-

lysts: Preparation, characterization and catalytic activity for ester hydrogen-
olysis, J . Mol. Catal., 25, 327-336 (1984).
57. C. Travers, J.-P. Bournonville, and G . Martino, New route to rhodium-tin
bimetallic catalysts selective for the hydrogenation of esters into alcohols,
Proc. Int. Congr. Cutul., 8, IV891-IV902 (1984).
58. A. El Mansour, J. P . Candy, J. P. Bournonville, 0. A . Ferretti, and J . M.
Basset, Selective hydrogenation of esters to alcohols with a catalyst prepared
from Rh,O,, Sn(n-C,H,),, and SIO,: Evidence for site isolation, Angew.
Chern. Int. Ed. Engl., 28, 347-349 (1989).
59. M. Agnelli, J. P. Candy, J . M. Basset, J. P. Bournonville, and A. 0. Ferretti,
Surface organometallic chemistry on metals. 111. Formation of bimetallic Ni-
Sn phase generated by reaction of a Sn(n-C,H,), and silica-supported nickel
oxide, J . Catal., 121, 236-247 (1990).
60. R. Snappe and J. P. Bournonville, Alcohol production by catalytic hydro-

genation of organic acid esters, Ger. Patent 3,217,429 (December 9, 1982).
61. J. W. Evans, M. S. Wainwright, N . W. Cant, and D. L. Trimm, Structural
and reactivity effects in the copper-catalyzed hydrogenolysis of aliphatic
esters, J . Catul., 88, 203-213 (1984).
62. R. W. Taft, in Steric Effects in Organic Chemistry (M. S. Newman. ed.),
Wiley, New York, 1956.
63. 0. A. Ferretti, J. P. Bournonville, G. Mabillon, G. Martino, J. P. Candy,
and J.-M. Basset, Surface organometallic chemistry on metals. Part 1V.
Selective hydrogenation of ethyl acetate to ethanol on Rh-Sn/SiO, bimetallic
catalysts: A mechanistic study, J . Mol. Cutul., 67, 283-294 (1991).
64. P. Claus, M. Lucas, and B. Lucke. Selective hydrogenolysis of methyl and
ethyl acetate in the gas phase o n copper and supported group VIII metal
catalysts, Appl. Cutal. A: General, 79, 1-18 (1991).
65. C. J . G . van der Grift, A. F. H . Wielers, B. P. J. Joghi, J. van Beijnum,
M. de Boer, M. Versluus-Helder, and J. W. Geus, Effect of reduction
treatment on the structure and reactivity of silica-supported copper particles,
J . Catul., 131, 178- 189 (1991).
66. A . K. Agarwal, M. S. Wainwright, D . L. Trimm, and N. W. Cant, Acet-
aldehyde hydrogenation over a copperisilica catalyst, J . Mol. Catal., 45,247-
254 (1988).
61 M. A. Kohler, N. W. Cant, M. S. Wainwright, and D. L. Trimm, The
mechanism of the catalytic chemistry of ester hydrogenolysis on copper sur-
faces, Proc. Int. Congr. Cutal., 9 , 1044-1050 (1988).
68. J . C. Kenvin and M. G. White, Supported catalysts from mononuclear copper
complexes: Catalytic properties, J . Catul., 135, 81-9 1 (1992).
69. B. W. Kiff and D. J . Schreck, Ethanol from acetic acid, US Patent 4,421.939
(December 20, 1983).
70. M. W. Bradley, N . Harris, and K. Turner, Ethanol production, World Patent
83 03,409 (October 13, 1983).
71. J. W. Kippax and C. Rathmell, Ethanol, Br. Patent 2,162,172 (January 29,
1986).
72. C. G . Wan, Ethanol from methanol, carbon monoxide and hydrogen, US
Patent 4,497,967 (February 5 , 1985).
73. B. Juran and R . V. Porcelli, Convert methanol to ethanol, Hydrocarbon

Process, October 1985, pp. 85-87.
74. W. Normann, Uber die katalytische Reduktion der Carboxylgruppe, 2.
Angew. Chem., 44, 714-717 (1931).
75. 0. Schmidt, Catalytic hydrogenation of the carboxyl group in organic com-
pounds, especially those of higher molecular weight, Ber. Dtsch. Chem. Ges.,
64, 2051-2053 (1931).
76. W. Schrauth, 0. Schenck, and K. Stickdorn, Preparation of hydrocarbons
and alcohols by high-pressure reduction of fats, Ber. Dtsch. Chem. Ges.,
64, 1314-1318 (1931).
77. W. Schrauth, Hochdruckhydrierung und Fettchemie, 2. Angew. Chem., 46,
459-461 (1933).
78. H. Adkins and K. Folkers, The catalytic hydrogenation of esters to alcohols,
. I A.m . Chern. Soc., 53, 1095-1097 (1931).
79. W. A. Lazier, Catalytic hydrogenation of glycerides of aliphatic carboxylic

acids, US Patent 2,109,844 (March 1, 1938).
80. G. Calingaert and G . Edgar, Small-plant-scale liquid-phase hydrogenation
under high pressure, Ind. Eng. Chem., 26, 878-880 (1934).
81. K. Noweck and H. Ridder, Fatty alcohols, Ullman’s Encyclopedia of In-
dustrial Chemistry (W. Gerhartz, ed.), 5th ed., Verlag Chemie, Weinheim,
1987, A-10, pp. 277-295.
82. H. Bertsch, H. Reinheckel, and K. Haage, Uber die Reduktion ungesattigter
Fettsauren und deren Ester zu ungesiittigten Fettalkoholen durch selektive
katalytische Hochdruckhydrierung , Fette- Seven -Anstrichm. , 66, 763- 773
(1964).
83. T. Voeste and H. Buchhold, Production of fatty alcohols from fatty acids,
J . Am. Oil Chem. Soc., 61, 350-352 (1984).
84. E. Haidegger, L. Hodossy, and J. Metzing, Eine neue Fabrik zur Fettal-
kohol-Herstellung in Ungarn, Fette-Seven-Anstrichm., 66,540-544 (1964).
85. K. M. K. Mutzall and P. J. van den Berg, Hydrogenation of fatty acid esters
to fatty alcohols, Proc. 4th Eur. Symp. Chem. React. Eng., Pergamon Press,
1968, pp. 277-285.
86. J. W. E . Coenen, Katalytische Prozesse auf dem Gebiet industrieller Fett-
saureprodukte I, Seifen-Oele-Fette- Wachse, 14, 341-347 (1958).
87. J. M. Church and M. A . Abdel-Gelil, Catalytic hydrogenation of methyl
laurate to lauryl alcohol, Ind. Eng. Chem., 49, 813-817 (1957).
88. K. Folkers and H. Adkins, The catalytic hydrogenation of esters to alcohols
11, J . Am. Chem. Soc., 54, 1145-1154 (1932).
89. T. W. Riener, An improved laboratory preparation of copper-chromium
oxide catalyst, J . Am. Chem. Soc., 71, 1130 (1949).
90. B. Miya, F. Hoshino, and I. Iwasa, Studies of the copper chromite catalyst.
111. Increase in the activity of the copper chromite catalyst by the water-
gas reaction, J . Catal., 5 , 401-41 1 (1966).
91. E. Haidegger and L. Hodossy, Technologische Bedingungen zur Herstellung
von Fettalkoholen durch katalytische Hochdruck-Hydrierung, Fette- Seifen-
Anstrichm., 64, 326-329 (1962).
92. H. Bertsch, H . Reinheckel, and E. Konig, Uber die Reduktion ungesattigter
Fettsauren und deren Ester zu ungesiittigten Fettalkoholen durch selektive
katalytische Hochdruckhydrierung-11: Z u i Isomerisierung und Sattigung der
Doppel-bindungen, Teil I, allgemeines und Monoensauren, Fette-Seifen -

Anstrichm., 69, 387-393 (1967).
Fettsauren und deren Ester zu ungesattigten Fettalkoholen durch selektive
katalytische Hochdruckhydrierung 111: Metallische und metall-oxidische
Kupfer-Cadmiurn-Kontakte, Fette- Seifen- Anstrichm. ,71,357-362 (I 969).
Fettsauren und deren Ester zu ungesattigten Fettalkoholen durch selektive
katalytische Hochdruckhydrierung IV: Oxidische kupfer- und cadmiumhal-
tige Kontakte, Fette-Seifen-Anstrichm., 71, 785-791 (1969).
95. B. Miya, B. Hoshino, and M. Matsuda, Increasing activity of copper chro-
mite catalysts, Japanese Patent 74,29,819 (August 7, 1974) ( C A , 82, 116754~).
96. D. S. Thakur, E . Palka, T. J. Sullivan, E. Nebesh, and B. D. Roberts,
Process for preparing catalyst with copper or zinc and with chromium, mo-
lybdenum, tungsten, or vanadium, and product thereof, US Patent 5,134,108

(July 28, 1992).
97. B. Miya, Method of producing copper-iron-aluminium catalysts, Br. Patent
2,026,337 (February 6, 1980).
98. B. Miya, Hydrogenation catalysts made from copper, iron and aluminum,
Ger. Patent 3,008,988 (October 9, 1980).
99. B. Miya and Y. Sawamoto, Mixed copper-iron oxide catalyst for hydrogen-
reduction of fatty acid methyl ester to higher alcohol, Japan. Patent 77,156,192
(December 26, 1977) ( C A , 88, 136145a).
100. B. Miya, Y. Sawamoto, K. Hashiba, and S. Hisamitsu, Copper-iron-alu-
minum catalysts, Ger. Patent 2,800,384 (July 27, 1978).
101. H. Schuett and K. Reinhold, Catalysts and process for fixed-bed hydrogen-
olysis of fatty acid methyl esters, Ger. Patent 3,610,698 (October 1, 1987).
102. F. V. Linchevskii, Z . A. Min’kova, and Y. G. Lysogor, Use of an aluminum-
zinc-chromium catalyst for the hydrogenation of fatty acid methyl esters to
alcohols, Neftepererab. Neftekhim., 1972, pp. 42-44 ( C A , 77, 7656s).
103 R. A . Gorbacheva, S. V. Makarov, and V. 1. Ul’yanenko, Preparation of
unsaturated alcohols from cottonseed oil soapstocks, Maslo-Zhir. Prom-st.,
1978, pp. 18-20 ( C A , 89, 181483r).
104. C . S. Narasimhan, V. M. Deshpande, and K. Ramnarayan, Selective hy-
drogenation of methyl oleate to oleyl alcohol on mixed rutheniurn-tin boride
catalysts, Appl. Catal., 48, L1-L6 (1989).
105. C. S. Narasimhan, V. M. Deshpande, and K. Ramnarayan, Mixed ruth-
enium-tin boride catalysts for selective hydrogenation of fatty acid esters
to fatty alcohols, Ind. Eng. Chem. Res., 28, 1110-1112 (1989).
106. V. M. Deshpande, K. Ramnarayan, and C. S. Narasimhan, Studies on
ruthenium-tin boride catalysts. 11. Hydrogenation of fatty acid esters to
fatty alcohols, J . C a t d . , 121, 174-182 (1990).
107. P. Svoboda, J . Hetfleijs, and J. Soucek, Catalysis by metal complexes. Part
LVlll. Selective hydrogenation of methyl esters of soybean oil on Ziegler-
type nickel catalysts, Chem. Pvum., 30, 89-93 (1980) ( C A , 92, 148891m).
108. K. Fukuzumi, T. Nishiguchi, and T. Tagawa, Studies on homogeneous trans-
fer hydrogenation of unsaturated fatty acid ester. Discovery and discussion
of the reaction system having 100% selectivity and no trans isomers produced,
Asahi Garasu Kogyo Gijutsu Shoreikai Kenkyu Hokoku, 31,351-362 (1977)

( C A , 89, 1461358).
109. A. Mugishima, Higher fatty alcohols by gas-phase hydrogenation of fatty
acid methyl esters at atmospheric pressure, Jpn. Patent 76,08,203 (January
23, 1976) ( C A , 85, 45961k).
110. G. Demmering, Continuous manufacture of fatty alcohols, Ger. Patent
2,613,226 (September 29, 1977).
111. E. K. Poels, D. R. E. Folman, and J. J. Vreeswijk, Process for the prep-
aration of fatty alcohols by hydrogenolysis of fatty ester over a copper-
containing catalyst in the presence of water vapor, Br. Patent 2,250,287
(June 3, 1992).
112. R. Dupont, L. Ferenczi, and G . Simonet, Process and apparatus for the
manufacture of fatty alcohols, Eur. Patent 365,387 (April 25, 1990).
113. T. Fleckenstein, G . Goebel, F. J. Carduck, N. Bremus, and R. Eltner,
Hydrogenolysis of glycerides to fatty alcohols and diols, Ger. Patent 3,809,270

(September 28, 1989).
114. R. G . Wall, Hydrogenation of esters to alcolhols, Belg. Patent 864,567 (July
3, 1978).
115. J. B. Wilkes, Hydrogenation catalysts, Belg. Patent 873,167 (April 17, 1979).
116. Ube Industries, Ethylene glycol, Jpn. Patent 82,123,127 (January 26, 1981)
( C A , 97, 215521j).
117. S. Furusaki, T. Matsuzaki, and Y . Yamazaki, Preparation of copper-silica
catalysts for hydrogenation of carboxylic acid esters, Jpn. Patent 02164449
(June 25, 1990) (CA, 113, 151826b).
118. L. R. Zehner and R. W. Lenton, Process for the preparation of ethylene
glycol, US Patent 4,112,245 (September 5 , 1978).
119. F. Poppelsdorf, Process for the preparation of ethylene glycol, Eur. Pat.
Appl. 60,787 (September 22, 1982).
120. J. W. Kippax, N. Harris, K. Turner, A . B. Carter, and C . Rathmell, Hy-
drogenolysis of carboxylic acid esters, Ger. Patent 3,443,277 (June 5 , 1985).
121. H. Miyazaki, K. Hirai, T. Uda, Y. Nakamura, H. Ikezawa, and T. Tsuchie,
Process for producting lower alkylene glycol, catalyst composition used therefor
and process for production thereof, US Patent 4,511,744 (April 16, 1985).
122. K. Hirai, T. Uda, and Y. Nakamure, Catalyst composition for producing
ethylene glycol and process for producing the catalyst composition, US Pat-
ent 4,614,728 (September 30, 1986).
123. W. J. Bartley, Process for the preparation of ethylene glycol, US Patent
4,628,129 (December 9, 1986).
124. W. J . Bartley, Process for the preparation of ethylene glycol, US Patent
4,677,234 (June 30, 1987).
125. D. J. Thomas, Studies of the hydrogenolysis of dimethyl succinate and diethyl
oxalate over copper-based catalysts, Ph.D. Thesis, University of New South
Wales (1990).
126. D. J . Thomas, J. T. Wehrli, M. S. Wainwright, D. L. Trimm, and N. W.
Cant, Hydrogenolysis of diethyl oxalate over copper-based catalysts, Appl.
Cutal. A: General, 86, 101-114 (1992).
127. Chemical Week, March 15, 1969, p. 63.
682 TUREK,TRIMM, AND CANT
128. J. Kanetaka, T. Asano, and S. Masamune, New process for production of

tetrahydrofuran, Ind. Eng. Chem., 62, 24-32 (1970).
129. S. Masamune, Industrialization of tetrahydrofuran production, Kagaku Ko-
gaku, 36, 1275-1279 (1972) ( C A , 78, 6 0 1 8 9 ~ ) .
130. B. Miya, F. Hoshino, and T. Ono, Synthesis of tetrahydrofuran from maleic
anhydride in the vapor phase with a bifunctional catalyst, Prepr. Div. Pet.
Chem. Am. Chem. SOC.,18, 187-192 (1973).
131. S. M. Loktev, V. D . Dyshlis, and A. Y. Rozovskii, Mechanism of the
catalytic hydrogenation of maleic anhydride on promoted nickel- kieselguhr
catalysts, Kinet. Katal., 20, 567-571 (1979).
132. S. M. Loktev, V. D. Dyshlis, and A. Y. Rozovskii, Mechanism of the
catalytic hydrogenation of y-butyrolactone and maleic anhydride on nickel
and cobalt catalysts, Kinet. Kafal., 20, 572-575 (1979).
133. R. Fischer, H. J . Gosch, W. Harder, and K. D. Malsch, Process and catalysts
for manufacture of 1 ,Cbutanediol from maleic or succinic anhydrides or

maleate or succinate alkyl esters, Ger. Patent 3,726,509 (February 16, 1989).
134. J. R. Budge and T. G . Attig, Vapor-phase hydrogenation of maleic anhy-
dride to tetrahydrofuran and gamma-butyrolactone, US Patent 4,965,378
(October 23, 1990).
135. J. R. Budge, Process and catalysts for the hydrogenation of maleic anhydride
or succinic anhydride to tetrahydrofuran and gamma-butyrolactone, Eur.
Pat. Appl. 404,408 (December 23, 1990).
136. M. A. Mabry, W. W. Pritchard, and S. B. Ziemecki, Process for making
tetrahydrofuran and 1,4-butanediol using PdiRe hydrogenation catalyst, US
Patent 4,550,185 (October 29, 1985).
137. M. A. Mabry, W. W. Pritchard, and S. B. Ziemecki, PdlRe hydrogenation
catalyst for making tetrahydrofuran and 1,4-butanediol, US Patent 4,609,636
(September 2, 1986).
138. G. L. Castiglioni, C. Fumagalli, R. Lancia, M. Messori, and A . Vaccari,
Improved copper chromite catalyst for the hydrogenation of maleic anhy-
dride to y-butyrolactone, Chem. Ind., July 5 , 1993, pp. 510-511.
139. A. Murata and H. Kobayashi, 1,4-butanediol from y-butyrolactone, Ger.
Patent 2,043,349 (March 9, 1972).
140. M. Yamaguchi and Y. Kageyama, Tetramethylene glycol by catalytic hy-
drogenation of y-butyrolactone, Ger. Patent 2,144,316 (March 16, 1972).
141. M. W. Bradley, N. Harris, and K. Turner, Hydrogenolysis of carboxylic
acid esters, Belg. Patent 892,958 (August 16, 1982).
142. J. N. Cawse, N. E. Johnson, and M. T. Whitaker, Hydrogenation of lactones
to glycols, US Patent 4,652,685 (March 24, 1987).
143. H. J . Weyer, R . Fischer, F. J . Mueller, and H. Zimmermann, Process and
catalysts for manufacture of polyhydric alcohols from lactones, Ger. Patent
3,903,363 (August 23, 1990).
144. N. E. Johnson, R . T. Miskinis, and R . A. Shafer, Process for the production
of butanediol, US Patent 5,030,773 (July 9, 1991).
145. I. B. Blanshtein, Y. L. Moskovich, D . V. Mushenku, B. G . Freidin, V. V.
Semenova, and Y. V. Blandin, a,o-Diols, USSR Patent 400,567 (October
1, 1973) ( C A , 80, 47449~).
146. A . N . Bashkirov, L. A. Morozov, and A. 1. Prudnikov, Hydrogenation of
methyl esters of dicarboxylic and hydrocarboxylic acids (glycol synthesis),

Neftekhimiya, 16, 230-234 (1975) ( C A , 85, 77548~).
147. W. Couteau, M. L. Dungelhoeff, A. Hendrickx, and R. Verbeest, Catalytic
process for the production of butane-l,4-diol from butenedioic acid, Ger.
Patent 2,553,959 (June 10, 1976).
148. J. A. Kouba and A. Zletz, Hydrogenation using copper aluminium borate
catalysts, US Patent 4,613,707 (September 23, 1986).
149. G. hick, P. N. Mercer, and K. E. Simmons, Catalyst composition and their
use in the hydrogenation of carboxylic acid esters, US Patent 4,929,777 (May
29, 1990).
150. M. Sharif and K. Turner, Butane-1,4-diol preparation, Eur. Patent Appl.
143,634 (June 5 , 1985).
151. M. Sharif and K. Turner, Process for the production of butane-l,bdiol, US
Patent 4,584,419 (April 22, 1986).
152. J. Scarlett and M. A. Wood, Manufacture of a mixture of THF, 1 , 4 4 1 ~ -

tanediol, and y-butyrolactone by oxidation and esterification of a C, and C,
hydrocarbon feedstock, Br. Patent 2,207,419 (February 15, 1989).
153. M. W. Tuck, Conversion of butane to petrochemicals: Maleic anhydride and
butanediol, EUROGAS 90, Proc. Eur. Appl. Res. Conf. Nut. Gas, 1990,
pp. 165-178.
154. N. Harris and M. W. Tuck, Butanediol via maleic anhydride, Hydrocarbon
Process, May 1990, pp. 79-82.
155. D. J. Thomas, M. R. Stammbach, N. W. Cant, M. S. Wainwright, and D.
L. Trimm, Hydrogenolysis of dimethyl succinate over Raney copper cata-
lysts: A correction, Ind. Eng. Chem. Res., 29, 204-208 (1990).
156. D. J. Thomas, D. L. Trimm, M. S. Wainwright, andN. W. Cant, Modelling
of the kinetics of the hydrogenolysis of dimethyl succinate over Raney cop-
per, Chem. Eng. Process., 31, 241-245 (1992).
157. W. Reppe, Athinilierung, Liebigs Ann. Chem., 596, 1-224 (1955).
158. M. Bartok, A. Molnar, and F. Notheisz, Chemical transformation of diols
and cyclic ethers. XXXV. Dehydration of diols on copper catalysts, Act0
Phys. Chem., 18, 207-211 (1972).
159. Q . Zhang and Z. Wu, Kinetics of the gas phase hydrogenation of diethyl
succinate, Cuihua Xuebao, 12, 346-352 (1991).
160. T. Turek, D. L. Trimm, D. StC. Black, and N. W. Cant, Hydrogenolysis
of dimethyl succinate on copper-based catalysts, Appl. Catal. A . Gen., in
press.
161 K. Weissermel and H. J . Arpe, Industrial Organic Chemisry , Verlag Chemie
New York, 1978, pp. 350-351.

Acetato de Etilo GPS

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Acetato de Etilo GPS

Загружено:

Авторское право:

Доступные форматы

This article was downloaded by: [Stanford University Libraries]

On: 14 June 2012, At: 18:42

Catalysis Reviews: Science and

The Catalytic Hydrogenolysis of Esters to

Available online: 23 Sep 2006

To link to this article: http://dx.doi.org/10.1080/01614949408013931

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions

T. TUREK and D. L. TRIMM*

School of Chemical Engineering and Industrial Chemistry

"To whom correspondence should be sent.

Copyright 0 1994 by Marcel Dekker, Inc.

V. PRODUCTION OF DIOLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666

Key Words: Alcohols; Copper catalysts; Esters; Hydrogenolysis.

The hydrogenolysis of esters to alcohols is a reaction between esters

11. HYDROGENOLYSIS OF FORMATES

The hydrogenolysis of methyl formate is of particular interest as it has

While the common industrial manufacture of methanol via CO hydroge-

CH,OCHO + 2H2 .+ 2 CH,OH (4)

was found to be:

2. Kinetics of the Gas-Phase Reaction

r, = k,, exp { s}fi i= I

H y drogenol ysis 3.6.10" 117 0.39 -0.17

FIG. 1. Arrhenius plot of rate constants for the hydrogenolysis of methyl

3. Kinetics of the Liquid-Phase Reaction

with an activation energy of EA = 62 kJ/mol. The effect of carbon monoxide

and methanol (12). The aldehyde is then instantly hydrogenated to methanol

et al. 1401 reported that inhibition by CO decreases with increasing tem-

Christiansen I l l ] also proposed a more general preparation method

were determined experimentally and found to be constant in the temper-

activation energy determined in the temperature range 403 to 443 K .

FIG. 2. Methanol selectivity as a function of formate conversion (condi-

111. HYDROGENOLYSIS OF MONOESTERS

This section deals with the hydrogenolysis of monoesters other than

Yan et al. [50]studied, besides a series of fluorinated esters, the liquid-

Grey et al. [52, 531 developed an anionic ruthenium hydride complex

210" to 280°C. The hydrogenolysis of ethyl acetate (19) was complicated by

with an apparent activation energy E, of 88 kJ/mol.

obtained at a molar ester to hydrogen ratio of 20 during hydrogenolysis at

terification to yield ethyl acetate (24), and finally, hydrogenolysis of ethyl

Table 5 summarizes the calculated rate constants k, at the actual tem-

503 6.2 174.2 14.4 2.34

E A , kJ/mol 125.6 56.2 118.5

FIG. 3 . Comparison between experimental (points) and calculated (curves)

A mechanism for acetate hydrogenolysis was proposed by Yan et al.

The obtained ester could then be hydrogenated over a Cu/ZnO catalyst to

The latter was then dehydrated back to the alkene.

IV. HYDROGENOLYSIS OF FATTY ACID ESTERS

The high-pressure hydrogenolysis of fatty acid esters is a widely used

are mainly used as intermediates for the production of synthetic detergents

tween 20 and 30 MPa. Unsaturated alcohols can be obtained using mild

K = 9.65.10-x.exp {s} for coconut oil

K = 16.8.10--8-exp for tallow oil

Equilibrium constants for the hydrogenolysis of pure C, to Clxfatty

rated fatty acid esters. The formation of hydrocarbons according to (34) is

B. Kinetic Studies and Reuction Mechanism

Church and Abdul-Gelil [87] conducted a series of experiments at

klO/h-I atmP2 = lo3. exp {%}

Coenen [86] used data reported by Haidegger and Hodossy [91] to

currence of hemiacetals in the case of the hydrogenolysis of fluorinated

Further research effort has been directed at both the development of

A reduction of the hydrogen excess during the gas-phase hydrogen-

Early work by Adkins and co-workers, reviewed in Ref. 1, showed

However, higher ethylene glycol yields under mild reaction conditions