US006403839B1

(12) United States Patent (10) Patent N0.: US 6,403,839 B1

Gracey (45) Date of Patent: Jun. 11,2002

(54) PROCESS FOR MAKING BUTYRALDEHYDE (56) References Cited

FROM BUTADIENE
U.S. PATENT DOCUMENTS
(75) Inventor: Benjamin Patrick Gracey, Hull (GB) 3,391,192 A 7/1968 Zuech et al.
5,705,707 A * 1/1998 Kanand et al. ........... .. 568/487
(73) Assignee: BP Chemicals Limited, London (GB) 5,892,125 A * 4/1999 Kanand et al. ........... .. 568/449

(*) Notice: Subject to any disclaimer, the term of this

FOREIGN PATENT DOCUMENTS
patent is extended or adjusted under 35
USC 154(b) by 0 days. WO 95/19334 7/1995
WO 96/07630 3/1996
(21) Appl. No.: 09/878,313 WO 98/41494 9/1998

(22) Filed: Jun. 12, 2001 * cited by examiner

Related US. Application Data
Primary Examiner—Sreeni Padmanabhan
(63) Continuation of application No. PCT/GB99/O4171, ?led on (74) Attorney, Agent, or Firm—NiXon & Vanderhye
Dec. 10, 1999.
(57) ABSTRACT
(30) Foreign Application Priority Data
Process for making butyraldehyde from an n-butenyl ester of
Dec. 22, 1998 (GB) ........................................... .. 9828338
a carboXylic acid, Wherein the n-butenyl ester is hydrolyzed
(51) Int. Cl.7 .............................................. .. C07C 47/02 to form the corresponding n-butenyl alcohol n-butenyl alco
(52) US. Cl. .............. .. . 568/484; 568/449; 568/450 hol so produced is isomeriZed to form butyraldehyde.
(58) Field of Search ..................... .. 568/449, 450,
568/484 17 Claims, No Drawings
 US 6,403,839 B1
1 2
PROCESS FOR MAKING BUTYRALDEHYDE The selectivity of the above processes has been found to
FROM BUTADIENE be limited by the formation of by-products. Such
by-products include C8 and higher species formed, for
This is a continuation of PCT/GB99/04171 ?led Dec. example, by dimerisation and oligomerisation reactions of
C4 species. In the process of DEA-4431528 , by-products
10,1999. may also be produced by amine catalysed aldol condensa
The present invention relates to a process for making tion reactions of butyraldehyde.
butyraldehyde by hydrolysing an n-butenyl ester to form the We have noW found that the selectivity of the butyralde
corresponding n-butenyl alcohol and isomerising the latter hyde production process can be increased by forming
to form butyraldehyde. butyraldehyde from a butenyl ester.
It is knoWn that butyraldehyde can be produced by a 10 Accordingly, the present invention provides a process for
number of routes. For instance, US. Pat. No. 5,705,707 making butyraldehyde from an n-butenyl ester of a carboXy
discloses a method of making n-butyraldehyde and/or lic acid, said process comprising i) hydrolysing the
n-butanol by reacting butadiene With an alcohol in the n-butenyl ester to form the corresponding n-butenyl alcohol
presence of an acidic catalyst. The reaction produces a and ii) isomerising the n-butenyl alcohol produced in step i)
miXture of isomeric adducts, 1-alkoXybutene-2 (a) (also 15 to form butyraldehyde.
knoWn as crotyl ether) and 3-alkoXybutene-1 (b): By “isomerising” is meant performing any process Which
results in the direct or indirect conversion of the n-butenyl
CH3.CH:CH.CH2.OR (a) alcohol to butyraldehyde.
CH2:CHCH(OR).CH3 (b) Steps i) and ii) may be carried out simultaneously or
20 sequentially. Whilst carrying out steps i) and ii) simulta
Compound (b) can be isomerised into compound (a). neously may alloW the process to be operated more
Compound (a) is isomerised in the presence of a homoge economically, the sequential hydrolysis and isomerisation
neous or heterogeneous transition metal catalyst to form the stages may increase the selectivity of the overall process.
enol ether of the formula (c): Step i) may also be carried out before step ii). Thus, in one
25 embodiment of the present invention, n-butenyl ester is ?rst
CH3CH2CH:CHOR (c) hydrolysed to form n-butenyl alcohol, Which is conveniently
separable from the hydrolysis miXture as an aZeotrope. The
Ether (c) reacts With Water to liberate butyraldehyde. This separated n-butenyl alcohol is then isomerised into the
hydrolysis reaction is catalysed by acids and bases. The butyraldehyde product.
butyraldehyde product can be hydrogenated With suitable
30 Preferably, the n-butenyl ester is an n-butenyl ester of a
homogeneous or heterogeneous catalysts to yield n-butanol.
Thus compound (c) in the presence of Water and hydrogen saturated, aliphatic carboXylic acid.
and a homogeneous or heterogeneous catalyst produces In the present process, the n-butenyl ester (also knoWn as
butanol and the parent alcohol ROH. The parent alcohol can “crotyl ester”) may not be readily available commercially.
then be recycled to the addition reaction stage. Instead it may be produced by reacting butadiene With a
A similar isomerisation hydrolysis reaction has been 35 saturated, aliphatic carboXylic acid. As butadiene is a rela
repeated With amines in DEA-4431528. This document tively inexpensive by-product of the re?ning process, it
describes a process for the production of butyraldehyde provides a convenient feedstock for making butyl esters.
Which comprises the addition of an amine to a butadiene. Thus, a preferred embodiment of the present invention
The reaction produces a miXture of isomers, provides a process for the production of butyraldehyde
CH3CH=CHCH2NR2 and CH3CH(NR2)CH=CH2. The 40 Which comprises:
CH3CH(NR2)CH=CH2 isomer is recycled back to the a) the addition reaction of butadiene to a carboXylic acid
addition reaction, Whilst the CH3CH=CHCH2NR2 isomer to produce a mi)cture of sec-butenyl ester and
is converted to the corresponding enamine, n-butenyl ester; and
CH3CH2CH=CHNR2. This enamine is hydrolysed to pro b) hydrolysing the n-butenyl ester formed in step a) to
duce butyraldehyde for possible further processing and also 45 form the corresponding n-butenyl alcohol, and (ii)
liberates the initial amine for re-use. The butyraldehyde may isomerising of the n-butenyl alcohol produced in step
be hydrogenated to the corresponding alcohol, if desired. bi) to form butyraldehyde.
The process of DEA-4431528 is summarised in the diagram Steps and (ii) may be carried out simultaneously or
beloW: sequentially.

—
Isomerisation

Amine recycle
 US 6,403,839 B1
3 4
The diagram below summarises the reactions Which may It has been found that moderately loW levels of Water are
take place in this preferred embodiment of the invention. required: at levels above 5%W/W the catalyst activity is
signi?cantly reduced, Whereas at levels beloW 0.05%W/W,
the activity though high is rapidly lost due to deactivation of
the catalyst. Consequently the Water level in the reaction
Zone is suitably in the range from 0.05 to 5%W/W on the
lCatalyst 1 carboxylic acid, preferably from 0.05 to 1%W/W.
The butadiene feedstock may be employed either as a
\ Recycle to addition reaction puri?ed chemical, or in the form of a hydrocarbon stream
or Crack to butadiene +
V x’ carboxylic acid or hydrolysis 10
comprising butadiene. Such hydrocarbon streams include
re?nery streams such as mixed C4 streams containing
WOZCR V isomerisation to methyl ethyl
OZCR ketone butadiene, as Well as other C4 species such as butane,
H2O 1-butene, 2-butene, isobutane, and isobutene. The addition
reaction (step (a)) can be used to remove butadiene from
Catalyst 2 such hydrocarbon streams, thereby avoiding the need to
15 remove butadiene in a separate processing stage.
- - - - -> Recycle to addition
The butadiene employed may be dissolved in the reaction
reaction stage
mixture, or introduced into the reactor as a gaseous reactant.
Isomerisation In certain embodiments, the reaction is carried out in multi
catalyst 3 phase, With butadiene being present in the liquid reaction
20 mixture, and as a gaseous phase.
W0 The carboxylic acid (RCOZH) feedstock suitably com
prises any saturated carboxylic acid feedstock. Dicarboxylic
acids such as succinic acid may be employed, although
In step a), butadiene is reacted With a carboxylic acid mono-carboxylic acids, and in particular, aliphatic mono
R‘CO2H in the presence of an addition catalyst, catalyst 1. carboxylic acids are generally preferred. Suitable mono
Catalyst 1 may be a homogeneous or heterogeneous catalyst. carboxylic acids comprise 1—6 carbon atoms. Preferably, the
Heterogeneous catalysts may be advantageous in certain acid is acetic acid.
situations as they facilitate separation of, for example, The relative mole ratios of butadiene to the carboxylic
reaction products from the reaction mixture. They may also acid reactant in the addition reaction is suitably in the range
alloW the catalyst to be conveniently separated from reaction from 5:1 to 1:50, preferably in the range from 1:1 to 1:10.
by-products (Which typically comprise high boiling point This addition reaction is suitably carried out at a tem
butadiene oligomeric species). The preferred catalysts are
based on strong acid ion-exchange resins, such as Amberlyst perature in the range from 20 to 150° C., preferably from 40
15® and Amberlite IR120®. Other suitable examples of to 90° C. The reaction is suitably carried out at the autoge
heterogeneous catalysts include ?uorinated ion-exchange neous reaction pressure Which is determined by factors such
resins such as Na?on®, phosphoric acid functionalised 35 as the reaction temperature, presence of absence of solvent,
polymers, and acidic oxides, for example, HY Zeolites. excess of reactants and impurities present in the butadiene
A proportion of the acidic sites of such ion-exchange stream. An additional pressure may be applied to the system
catalysts may be exchanged With bulky counterions, such as if the reaction is carried out in a single phase, for example,
alkyl pyridinium, quaternary alkyl ammonium, quaternary if substantially all the butadiene present is present in the
arsonium and quaternary phosphonium. These counterions 40 liquid phase in the reaction mixture.
exchange With some of the acid sites on the support and can It may also be advantageous to use polymerisation inhibi
be added to the catalysts as salts, such as halides, sulphates tors such as eg alkylated phenols such as 2,6-di-tert-butyl
or carboxylates. p-cresol (also knoWn as “BHT” or butylated
The heterogeneous catalyst phase may be a partially or hydroxytoluene). Other related compounds include the Irga
fully insoluble liquid phase. Such catalysts may take the nox® series of materials (ex Ciba Gigy), the LoWinox®
form of acidic ionic liquids, liquid acidic polymers and series of materials (ex Great Lakes Chemical Corporation);
partially solvated polymers. The catalyst may also be a solid the Tropanol® series (ex ICI), t-butylcatechol, nitroxides
phase, for example, I) an HY Zeolite, II) a strong acid such as di-tert-butylnitroxide, N,N-dimethyl-4
macroreticular, macronet or gel ion-exchange resin, or III) a
heteropolyacid of tungsten or molybdenum, Which has been nitrosoaniline, nitric oxide, and stable radicals, such as
ion-exchanged and/or supported on a carrier material. 2,2,6,6-tetramethyl-piperidine-1-oxyl, 2,2,6,6-tetramethyl
In certain circumstances, the activity of heterogeneous 4-hydroxypiperidine-1-oxyl and 2,2,6,6
catalysts may decrease considerably after prolonged periods tetramethylpyrrolidine-1-oxyl.
of use. In such cases, it may be advantageous to carry out the The reaction betWeen butadiene and the carboxylic acid
process of the present invention in a homogeneous phase. produces a mixture of butenyl esters: n-butenyl ester and
Suitable homogeneous catalysts include sulphonic acids, 55 sec-butenyl ester. The n-butenyl ester is converted into the
heteropolyacids, tri?ic acid (i.e. tri?uoromethane sulphonic butyraldehyde end-product by hydrolysis isomerisation
acid) and tri?ate salts. Suitable heteropolyacids include (step The sec-butenyl ester, on the other hand, may be
Keggin structure heteropolyacids based on tungsten, and removed, for example, for use, sale or further reaction. An
strong acid ionic liquids such as those described in prior example of such a further reaction is the conversion of
published EP-A-693088, WO-A-95/21872 and EP-A 60 sec-butenyl ester into methyl ethyl ketone and carboxylic
558187. Suitable organic sulphonic acids include methane acid. Such a conversion step may be carried out by subject
sulphonic acid, p-toluenesulphonic acid and sulphonated ing the ester to simultaneous or sequential stages of hydroly
calixarenes. Examples of tri?ate salts include lanthanide sis and isomerisation. As With the n-butenyl isomer, simul
tri?ates, such as lanthanum tri?uoromethanesulphonic acid taneous hydrolysis and isomerisation may alloW the process
salts. 65 to be operated more economically. HoWever, sequential
The presence of Water as a reaction adjuvant can also hydrolysis and isomerisation stages may increase the selec
bene?cially affect the activity and selectivity of the catalysts. tivity of the overall process.
 US 6,403,839 B1
5 6
Where the hydrolysis and isomerisation steps are carried molybdenum, tungsten, manganese, rhenium, iron, cobalt,
out sequentially, it is preferable for the sec-butenyl ester to nickel, ruthenium, rhodium, palladium, platinum, osmium
be hydrolysed before it is isomerised. This is because the and/or iridium. Preferably, a transition metal catalyst sup
conversion of the allylic ester to its vinyl isomer has been ported on an acidic residue is employed. Examples of
found to be thermodynamically unfavourable. Thus, in one suitable acidic residues include strongly acidic ion-exchange
embodiment of the present invention, sec-butenyl ester is resins and sulphonic acids such as para-toluene sulphonic
?rst hydrolysed to form but-l-en-3-ol, Which is conveniently acid. Mineral acids such as sulphuric acid and halogen acids;
separable from the hydrolysis mixture as an aZeotrope. The acidic oxides such as HY Zeolite; LeWis acids such as
separated alcohol is then isomerised into the ketone product. lanthanide tri?ates; and organic acids such as tri?ic acid may
Instead of (or in addition to) converting the sec-butenyl 10 also be suitable. One advantage of carrying out the hydroly
ester into methyl ethyl ketone, the sec-butenyl ester may also sis and isomerisation steps simultaneously is that it mini
be recycled back to the addition reaction (step (a)). Under mises the total number of process stages required for the
the reaction conditions, sec-butenyl interconverts With production of the ?nal product. The butyraldehyde produced
butadiene, free carboxylic acid and the n-butenyl ester. may be recovered from the reaction mixture by distillation,
Rather than recycling the sec-butenyl ester to the addition 15 preferably, Whilst the hydrolysis/isomerisation reaction is in
reaction directly, hoWever, it is also possible to convert the process.
sec-butenyl ester back into butadiene and carboxylic acid The simultaneous hydrolysis and isomerisation step may
separately. The conversion of the sec-butenyl ester to free be carried out in the liquid phase, optionally, in the presence
carboxylic acid and butadiene can be achieved by treatment of a solvent such as an aromatic hydrocarbon solvent.
in the vapour phase With an acidic support. Suitable supports 20 Suitable solvents include toluene and ethers, such as methyl
include silica-aluminas. The butadiene and carboxylic acid tertiary butyl ether and tetrahydrofuran. The reaction may be
produced may then be returned to the addition reactor. This carried out at a temperature of from 25 to 250° C.,
may have a bene?cial effect on productivity and selectivity. preferably, from 50 to 150° C. and more preferably, from 80
Alternatively, at least one of the butadiene and carboxylic to 120° C.
acid may be sold, or used for further reaction. 25
When the hydrolysis and isomerisation steps are carried
The addition reaction may be carried out in a plug ?oW
out sequentially, the hydrolysis step may be carried out in
the presence of an acid or a base, such as a Bronsted acid or
reactor, With the unused butadiene being ?ashed off and base (catalyst 2). Suitable isomerisation catalysts (catalyst 3)
recycled to the reactor via a vapour liquid separator. Some include transition metal complexes. Preferred transition
of the butadiene may be present as a separate gas phase, metal complexes are those containing elements from Group
Whilst the remainder of the butadiene is dissolved in the 30
Ib, Vb, VIb, VIIb and VIIIb of the Periodic Table of
reaction mixture. This results in either a trickle bed or bubble Elements on pages 448 and 449 of the Handbook of Physics
bed operation. A typical LHSV (liquid hourly space & Chemistry (44”1 Edition) published by the Chemical
velocity=volume of liquid feed /catalyst bed volume) for the Rubber Publishing Company, Ohio USA (Reprint, April
carboxylic acid is 0.5 to 20 more preferably 1 to 5. 1962), particularly copper, vanadium, chromium,
The addition reactor may alternatively be carried out in a 35 molybdenum, tungsten, manganese, rhenium, iron, cobalt,
slurry reactor. In such a reactor, the deactivated catalyst may nickel, ruthenium, rhodium, palladium, platinum, osmium
be continuously removed from the reactor as a bleed stream. and/or iridium.
It is economically advantageous to run With catalyst in The n-butenyl ester, upon hydrolysis, Will produce an
various stages of deactivation to improve the utilisation of equilibrium mixture of n-butenyl (i.e. crotyl) alcohol and the
catalyst. In this case, the total loading of catalyst (activated+ 40 carboxylic acid. In order to force the equilibrium in the
deactivated) can reach high levels such as 50%W/W of the desired direction it may be necessary to remove the car
reaction charge. boxylic acid, or alcohol from the equilibrium mixture. This
The butadiene may be added gradually to the carboxylic may be achieved by removing the alcohol as an aZeotrope.
acid, for example, by multiple injection at constant pressure. The hydrolysis step may be carried out in the liquid phase,
optionally, in the presence of a solvent such as an aromatic
This may be carried out in a batch reactor. By adding the 45
hydrocarbon solvent. Suitable solvents include toluene and
butadiene gradually in this manner, side reactions leading to, ethers, such as methyl tertiary butyl ether and tetrahydrofu
for example, the polymerisation of the butadiene may be ran. The reaction may be carried out at a temperature of from
minimiZed. 25 to 250° C., preferably, from 50 to 150° C. and more
The products produced by the addition reaction may be preferably, from 80 to 120° C. The crotyl alcohol formed as
separated from the reactants by distillation. A small amount a result of this hydrolysis step may be recovered by distil
of Water aZeotroping of reaction products may occur due to lation or by phase separation into a suitable solvent. This
the loW levels of Water employed. HoWever, this is minor crotyl alcohol is then isomerised in a separate stage to give
and does not signi?cantly effect the separation of the iso butyraldehyde.
meric butenyl esters, ie the n-butenyl ester and secondary The present invention is further illustrated, by Way of
butenyl ester. 55 example, With reference to the folloWing examples:
The n-butenyl ester produced in the addition step is
EXAMPLES
converted to butyraldehyde in step b). This is achieved by i)
hydrolysis and ii) isomerisation. Where steps i) and ii) are The Preparation of Butyraldehyde from Crotyl
carried out simultaneously, a transition metal catalyst may acetate
be used in the presence of an acid or base to perform the 60
purpose of catalysts 2 and 3 (see diagram). Preferred tran The folloWing chemicals Were used in the preparation:
sition metal complexes are those containing elements from Crotyl acetate: 91 g (100 ml, 0.79 mol)
Group Ib, Vb, VIb, VIIb and VIIIb of the Periodic Table of RuCl3: 1 g (0.005 mol)
Elements on pages 448 and 449 of the Handbook of Physics NaOH: 2.1 g (0.05 mol)
& Chemistry (44”1 Edition) published by the Chemical 65 de-ionised Water
Rubber Publishing Company, Ohio USA (Reprint, April Under a steady How of nitrogen as inert gas, crotyl acetate
1962), particularly copper, vanadium, chromium, (91.0 g, 100 ml, 0.79 mol) and 100 ml of an aqueous solution
 US 6,403,839 B1
7 8
of RuCl3 (1 g, 0.005 mol in 50 ml deinonised Water) Were 8. A process as claimed in claim 7, Wherein the step i) is
mixed in a three-necked round-bottomed ?ask equipped carried out in the presence of an acid or a base, and step ii)
With a 15 plate OldershaW separation column to Which a is carried out in the presence of a transition metal catalyst.
liquid re?ux splitter Was ?tted. A pressure equalising drop 9. A process as claimed in claim 7, Wherein step i) is
ping funnel Was also connected to the reaction ?ask. The carried out in the presence of an acid selected from the group
reaction mixture Was stirred and heated to ca. 90° C. and a consisting of: sulphonic acid, sulphuric acid, halogen acid,
dropping funnel Was used to sloWly add aqueous sodium HY Zeolite, lanthanide tri?ate and tri?ic acid, and step ii) s
hydroxide solution (2.1 g, 0.05 mol in 100 ml de-ionised carried out in the presence of a transition metal catalyst
Water) over a period of 2—3 hours. The temperature at the top containing at least one of copper, vanadium, chromium,
of the separation column Was constantly monitored and the 10 molybdenum, tungsten, manganese, rhenium, iron, cobalt,
?rst distillation fraction of a Water/butyraldehyde Was col nickel, ruthenium, rhodium, palladium, platinum, osmium
lected betWeen 68—72° C. and an additional fraction betWeen and/or iridium.
80—82° C. (Water/crotyl alcohol). The ?rst fraction contained 10. A process as claimed in claim 7, Wherein step i)
the major amount of the butyraldehyde product (as deter carried out in the liquid phase, in the presence of an aromatic
mined by GC analysis) and Was Worked up by separating the 15 hydrocarbon solvent.
Water layer from an organic layer comprising butyraldehyde 11. Aprocess as claimed in claim 1, Wherein the n-butenyl
in a separating funnel. The second fraction mainly contained ester is produced by reacting butadiene and a carboxylic acid
crotyl alcohol. Subsequently, the organic layer containing to produce a mixture of sec-butenyl ester and n-butenyl
the desired butyraldehyde product Was dried over magne ester.
sium sulphate overnight and butyraldehyde Was obtained 20 12. A process as claimed in claim 11, Wherein the buta
With an estimated yield of 80% (46.8 g, 58.5 ml, 0.632 mol). diene is reacted With the carboxylic acid in the presence of
I claim: a heterogeneous catalyst selected from the group consisting
1. Aprocess for making butyraldehyde from an n-butenyl of: Amberlyst 15®, Amberlite IR120®, Na?on®, phospho
ester of a carboxylic acid, said process comprising hydrol ric acid functionalised polymers, supported heteropolyacids
ysing the n-butenyl ester to form the corresponding 25 and HY Zeolites.
n-butenyl alcohol and ii) isomerising the n-butenyl alcohol 13. A process as claimed in claim 11, Wherein butadiene
produced in step i) to form butyraldehyde. is reacted With the carboxylic acid in the presence of a
2. A process as claimed in claim 1, Wherein steps i) and homogeneous catalyst selected from the group consisting of
ii) are carried out simultaneously. sulphonic acids, heteropolyacids, tri?ic acid and tri?ate
3. A process as claimed in claim 1, Wherein said steps i) 30 salts.
and ii) are carried out simultaneously using a transition 14. A process as claimed in claim 11, Wherein the buta
metal catalyst in the presence of an acid or base. diene employed is in the form of a hydrocarbon stream
4. Aprocess as claimed in claim 1, Wherein the transition comprising butadiene.
metal catalyst contains at least one of copper, vanadium, 15. A process as claimed in claim 11, Wherein the car
chromium, molybdenum, tungsten, manganese, rhenium, 35 boxylic acid is an aliphatic mono-carboxylic acid.
iron, cobalt, nickel, ruthenium, rhodium, palladium, 16. A process as claimed in claim 11, Wherein the sec
platinum, osmium and iridium. butenyl ester produced by the reaction betWeen the butadi
5. A process as claimed in claim 1, Wherein said steps i) ene and the carboxylic acid is converted into methyl ethyl
and ii) are carried out simultaneously using a transition ketone by hydrolysing the sec-butenyl ester to form the
metal catalyst in the presence of an acid selected from the 40 corresponding but-1-en-3-ol and ii) isomerising the but-1
group consisting of: sulphonic acid, sulphuric acid, halogen en-3-ol produced to form methyl ethyl ketone.
acid, HY Zeolite, lanthanide tri?ate and tri?ic acid. 17. A process as claimed in claim 11, Wherein the sec
6. A process as claimed in claim 1, Wherein steps i) and butenyl ester is recycled directly back to the butadiene/
ii) are carried out simultaneously in the liquid phase, in the carboxylic acid reaction, or converted back into butadiene
presence of an aromatic hydrocarbon solvent. and carboxylic acid in a separate reaction step.
7. A process as claimed in claim 1, Wherein step i) is
carried out before step ii). * * * * *