United States Patent (10) Patent N0.: US 6,743,952 B2

US006743952B2
(12) United States Patent
(10) Patent N0.:
Kantham et al.
(54)
US 6,743,952 B2
(45) Date of Patent:
*Jun. 1, 2004
SELECTIVE LIQUID PHASE AIR
(52)
US. Cl. ...................... .. 568/431; 568/815; 562/409
OXIDATION OF TOLUENE CATALYSED BY
(58)
Field Of Search ............................... .. 568/431, 435,
COMPOSITE CATALYTIC SYSTEM

(75)
568/815; 562/409
Inventors: Mannepalli Lakshmi Kantham,
Andhra Pradesh (IN); Pentlavalli

Sreekanth, Andhra Pradesh (IN);
Kottapalli Koteshwara Rao, Andhra
(56)
References CIted
U-S- PATENT DOCUMENTS
Pradesh (IN); Thella Prathap Kumar,
6,495,726 B1 * 12/2002 Kantam et a1.
Andhra Pradesh (IN); Bhavnari Purna

0 R210, Andhra Pradesh (IN); Beyapati
FOREIGN PATENT DOCUMENTS
Manoranjan Choudary, Andhra

Pradesh (IN)
(73)
JP
Assignee: Council of Scienti?c and Industrial
2001 097913 A
4/2001
* Cited by examiner
Research, NeW Delhi (IN)

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

Pawnt is extended or adjusted under 35
Primary ExaminerJohann Richter

Assistant Examiner_sikarl A_ witherspoon
(74) Attorney, Agent, or FirmBurns, Doane, SWecker &
U.S.C. 154(b) by 0 days.
Mathis, L_L_p_
This patent is subject to a terminal disClalmer~
(57)
ABSTRACT
The present invention provides an improved process for the
production of benZaldehyde With 4050% selectivity by the

catalytic liquid phase air oxidation of toluene using a
(21) Appl. No.: 10/107,215

.
(22)
(65)
Flled'
composite catalytic system comprising salts of iron, cobalt,
Mar 28 2002
Prior Pubhcation Data
manganese, molybdenum or nickel as recyclable catalyst,

salts of manganese or copper as recyclable co-catalyst and
cobalt bromide, sodium bromide, sodium chloride and Zinc
US 2003/0187304 A1 Oct. 2, 2003
(51)
bromide as promoter
Int. Cl.7 ....................... .. C07C 45/28; C07C 27/00;
C07C 51/16
15 Claims, 1 Drawing Sheet
U.S. Patent
Jun. 1, 2004
US 6,743,952 B2
Fig. 1
Recyle Experiments
Percntage
5
8
6o
No. cycles
+ Conversion
__ Benzaldehyde
__ Benzyl alcohol
._D_ Benzoic acid
Reaction Volume: 200 ml; Toluene: 64.32 w/v% ; Cobalt acetate : 0.01 gmol/L;
Manganese acetate 2 0.0008 grnol/L; Sodium bromide : 0.0036gmo1/L; Time : 1 h;
Temperature : 120C; Pressure : 10 bar; Air ?ow : 2 L/min.
For each recycle, 5% of Cobalt acetate, 5% of Manganese acetate and 100% of

Sodium bromide was added.
US 6,743,952 B2
1
2
Reference may be made to another patent, US. Pat. No.
SELECTIVE LIQUID PHASE AIR

OXIDATION OF TOLUENE CATALYSED BY
COMPOSITE CATALYTIC SYSTEM
3,989,674, Nov. 2, 1976, Wherein a mixture of toluene,

oxygen and a helium diluent in molar ratio 128 is passed
over the Cu Au silica catalyst at atmospheric pressure
and temperatures in the range of 450600 F. With 2001000
volumes of gas/h/volume of catalyst. The selectivity of
FIELD OF THE INVENTION
benZaldehyde is 7580% at conversion levels 1530%.

Reference may be made to another patent, US. Pat. No.
4,137,259, Jan. 30, 1979, Wherein a process for the vapour
The present invention relates to a process for the produc
tion of benZaldehyde With 4050% selectivity by catalytic

liquid phase air oxidation of toluene using a composite
catalytic system.
10
phase catalytic oxidation of toluene to benZaldehyde and

benZoic acid at a temperature ranging from 300500 C. in
The N.F./F.C.C. grade of benZaldehyde is Widely used in
the presence of a silver-iron vanadate on silica With conver
?avors such as almond and cherry and in various fragrances
sion 21%, selectivity to aldehyde 33% is described. Refer
for soap and toiletries. BenZaldehyde is an FDA. sanc
tioned synthetic ?avoring substance generally recogniZed as

safe for food. The technical grade is a versatile chemical
ence may be made to a patent US. Pat. No. 4,390,728, Jun.

15
of toluene in the presence of a catalyst composed of the

oxides of Cu, Fe, Pb, U, Mo, and P, Which can also include
intermediate in the manufacture of pharmaceuticals, dyes,

perfume and ?avoring chemicals. The technical grade of
some other promoter elements. The reaction conditions are
benZoic acid is used as at intermediate in the manufacture of
chemicals, alkyd resins, polyesters, plasticiZers, dyestuffs,

preservatives, and rubber activators and retardants. BenZoic
475550 C., 010 atm. pressure, per pass conversion is

20
25
BenZaldehyde is currently produced by the hydrolysis of

the corresponding side chain halogenated toluene com
is generally not more than 70%, With CO2 as main product.

Further, the loW concentration of toluene in the toluene-air
feed mixture poses problems of recovery. The draWbacks in
the above processes are the use of higher reaction
temperatures, generation of carbon dioxide in large amounts
pound. Reference may be made to a patent US. Pat. No.
4,229,379, Oct. 21, 1980, Wherein benZaldehyde is prepared
3550%, selectivity to benZaldehyde 4070%. Reference

may be made to a publication by Ray et al, Ind. J. Technol.,
21(4), 137, 1983, Where they have reported a process for the
oxidation of toluene to benZaldehyde. But, the conversion
per pass is restricted to ~15% and the yield of benZaldehyde
acid, industrial grade, is used as a chemical intermediate and

as a diverting agent in crude oil recovery applications.
BACKGROUND AND PRIOR ART OF THE
INVENTION
28, 1983, Wherein benZaldehyde is formed by the oxidation
30
by hydrolysis of benZyl chloride at 100200 C. at normal
contributing global Warming. Therefore, these processes do

not appear to be attractive.
or under increased pressures in the presence of an excessive
Reference may be made to US. Pat. No. 5,476,827, Dec.
aqueous hydrochloric acid. Reference may be made to
19, 1995, Wherein aldehydes are prepared by the reduction
another patent, US. Pat. No. 4,450,298, May 22, 1994,
Wherein vapour phase catalytic hydrolysis of benZylchloride

to form benZaldehyde by using activated carbon treated With
of acids, esters in vapour phase in the presence of a

35
oxidation of toluene, a desired raW material to benZoic acid
HZSO4 or impregnated With a metal chloride such as FeCl3

or a metal sulphate such as cupric sulphate. The draWbacks
in the above processes are generation of large excess of
ef?uents and the benZaldehyde produced does not meet food
grade speci?cations.
and reduction of benZoic acid to benZaldehyde With hydro

gen. Eventually, this process becomes uneconomical, When
compared to a process of selective oxidation of toluene to
40
al (J. Chem. Soc. Sect. B, 62, 1967), Fields et al (Adv. Chem.
Ser., No. 76(2), 395) and Kamiya (Adv. Chem. Ser., No.
76(2), 193, 1968), they have reported that liquid phase air
45
achieved. Several patents have been ?led describing inno
oxidation provides high yield of benZaldehyde When oxida

tion is carried out in acetic acid medium With cobalt acetate
as catalyst and sodium bromide as promoter. The draWbacks
are that this process suffers from the disadvantages of
vation in air oxidation of toluene and its derivatives both in
liquid and vapour phase.

One of the prevalent industrial practices for the vapour
phase oxidation of toluene to benZaldehyde involves a
benZaldehyde.
Reference may be made to a publication by Morimoto et
Air oxidation of toluene and its derivatives offers green

technology path provided the desired selectivities are rea
lised for market driven products and minimisation of halo
genated and unWanted by-products causing ef?uents is
bimetallic catalyst. The draWback is tWo-step process of
50
relatively loW yield. Reference may be made to US. Pat. No.

2,959,613, Wherein the liquid phase oxidation of toluene or
Chemicals, 3rd Ed., John Wiley & Sons, Inc., NeW York,
its nucleus substituted materials of toluene such as xylene is

carried out by oxygen under the presence of a catalyser
containing a bromine compound and a heavy metallic com
1965; US. Pat. No. 3,579,589). Reference may be made to
pound (such as cobalt compound or manganese compound)
uranium oxide/molybdenum oxide catalyst at 500600 C.

(W. L. Faith, D. B. Keyes and R. L. Clark, Industrial
a patent, US. Pat. No. 3,946,067, Wherein a process is 55 along With a Zinc compound or an alkaline earth metallic
compound or an alkaline metallic compound. The draW
described for the preparation of aromatic aldehydes such as
backs in this method are that the main product is the
benZaldehyde or substituted benZaldehydes involving the
corresponding aromatic carbonic acid and either there is

absolutely no production of the corresponding aromatic
vapour phase oxidation of aralkyl compounds such as tolu

ene or substituted toluenes, respectively, at temperatures of
less than ~250 C. in the presence of a catalyst composition
60
aldehyde or it is produced in a very small quantity as a
containing phosphoric acid and a catalytically effective
by-product.
amount of palladium metal. The aromatic aldehydes are

produced in a single reaction step. The draWbacks in this
signi?cant amount of carbon dioxide is also formed in this
Reference may be made to Japanese patent No. SHO-53

5132, Wherein in order to increase the selectivity of benZal
dehyde or its nucleus substituted material, a large quantity of
catalyser containing a cobalt compound and bromine com
pound is used. Reference may be made to another Japanese
process.
patent No. SHO-56-108728, Aug. 28, 1981, Wherein the
process are the conversion of toluene has to be kept very loW
<4% to attain high selectivity (>70%) of benZaldehyde and
65
US 6,743,952 B2
4
3
liquid phase air oxidation of toluene is carried out by a
One more object of the present invention is to recycle the
catalyst composing a heavy metallic compound, Zinc and
catalyst containing Co, Mn salts for 10 cycles With almost

consistent activity and selectivity.
bromine compound at 30180 C. and loW pressure. The

transformation percentage of toluene is maintained Within a
speci?c range With the advantage of the execution of the
reaction employing carboxylic acid as solvent in the range
One another object of the present invention is to provide

a process for the production of benZaldehyde (4050%)
using very loW concentration of catalyst thereby rendering
0.52.0 times With respect to toluene or its substituted
the process economical.

Another object of the present invention is to provide a
material. By this method the selectivity of benZaldehyde is

increased While formation of benZyl bromide is reduced to
2 mol %. HoWever, the turn over number is 350 in these air
oxidation reactions. The draWbacks in the above processes
10
are loW turn over numbers render the process uneconomical,
the use of higher catalyst concentration hasten corrosion of

reactors and excessive production of benZyl bromide is
detrimental to the achieve desired quality of the product.
Reference may be made to US. Pat. No. 3,969,405 Wherein
the oxidation of toluene in the presence of cobalt acetate,
acid activator and molecular oxygen oxidant gives high
15
20
acid, 55.6% yield. The draWbacks in the above processes are

there is excessive production of benZyl bromide or its
SUMMARY OF THE INVENTION
nucleus substituted material and therefore such a method 25

cannot be said to be a satisfactory one from the point of vieW
of industrial production.
pean patent EP 1088810, (US. application Ser. No. 09/414,

30
the catalytic liquid phase air oxidation of toluene using a

manganese, molybdenum or nickel as recyclable catalyst,
salts of manganese or copper as recyclable co-catalyst and
cobalt bromide, sodium bromide, sodium chloride and Zinc
bromide as promoter.
bromide. Conversion is <25% With 3540% benZaldehyde

and 5055% benZoic acid selectivities.
DETAILED DESCRIPTION OF THE PRESENT

INVENTION
Reference may be made to a publication K. BahranoWski

35
double hydroxides (LDHs) are used for oxidation of aro

matic hydrocarbons With hydrogen peroxide as an oxidant.
Reference may be made to a publication M. W. de Lange
et.al. (Appl. Catal. A, 220, 2001, 41) Wherein a divergent

approach, deoxygenation of benZoic acid to benZaldehyde is
reported recently using molecular hydrogen. These pro
The present invention provides an improved process for
the production of benZaldehyde With 4050% selectivity by
composite catalytic system comprising salts of iron, cobalt,
Reference may be made to the Applicants earlier Euro
et.al. (Appl. Clay Science, 18, 2001, 1993) Wherein Layered
Afurther object of the present invention is to eliminate the

formation of benZyl bromide Which is detrimental to the
quality of benZaldehyde.
cobalt acetate, sodium bromide and hydrogen peroxide.

Conversion is 90.6%, benZaldehyde 29.0% yield, benZoic
473) Wherein the oxidation of toluene carried out in the

presence of cobalt acetate, manganese acetate and Zinc
Yet another object of the present invention is to provide a

process for preparing benZaldehyde at loWer reaction tem
peratures normally in the range of 60130 C.
Still another object of the present invention is to terminate
the reaction to obtain high selectivity of benZaldehyde.
yield of benZoic acid With selectivity to benZaldehyde 35%.

Reference may be made to US. Pat. No. 5,473,101 Wherein
the oxidation of toluene is carried out in the presence of
process for the production of benZyl alcohol (510%),

another value added product of toluene, along With the
production of benZaldehyde using very loW concentration of
catalyst thereby rendering the process economical.
40
Accordingly, the present invention provides an improved

process for preparing benZaldehyde With 4050% selectivity
and transformation % <25% by catalytic liquid phase oxi
dation of toluene by using a composite catalytic system
along With production of value added products benZyl
cesses are uneconomical due to the use of expensive hydro
alcohol (510%) and benZoic acid Without any trace

amounts of benZyl bromide, said process comprising: cata
gen peroxide and molecular hydrogen.

Obviously different approaches have been employed both
lytic liquid phase air oxidation of toluene With continuous

flow of air employing signi?cantly reduced quantities of
at laboratory and commercial scale to prepare benZaldehyde

and the traditional process has the disadvantage of forming
45
salts of Iron, Cobalt, Manganese, Molybdenum or Nickel as

recyclable catalysts, manganese or copper salts as recyclable
unWanted and corrosive halogenated by-products. Thus,
co-catalysts and cobalt bromide, sodium bromide, sodium
there still exist a need for an improved process for preparing
chloride and Zinc bromide as promoters in presence of a

bromine source and 0.05 to 0.4% by Wt. of a carboxylic acid
at a temperature of 60130 C. and a it pressure of 110 bar
for a period of 0.51.5 hrs.
In an embodiment of the present invention, the conversion
is restricted to 1525%.
benZaldehyde With high selectivity.

OBJECT OF THE PRESENT INVENTION
50
The main object of the present invention is to provide an
improved process for the production of benZaldehyde With
4050% selectivity by the catalytic liquid phase air oxida

tion of toluene using a composite catalytic system, Which
In another embodiment of the present invention, the

55
obviates the draWbacks as detailed above.
Another object of the present invention is to maintain
transformation percentage <25% in the catalytic liquid phase

air oxidation of toluene.
Still another object of the present invention is to use
homogeneous metal salts comprising Co, Fe, Mn, Mo, Cu as

catalysts and cobalt bromide, sodium bromide, Zinc
bromide, sodium chloride as promoters and bromine and
chlorine sources in very loW concentrations.
Yet another object of the present invention is to use

sodium bromide and sodium chloride as promoter at loWer
ratios to achieve higher selectivity.
60
selectivity to benZaldehyde is 4050%.

In still another embodiment of the present invention, the
selectivity to benZyl alcohol is 510%.
In yet another embodiment of the present invention, the
carboxylic acid is selected from acetic acid, propionic acid
and benZoic acids.
In a further embodiment of the present invention, the
carboxylic acid is acetic acid.

In one more embodiment of the present invention, air is
65 used as the oxidant.
In one another embodiment of the present invention, the

temperature is kept in the range from 60130 C.
US 6,743,952 B2
5
In an embodiment of the present invention, the pressure is

kept in the range of 110 bar.
residence time is 0.5 to 1.5 hrs.
Zinc bromide as promoters as Well as bromine source and
loW content of carboxylic acid such as acetic, propionic,

benZoic acids as solvent in the range of 0.05 to 0.4 Wt times
With respect to toluene, at the temperatures of 60130 C.

and pressures in the range of 110 bar for a period of 0.51.5
hrs.
catalyst contains a heavy metallic compound such as cobalt,
In the applicants earlier patent EP 1088810 (US. appli
molybdenum or iron as catalyst.
In yet another embodiment of the present invention, the

concentration of the heavy metallic catalytic salts With
respect to toluene in the reaction system is in the range of
10
cation Ser. No. 09/414,473), the oxidation of toluene Was

carried out in the presence of 0.02, 0.0012, 0.04 gmol/L of
cobalt acetate, manganese acetate and Zinc bromide respec
tively. Conversion is <25% With 3540% benZaldehyde and

5055% benZoic acid selectivities. The novelty of the
present method is using very loW concentration of composite
0.010.027 gmol/L.
co-catalyst contains a heavy metallic compound such as
catalytic system consisting of cobalt acetate (0.01 gmol/L)
manganese or copper and their concentration With respect to 15 as catalyst, manganese acetate (0.0008 gmol/L) as
toluene is in the range of 0.0010.002 g mol/L.
co-catalyst and Zinc bromide (0.0147 gmol/L) or sodium
In one more embodiment of the present invention, the
bromide (0.032 gmol/L) as promoter. When compared With
catalyst and co-catalyst are organic acid salts such as formic
our earlier patent, the reduction of the bromine content by
acid salts, acetic acid salts and propionic acid salts of the
832 times sloWs doWn corrosion of the reactor, a very
heavy metallic compound.

promoter is a bromine compound such as cobalt, sodium or
Zinc bromide.
In an embodiment of the present invention, the concen
tration of the promoter in the reaction system With respect to
the toluene is in the range of 0.0010.215 gmol/L.
admix of CI to Br- ions available from the co-catalyst
enhances the rate of air oxidation of toluene and ensures the
product mix devoid of benZyl bromide.
20
Another novelty of the present method is realisation of the
high productivity benZaldehyde and benZyl alcohol in the air

oxidation of toluene, With high turn over number. The use of
manganese acetate as an initiator improved the conversion
25
thus recorded higher rate of productivity even at a loW
Even With the reduction of Br content by 550 times as

30
In yet another embodiment of the present invention, loW

concentration of catalyst, co-catalyst and promoter sloWs
40
catalyst and co-catalyst are recycled for 10 cycles, Which

shoWs almost consistent activity and selectivity.
45
as a by-product.
50
selectivities. UV-VIS studies identi?ed mononuclear Co and

Mn complexes as active species for selective oxidation of
toluene to benZaldehyde. The process is environmentally
safe since there is no effluent disposal problem as encoun
tered in chlorination of toluene folloWed by oxidation.
process is environmentally safe since there is no ef?uent
disposal problem.
55
BRIEF DESCRIPTION OF THE

ACCOMPANYING DRAWING
FIG. 1 represents the results of the recycle experiments.
An improved process for the production of benZaldehyde
The present invention is further described With reference

to the folloWing examples Which are given by Way of
With 4050% selectivity by catalytic liquid phase air oxi

60
dehyde (4050%), benZyl alcohol (510%) and benZoic acid

in large proportions Without any trace amounts of benZyl
bromide maintaining transformation percentage <25 % in the
catalytic liquid phase air oxidation of toluene With continu
ous How of air employing the signi?cantly reduced quanti
ties of salts of Fe, Co, Mn, Mo, Ni, as recyclable catalysts
and cobalt bromide, sodium bromide, sodium chloride and
described is very important to enable to choose the required

composition of Br_/Cl_ to obtain the desired product in
excess quantities to meet the changing demands. Aprotocol
for recovery and reuse of the composite catalyst is devel
oped. Recycle and aging studies alloWed to evolve the

strategy for commercial production of benZaldehyde in high
process totally eliminates the formation of benZyl bromide
dation of toluene using a composite catalytic system Which

comprises the production of value added products benZal
reduces the process cost. As the market demand for each
product ?uctuates, the dynamic system developed here as
In one more embodiment of the present invention, the turn

over number is in the range of 9001200.

process is economical.
boxylic acids in our reaction designed to release adequate

free Br Which gives insitu free radical Br on interaction
With Mn (III) to the initiation of the reaction is employed to
minimise the loss of expensive bromine in the form of
volatile HBr and to minimiZe the corrosion problem. Use of
the reaction and to afford higher selectivity toWards benZal

dehyde and benZyl alcohol is the ultimate choice, since it
factor affecting economics of the project.
range of applications.
the toluene and selectivity and yields toWards benZaldehyde
mixture of NaBr/NaCl at loWer ratio to accelerate the rate of
doWn corrosion on the reactor Which is a very important
In an embodiment of the present invention, the benZal

dehyde produced is chlorine free and can be used for a Wide
NaBr replaces ZnBr2, it is observed that the conversion of

are not much affected. LoW concentration of solvent, car
identical conversions and selectivities Were obtained With

addition of promoter or bromide on each recycle.
35
of toluene and yields of benZaldehyde and benZoic acid and

concentration of cobalt and high concentration of toluene.
In still another embodiment of the present invention,

recycle reactions conducted With the recovered catalyst near
important factor affecting economics of the project.
illustration and therefore should not be construed to limit the

scope of the present invention in any manner.
EXAMPLE 1
65
Buchi glass autoclave of 500 ml capacity equipped With

a gas connecting tube, stirrer, temperature indicator and
pressure gauge Was deployed. The folloWing materials Were
taken in the reaction vessel: 225 ml toluene, 75 ml of acetic
US 6,743,952 B2
7
acid, and 1.50 g of cobalt acetate, 0.09 g of manganese

acetate.4 Water salt, 2.7 g of Zinc bromide. After ?ushing
With air three times, the solution Was heated slowly up to
110 C. While stirring the reaction mixture. After system
attained a constant temperature of 110 C., it Was pressurised
With air to 10 bar With 2 L/min out ?oW. After 1:15 hrs, the
reaction mixture Was taken out. Gas chromatographic and
titrimetric analysis on the product indicates conversion of
of manganese acetate.4 Water salt, 0.106 g of sodium
14.04% With selectivity of 42.3% benZaldehyde, 4.98%

benZyl alcohol and 52.72% benZoic acid.
bromide, 0.063 g of sodium chloride. After ?ushing With air

three times, the solution Was heated sloWly up to 120 C.
While stirring the reaction mixture. After system attained a
constant temperature of 120 C., it Was pressurised With air
to 10 bar With 2 L/min out ?oW. After 1:00 hr, the reaction
mixture Was taken out. Gas chromatographic and titrimetric
analysis on the product indicates conversion of 14.48% With
selectivity of 36.26% benZaldehyde, 10.25% benZyl alcohol

10
and 53.49% benZoic acid.
EXAMPLE 2
EXAMPLE 6

taken in the reaction vessel: 150 ml of toluene, 50 ml of
acetic acid, and 0.5 g of cobalt acetate 4 Water salt, 0.04 g
of manganese acetate.4 Water salt, 0.66 g of Zinc bromide.
After ?ushing With air three times, the solution Was heated
15
sloWly up to 110 C. While stirring the reaction mixture.

After system attained a constant temperature of 110 C., it
20

acetic acid, and 1.5 g of cobalt acetate.4 Water salt, 5.0 g of
sodium bromide. After ?ushing With air three times, the

solution Was heated sloWly up to 110 C. While stirring the
reaction mixture. After system attained a constant tempera
ture of 110 C., it Was pressurised With air to 10 bar With 2
L/min out ?oW. After 2:00 hrs, the reaction mixture Was
taken out. Gas chromatographic and titrimetric analysis on
Was pressurised With air to 10 bar With 2 L/min out ?oW.

After 1:15 hrs, the reaction mixture Was taken out. Gas
chromatographic and titrimetric analysis on the product

indicates conversion of 15.78% With selectivity of 36.59%
benZaldehyde, 6.04% benZyl alcohol and 57.37% benZoic
acid.

25
the product indicates conversion of 14.79% With selectivity

of 49.41% benZaldehyde, 5.19% benZyl alcohol and 45.40%
benZoic acid.
EXAMPLE 3

acetic acid, and 0.5 g of cobalt acetate.4 Water salt, 0.04 g
EXAMPLE 7
30

pressure gauge Was deployed. The following materials Were
35

While stirring the reaction mixture. After system attained a
to 10 bar With 2 L/min out ?oW. After 1:15 hrs, the reaction
heated sloWly up to 110 C. While stirring the reaction

mixture. After system attained a constant temperature of
110 C., it Was pressurised With air to 10 bar With 2 L/min
out ?oW. After 1:15 hrs, the reaction mixture Was taken out.

EXAMPLE 4

of manganese acetate.4 Water salt, 0.66 g of sodium bro
mide. After ?ushing With air three times, the solution Was
45
Gas chromatographic and titrimetric analysis on the product

indicates conversion of 17.41% With selectivity of 40.60%
acid.

EXAMPLE 8
50
pressure gauge. The folloWing materials Were taken in the
reaction vessel: 150 ml of toluene, 50 ml of acetic acid, and

0.5 g of cobalt acetate.4 Water salt, 0.04 g of manganese
acetate.4 Water salt, 0.075 g of sodium bromide. After

While stirring the reaction mixture. After the system attained
a constant temperature of 110 C., it Was pressurised With air
to 10 bar With 2 L/min out ?oW. After 1:15 hrs, the reaction
55
60
EXAMPLE 5
graphic and titrimetric analysis on the product indicates

conversion of 14.09% With selectivity of 38.80%
acid.

?ushing With air three times, the solution Was heated sloWly
upto 120 C. While stirring the reaction mixture. After
system attained a constant temperature of 120 C., it Was
pressurised With air to 10 bar With 2 L/min out ?oW. After
1:00 hr, the reaction mixture Was taken out. Gas chromato


65
The reaction conditions, the concentration of the various

salts and acids used, the percentage selectivity of the reac
tion to benZaldehyde, benZyl alcohol and benZoic acid in
examples 1 to 8 are summarised in Table 1.
US 6,743,952 B2
10
TABLE 1
Catalytic Liquid Phase Air Oxidation of Toluenea
Ex.
Co.Ac
Mn.Ac
ZnBr2
NaBr
No.
(gmol/L)
(gmol/L)
(gmol/L)
(gmol/L)
1b
2
0.02
0.01
0.0012
0.0008
0.04
0.0147
3
4
5
0.01
0.01
0.01
0.0008
0.0008
0.0008
0.005
0.01
0.005
NaCl
Temp Time Conv
(gmol/L) (O C.) (hr)
(%)
Selectivity %
BAld BAlc BAcid
110
110
1:15
1:15
14.04
15.78
42.3
36.59
4.98
6.04
52.72
57.37
0.027
0.022
0.0054
110
110
120
1:15
1:15
1:00
14.34 42.61
3.83
15.36 37.71
8.38
14.48 36.26 10.25
53.56
53.91
53.49
6b
0.02
0.16
110
2:00
14.79
49.41
5.19
45.40
7
8
0.01
0.01
0.0008
0.0008
0.032
0.0036
110
120
1:15
1:00
17.41
14.09
40.60
38.80
5.16
5.32
54.24
55.88
a) Reaction Volume: 200 ml; Toluene: 64.32 W/v %; Pressure: 10 bar; Air floW: 2 L/min
b) Reaction Volume: 300 ml; Toluene: 64.32 W/v %; Pressure: 10 bar; Air floW: 2 L/min
Note:
BAld denotes benzaldehyde; BAlc denotes benzyl alcohol, and BAcid denotes benzoic acid
20
Catalyst Recycle Experiment
8. An ecofriendly process for the production of benZal

dehyde Without the formation of benZyl bromide Was
The reaction mixture of example 8 containing toluene,

acetic acid, benZaldehyde, benZoic acid, benZyl alcohol and
9. BenZaldehyde produced is free from chlorine and can
EXAMPLE 9
developed.
catalyst mixture Was taken for recycle study. Toluene and

acetic acid Were removed by distillation from the reaction
mixture and toluene Was added to the product mixture
25
residue to make it a homogeneous solution. Water Was then
11. The catalytic system is recyclable With almost con
added to the organic mixture and the catalyst Was extracted

into the aqueous layer, and organic and aqueous layers Were
separated. Organic layer Was subjected to distillation to get

toluene, benZaldehyde, benZyl alcohol and benZoic acid, and
sistent activity and selectivity.

30
the aqueous layer Was concentrated to get the catalyst

35

acetic acid, recovered catalyst composite mixture cake con

taining cobalt acetate, manganese acetate, sodium bromide
and make-up catalyst of 5% cobalt acetate, 5% manganese
acetate and 100% sodium bromide (Fresh amounts of Co
and Mn is charged to account for handling losses and sodium
bromide for consumption). After ?ushing With air three
times, the solution Was heated sloWly up to 120 C. While
stirring the reaction mixture. After the system attained a
to 10 bar With 2 L/min out ?oW. After 1 hour, the reaction
a catalytic liquid phase oxidation of toluene by using a

40
composite catalytic system along With production of value

added products benZyl alcohol and benZoic acid, said pro
cess comprising: conducting a catalytic liquid phase air
oxidation of toluene With a continuous flow of air in the
presence of a salt of Iron, Cobalt, Manganese, Molybdenum

45
or Nickel as a recyclable catalyst, manganese or copper salts
as a recyclable co-catalyst, and cobalt bromide, sodium

bromide, sodium chloride or Zinc bromide as a promoter,
and 0.05 to 0.4% by Wt. of a carboxylic acid at a temperature
of 60130 C. and a pressure of 110 bar for a period of
0.51.5 hrs,
Wherein the concentration of the recyclable catalyst With
respect to toluene is in the range of 0.010.027 gmol/L,
the concentration of the recyclable co-catalyst With

respect to toluene is in the range of 0.0010.002
55
gmol/L,
the concentration of the promoter With respect to the
toluene is in the range of 0.0010.215 gmol/L, and
cess is in the range of 4050%.
3. The selectivity for benZyl alcohol obtained in this
the turn over number is in the range of 9001200.
process is in the range of 510%.

60
is used.
5. The temperatures and pressures employed in the reac
tion are moderate.
6. The residence time in the reactor is short.

7. Acetic acid is used as the solvent and the amount used
is in the range of 0.05 to 0.4 Wt times With respect to
toluene.
14. The process is economical.

What is claimed is:
1. An improved process for preparing benZaldehyde With
and 47.64% benZoic acid. Like this 10 recycles Were con

ducted and the results Were presented in FIG. 1.
The main advantages of the present invention are:
4. LoW concentration of catalyst, co-catalyst and promoter
SlOWS doWn corrosion on the reactor, a very important
a 4050% selectivity and a conversion percentage of 25% by
1. The process is a catalytic liquid phase reaction.

2. The selectivity for benZaldehyde obtained in this pro
12. Employment of the loW concentration catalytic system
factor affecting economics of the project.

13. The present process is environmentally safe since
there is no effluent disposal problem.
composite mixture cake.

be used over a Wide range of applications.

10. High turn over number 9001200 is realised for the
?rst time.
65
2. Aprocess as claimed in claim 1, Wherein the conversion

percentage is 1525%.
3. Aprocess as claimed in claim 1, Wherein the selectivity
to benZyl alcohol is 510%.
4. Aprocess as claimed in claim 1, Wherein the carboxylic
acid is selected from the group consisting of acetic acid,
propionic acid and benZoic acids.
5. Aprocess as claimed in claim 4, Wherein the carboxylic
acid is acetic acid.
US 6,743,952 B2
11
12
6. A process as claimed in claim 1, wherein the catalyst

contains cobalt, molybdenum or iron.
7. A process as claimed in claim 1, Wherein the catalyst
and co-catalyst are organic acid salts.
8. Aprocess as claimed in claim 1, Wherein the promoter
is cobalt, sodium or Zinc bromide.
11. Aprocess as claimed in claim 1, Wherein the concen

tration of the promoter is effective to reduce corrosion of the
reactor in comparison With a concentration of promoter
having a greater bromine content.
less, by a catalytic liquid phase oxidation of toluene by using

a composite catalytic system along With production of value
added products benZyl alcohol and benZoic acid, Without

a 4050% selectivity and a conversion percentage of 25% or
a 4050% selectivity and a conversion percentage of 25 % or
less, by a catalytic liquid phase oxidation of toluene by using

a composite catalytic system along With production of value
added products benZyl alcohol and benZoic acid, Without
10
any trace amounts of benZyl bromide, said process compris
ing: conducting a catalytic liquid phase air oxidation of
any trace amounts of benZyl bromide, said process compris
toluene With a continuous How of air in the presence of a salt
ing: conducting a catalytic liquid phase air oxidation of
of Iron, Cobalt, Manganese, Molybdenum or Nickel as a
toluene With a continuous How of air in the presence of a salt
recyclable catalyst, manganese or copper salts as a recy
of Iron, Cobalt, Manganese, Molybdenum or Nickel as a
15
clable co-catalyst, and cobalt bromide, sodium bromide,
recyclable catalyst, manganese or copper salts as a recy
sodium chloride or Zinc bromide as a promoter, and 0.05 to
clable co-catalyst, and cobalt bromide, sodium bromide,
0.4% by Wt. of a carboxylic acid at a temperature of 60130

C. and a pressure of 110 bar for a period of 0.51.5 hrs,
sodium chloride or Zinc bromide as a promoter, and 0.05 to
0.4% by Wt. of a carboxylic acid at a temperature of 60130

C. and a pressure of 110 bar for a period of 0.51.5 hrs.
Wherein an admixture of C1 to Br ions available from
the co-catalyst enhances the rate of air oxidation of
toluene and ensures that the product mixture is devoid
of benZyl bromide.
Wherein the catalyst and co-catalyst are recycled for 10

20
cycles and provide almost consistent activity and selec
tivity.
13. A process as claimed in claim 1, Wherein no benZyl
bromide is formed as a by-product.
14. A process as claimed in claim 1, Wherein the benZal
10. A process as claimed in claim 1, Wherein the a 25 dehyde produced is chlorine free.
plurality of recycle reactions are conducted With the recov
15. Aprocess as claimed in claim 7, Wherein each organic
ered catalyst, Wherein each of the plurality of recycle

reactions provides near identical conversions and selectivi
acid salt is selected from the group consisting of formic acid

salts, acetic acid salts and propionic acid salts.
ties obtained With an addition of an amount of the promoter

or a bromide on each recycle.

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US006743952B2

(12) United States Patent

(10) Patent N0.:

(45) Date of Patent:

SELECTIVE LIQUID PHASE AIR

US. Cl. ...................... .. 568/431; 568/815; 562/409

OXIDATION OF TOLUENE CATALYSED BY

Field Of Search ............................... .. 568/431, 435,

COMPOSITE CATALYTIC SYSTEM

Inventors: Mannepalli Lakshmi Kantham,

Andhra Pradesh (IN); Pentlavalli

Pradesh (IN); Thella Prathap Kumar,

6,495,726 B1 * 12/2002 Kantam et a1.

Andhra Pradesh (IN); Bhavnari Purna

FOREIGN PATENT DOCUMENTS

Manoranjan Choudary, Andhra

Assignee: Council of Scienti?c and Industrial

Research, NeW Delhi (IN)

Subject to any disclaimer, the term of this

Primary ExaminerJohann Richter

U.S.C. 154(b) by 0 days.

This patent is subject to a terminal disClalmer~

production of benZaldehyde With 4050% selectivity by the

(21) Appl. No.: 10/107,215

composite catalytic system comprising salts of iron, cobalt,

manganese, molybdenum or nickel as recyclable catalyst,

US 2003/0187304 A1 Oct. 2, 2003

Int. Cl.7 ....................... .. C07C 45/28; C07C 27/00;

15 Claims, 1 Drawing Sheet

._D_ Benzoic acid

For each recycle, 5% of Cobalt acetate, 5% of Manganese acetate and 100% of

SELECTIVE LIQUID PHASE AIR

3,989,674, Nov. 2, 1976, Wherein a mixture of toluene,

volumes of gas/h/volume of catalyst. The selectivity of

FIELD OF THE INVENTION

benZaldehyde is 7580% at conversion levels 1530%.

The present invention relates to a process for the produc

tion of benZaldehyde With 4050% selectivity by catalytic

phase catalytic oxidation of toluene to benZaldehyde and

The N.F./F.C.C. grade of benZaldehyde is Widely used in

the presence of a silver-iron vanadate on silica With conver

?avors such as almond and cherry and in various fragrances

sion 21%, selectivity to aldehyde 33% is described. Refer

for soap and toiletries. BenZaldehyde is an FDA. sanc

tioned synthetic ?avoring substance generally recogniZed as

ence may be made to a patent US. Pat. No. 4,390,728, Jun.

of toluene in the presence of a catalyst composed of the

intermediate in the manufacture of pharmaceuticals, dyes,

some other promoter elements. The reaction conditions are

benZoic acid is used as at intermediate in the manufacture of

chemicals, alkyd resins, polyesters, plasticiZers, dyestuffs,

475550 C., 010 atm. pressure, per pass conversion is

BenZaldehyde is currently produced by the hydrolysis of

is generally not more than 70%, With CO2 as main product.

temperatures, generation of carbon dioxide in large amounts

pound. Reference may be made to a patent US. Pat. No.

4,229,379, Oct. 21, 1980, Wherein benZaldehyde is prepared

3550%, selectivity to benZaldehyde 4070%. Reference