United States Patent (113,624,147

72) Inventors Reginald David; 56) References Cited

Jean Estienne, both of Lyon, France FOREIGN PATENTS
21 Appl. No. 826,298 1,428,957 3/1965 France......................... 260/604 AC
22 Fied May 20, 1969 904,304 81 1962 United Kingdom.......... 260/533 N.
45 Patented Nov.30, 1971
(73) Assignee Rhone-Poulenc S.A. Primary Examiner-Lorraine A. Weinberger
Paris, France Assistant Examiner-Richard D. Kelly
(32) Priority May 21, 1968 Attorney-Cushman, Darby & Cushman
33 France
31 S2605
ABSTRACT: Acrylic acid is prepared by oxidizing propylene
with air in the presence of water and a platinum, rhodium,
54) PREPARATION OF ACRYLCACD rutheniun or palladium metal catalyst at a temperature above
7 Claims, No Drawings 50 C. and a pressure exceeding 5 bars gauge. A supported
(52) U.S. Cl........................................................ 260/533N,
palladium catalyst is preferred. Acrylic acid is obtained in
260/604 AC about 60 percent yield based on propylene converted and the
51 int.C......................................................... C07c57/04
small amounts of acrolein obtained may be oxidized to acrylic
acid.
50 Field of Search............................................ 260/533 N,
604 AC
 3,624,147
1. 2
PREPARATION OF ACRYLICACD acrylic acid by the usual methods. The unconverted propylene
can be recycled to the oxidation zone.
The present invention relates to a process for the prepara The examples which follow illustrate the invention.
tion of acrylic acid by the oxidation of propylene. EXAMPLE
Several processes for the oxidation of propylene to acrylic 5
acid by air or by oxygen in the gas phase have been described. Two-hundred cn.of water and 10.6 g. of a catalyst consist
The most commonly used catalysts are based on some form of ing of palladium deposited on carbon block (palladium con
molybdenum, for example the trioxide, which is frequently as- tent: 10 percent are introduced into a 1 litre stainless steel au
sociated with an oxide of a polyvalent metal such as cobalt, toclave. The apparatus is closed and flushed with nitrogen,
nickel or tin. These catalysts are generally used in the 0 and then introduced into an oven arranged on a vibratory
presence of acid promoters such as boron, phosphorus, agitator and charged with 42.6 g. of propylene (corresponding
vanadium, tellurium or arsenic oxide. Such processes have to a pressure of 11 bars).
been described in British Pat. specifications Nos. 893,077, The temperature of the contents of the autoclave is raised to
961.468,967,241 and 971,666. Regardless of the catalyst 5 90 C., with agitation, in 1 hour 40 minutes. The pressure is
used, high temperatures, of the order of 300 to 700 C., are then 30 bars. Air is introduced until a pressure of 100 bars
required. Further more, as emerges from French Pat. No. (corresponding to an air pressure of 70 bars) is established.
1433,572, the catalyst must meet certain conditions as to After 2 hours 5 minutes the pressure becomes stable at 84
composition so that acrylic acid is formed preferentially and at bars. The agitation is stopped and the contents of the au
the expense of the acrolein which is formed in varying 20 toclave are cooled to 20°C. The gas is removed from the ap
amounts during the oxidation of propylene. Thus the catalyst paratus through a bubbler containing hydroxylamine
has to be carefully prepared. - hydrochloride and then through a bubbler containing 5 N
The present invention provides a process for preparing potassium hydroxide solution.
acrylic acid which comprises oxidizing propylene with The reaction medium is withdrawn from the autoclave, and
molecular oxygen or a gas containing molecular oxygen in the 25 to it the 150 cm3of water used to rinse the apparatus are
presence of water and of a noble metal of group VIII of the added. This mixture is distilled under normal pressure and 30
Erics (i. with above 50C and under a cm of a fraction boiling below 99 C., which consists of an
a

Suitable noble metals include platinum, rhodium, rutheni- aqueous distillate containing various carbonycompounds, are
um, and particularly palladium. The metal may be used in a 30 collected.
the catalystThe acid-containing residue is filtered to remove
finely divided state or can be deposited on a carrier suchas for Analysis and determination of the products contained in the
example alumina, silica gel, aluminum oxide or aluminum sil- aqueous distillate, in the distillation resid d in the t
icate, pumice, active charcoal or bentonite. In this latter case l the followin results: Istriation residue and in the traps
it is advantageous to use catalysts containing to 20 percent 3. 3.
by weight of metal based on the total weight of carrier and 35 -
metal; these limits are, however, not essential. The amount of an 3. m 8. }
catalyst to be used may vary within wide limits depending on Acrylic acid 7.3xio-mo 3.
the reaction conditions. Thus the amount of catalyst expressed
as metal may vary from 0.01 to 10 percent by weight based on The yields, based on propylene converted during the reac
the reaction medium. ithin wide limits b 'tion, are 16.3 percent CO., 6.7 percent acrolein and 58.4 per
The reaction temperature I 'A'iti, wide "I "
the high temperatures required in the previously known
cent acrylic acid. The remainder of the propylene has been
converted to various carbonyl and carboxylic compounds.
processes are not necessary. In general temperatures between
50° and 200° C., and preferably between 70 and 120 C. are
suitable. 45 EXAMPLES 2-4
The process is carried out under gauge pressures greater
than 5 bars (i.e. an absolute pressure greater than 6 bars), The procedure described in example 1 is followed except
preferably 20 to 150 bars gauge. The pressure has no critical that an air pressure of 50 bars is used. By varying the tempera
upper limit but for technical and economic reasons, very high 50 ture the results shown in the table below were obtained. The
pressures are not of interest. yields are expressed based on the propylene converted.
Acrolein Acrylic acid CO
Temper- Propylene - - - - - - - - - - --
ature introduced Yield, Yield, Yield,
Examples in C. Duration in g. g. percent g. percent g. percent
2-------------- 80 3 hrs. 45 min-------- 4.5 0.49 8, 4.1 58.3 1.09 16.3
90 hr. 30 Inin --------- 4 47 8.9 3.71 4, 20 18.9
100 1 hr----------------- 42.5 0.23 5 3.40 56 26 22.2

The relative proportions of propylene and oxygen may vary 60 EXAMPLESS and 6
widely but for safety reasons explosive mixtures must be The procedure described in example 1 is followed using a
avoided and therefore in practice a large excess of propylene temperature of 90°o C., but varying
. the air pressure; the follow
is usually used. ing results were obtained:
Acrolein Acrylic acid CO2
Pressure Propylene w
of air introduced Yield, Yield, Yield,
Ekaples in bars. Duration in g. g. percent g. percent . . percent
: 50 hr. 30 min- 41 0.47 8.9 3.7 4, 20 8.9
6--- 60 2 hrs--------- A3.2 0.46 6.9 4, 62 53, 5 1. 44 7.8

The process of this invention may be carried out continu- EXAMPLE 7

ously or discontinuously in any type of apparatus usually used
for such a process. As well as the acrylic acid obtained in The same conditions as those described in example l are
about 60 percent yield based on the propylene converted, used except that the catalyst on carbon black is replaced by a
acrolein in less than 10 percent yield is formed. This acrolein, 75 catalyst on alumina, containing 10 percent by weight of pal
after separation from the acrylic acid, may be oxidised to ladium metal.
 3,624,147 a.
3 4.
The following results were obtained: 2. A process according to claim 1 wherein the metal catalyst
is deposited on a carrier.
Acrylic acid 7.65x10 mol (5.50 g.) 3. A process according to claim 2 wherein 1 to 20 percent
Acrolcin 0.86x10" mol (0.48 g.) by weight of metal based on the total weight of metal and car
CO, 7.54x10 moi (1.691.) 5 rier is used.
The yields, based on the propylene converted during the 4. A process according to claim 1 wherein 0.01 to 10 per
reaction, are 60.7 percent acrylic acid, 6.8 percent acrolein cent by weight of the metal catalyst based on the reaction
and 20 percent CO. medium is used.
EXAMPLES 8 TO
The procedure described in Example 1 is followed using a series of catalysts. The results obtained are shown in the table below:
Degree
of con
Yg Acroller Acrylic acid Saturated acids CO
of pro- - - ------ -----------rr

Example Catalyst Duration pylene, Mol, Yield,

percent X10 percenti Yield. Mol, Yield,
g. percent i X102 percent Litres Yield,
percent
8.--------------- 10% Pd on silica gel ------------ 3hrs. 5 mini---- 16.9 6 8.17 67.7 1.50 8.9 1,52 13,5
-- 10% Pd on silica-alumina 2.---- 4 hrs. 15 mini---- 12.1 0.94 7.2. 6.2 66 1.01 7.7 1.38 5.5
-- 7%. Pd on silica gel --- - 1 hr. 30 min.---- 13.5 0.42 3.1 S. 74 59 1.8 13.3 2 21.9
- - - - - - - Pd without carrier ----------...- 2 hrs. 15 Imini---- 13.1 0.80 5.7 5.65 56.2 2.05 4. 1.75 18.6
Based on the propylene converted.
21.06 g. of Pd metal are used, as catalyst.
3.18 g. of Pd metal are used as catalyst.
We clairn: 5. A process according to claim 1 wherein the temperature
1. A process for preparing acrylic acid which consists essen- 25 is 50 to 200 C.
tially of oxidizing propylene with molecular oxygen or a gas 6. A process according to claim 5 wherein the temperature
containing molecular oxygen in the presence of water and of is 70 to 120° C.
platinum, rhodium, ruthenium or palladium metal catalyst at a 7. A process according to claim 1 wherein the pressure is 20
temperature above 50 C., and under a pressure exceeding 5 to 150 bars.
bars gauge. 30 xk k k . . -

35

40

45

50

55

60

65

70

75