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United States Patent (19) : Fujii, All of Matsuyama, Japan Attorney, Agent, or Firm-Sherman & Shalloway
United States Patent (19) : Fujii, All of Matsuyama, Japan Attorney, Agent, or Firm-Sherman & Shalloway
formed
( acid -- benzyl alcohol -i- (mmol)
benzaldehyde --benzylbenzoate X ..)
Selectivity (%) = X ())
Consumed toluenc (mmol)
EXAMPLE 2 EXAMPLE 3
The same autoclave as used in Examplc was The same autoclave as used in Example 1 was
charged with 200 g of toluene, 1 g of benzaldehyde, charged with 200 g of toluene, 5 g of benzoic acid, 1 g
and cobalt naphthenate and manganese naphthenate of benzaldehyde, cobalt benzoate containing 47.5 mg
containing metallic Co and Mn in the amounts indi of Co and manganese acetylacetonate containing 2.5
catcd in Table 2. Air was blown into the autoclave mg of Mn. Air was blown into the autoclave under high
under a pressure of 7 kg/cm gauge and at a tempera speed agitation, under the pressure and at the tempera
ture of 160°C. under high speed agitation, while adjust ture indicated in Table 3, while adjusting the flow rate
ing the flow rate at the gas outlet to 1,000 cc/min. After 40 at the gas outlet to 1,500 cc/min. After the absorption
the absorption of oxygen started, the reaction was con of oxygen started, the reaction was conducted for the
ducted for 4.5 hours. After completion of the reaction, time indicated in Table 3. After completion of the reac
the reaction product was recovered, and the selectivity tion, the selectivity of the reaction, yield of formic acid
of reaction and yield of formic acid and acetic acid and acetic acid, and formation rate of benzoic acid
were calculated similarly to Example 1. The results 45 were calculated similarly to Example 1. The results
were as given in Table 2 below. were as given in Table 3.
Table 3
Yield of Formation
Run Reaction Reaction Reaction Selec- Formic Rate of
No. Temp. Pressure Time tivity Acid and Benzoic Remarks
(°C.) (kg/cm G) (hr.) (%) Acetic Acid
(%) (g/hr.)
3-a 125 1() Absorption of oxygen did not begin Control
even after 5 hours.
3-h 5() 1() 5 93.5 ().8 3.2 Example
3-c 185 () 3 93.8 ().7 41.5
3-d 22(3. 5 2 854 1.2 57.2
3-e 235 2) 2 82. .6 56.
3-f 25() 25 2 73.() 2.9 46.5 Control
Table 2
Run Amount of Catalyst Yield (f EXAMPLE 4
Nc). Selec- Formic Acic
( Co M tivity and Acetic Remarks A 500-cc stainless steel autoclave equipped with a
(ng) (mg) (A) Acid reflux condenser, a stirrer, and a gas inlet was charged
2-a 3().() () 88.6 1.3 c 65 with 190g of toluene, 5g of benzoic acid, 5g of benzal
2-b 29.94 ().06 90.2 1. Example dehyde, and cobalt acetate tetrahydrate (Co content:
i; 3.85 85 3.3 83 23.6%) and manganese acetate tetrahydrate (Mn con
2-e 28.5 15 94.() ().8 tent: 22.4%) of the amounts indicated in Table 4 re
3,903, 148
10
spectively. Air was blown into the autoclave under a ied, but the amounts officed were kept constant, which
pressure of 10 kg/cm gauge and at a temperature of were 29 mg as cobalt metal, and 1 mg as manganese
180°C. under high speed agitation, while adjusting the metal.
flow rate at the gas outlet to 1,500 cc/min. After the ab After completion of the reaction, the selectivity,
sorption of oxygen started, the reaction was conducted yield of formic acid and acetic acid, and the formation
for 3 hours. The condition of the feed was such that the rate of benzoic acid were calculated similarly to Exam
total sum of Co and Mn was varied for each run, while ple 1. The results were as given in Table 5.
Table
Catalyst Yield (f Formation
Rui Selectivity Formic Acid Rat (f
N. Citat Manganese (%) and Acetic Bonzoic
s Compound Compound Acid Acid
(%) (g/hr.)
5-a cobait finely divided 93.5 ().8 35
toluate mangancse metal
5-b ccbait manganese
acctylacctate carbonate 92.4 ().9 32,
5-c cobalt mangiancse
oleiate butyrate 92.) ().9 3).
5-d finely manganese
divided benzoate 93.2 ().8 29.8
cobalt mctal
We claim:
1. A process for preparing benzoic acid by oxidizing 2. A process for preparing benzoic acid in accor
toluene with molecular oxygen containing gas in the dance with claim 1, in which the oxidation is performed
liquid phase, which is characterized in that the oxida at a temperature between 135 and 235°C., the weight
tion is performed : - - ratio of the nickel metal to the manganese metal in the
1. in the substantial absence of lower fatty acids and 15 catalyst being within the range of 99.5/0.5 to 60/40.
for halogen compounds, and 3. A process for preparing benzoic acid in accor
2. in the presence of a catalyst composed of dance with claim 1, in which the oxidation is performed
A. component A which is a nickel compound, and at a temperature between 150 - 220°C.
B. component B which is a manganese compound, 4. A process for preparing benzoic acid in accor
3. the concentration of the catalyst being such that, 20 dance with claim 1, in which the oxidation is performed
when said components A and B are calculated as at a temperature between 150-220°C. and the weight
the respective metals, ratio of the nickel metal to the manganese metal in the
i. the total amount of nickel mctal and manganese catalyst is within the range of 99/1 to 75/25.
metal ranges from 0.003 to 0.5% by weight based 5. A process for preparing benzoic acid in accor
on the total oxidation reaction, mixture, 2 5 dance with claim.1, in which the sum of the nickel
. . ii. when the oxidation is performed at a tempera metal and manganesc metal is within the range of 0.005
ture not lower than 135°C. but lower than - 0.1% by weight based on the total oxidation reaction
185°C., the weight ratio of the nickel metal to the mixture.
manganese metal being 99.8/0.2 to 60/40, and 6. A process for preparing benzoic acid in accor
iii. when the oxidation is performed at a tempera 30 dance with claim 1, in which both catalyst components
ture between 185 – 235°C., the weight ratio of are at least partially soluble in the oxidation reaction
the nickel metal to the manganesc metal being mixture.
99.8/0.2 to 5/95.
40
45
55
60
65