JPS582218B2 - Fuhouwa aldehyde - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing unsaturated acids.

More particularly, the present invention utilizes catalysts comprising oxides of tin, tungsten, vanadium, molybdenum, and optionally other polyvalent metals to convert unsaturated aliphatic aldehydes to the corresponding unsaturated acids. related to things.

U.S. Pat. No. 3,576,773 describes a vanadium, tungsten and molybdenum catalyst useful in converting unsaturated aliphatic aldehydes to acids.

Chemical Week
Page 41, February 9, 1972), in the desirability of propylene oxidation procedures to obtain unsaturated acids, places great emphasis on finding effective catalysts to use in the oxidation reaction. .

The present invention is based on the results of studies in the second step of the oxidation reaction described above, which converts unsaturated aliphatic aldehydes to their corresponding unsaturated fatty acids.

The above method for converting unsaturated aliphatic aldehydes into corresponding unsaturated fatty acids is based on the following formula (where A is Fe,
Ni, Co, Zn, Mn, Mg, Cu or a mixture thereof, a is a number from O to 10, b is a number from 0.1 to 12,
C is a number from 0.1 to 6, d is a number from 0.5 to 12,
The effect is significantly improved by using a catalyst containing an element having the empirical formula: e is a number from 8 to 16, and X is the number of oxygen atoms satisfying the valence of the element in the catalyst. I discovered that it is possible to obtain

Using the catalyst of the present invention, unsaturated acids can be obtained in higher yields, the amount of by-products produced is lower, and the catalyst stability is higher than with conventional catalysts.

One of the important aspects of the invention lies in the catalyst used.

As the catalyst, any catalyst of the above formula can be used.

A preferred catalyst is one in which e in the above formula is 12, that is, Mo12.

In addition, other preferable catalysts are those in which A is Cu, Mn,
Fe, Co or a mixture thereof, where a is 0.1 to 6, and in this case a high single flow conversion rate can be obtained.

Particular preference is given to using copper.

Although the catalyst of the present invention has the desired activity even when used without a carrier material, it is usually used on a carrier.

Examples of suitable carrier materials are silica, titania, zirconia,
These include alumina, boron phosphate, aluminum phosphate, antimony phosphate, pumice, etc.

A preferred support material is silica. The catalyst of the present invention may further contain other components in addition to the above-mentioned catalyst components, as long as they do not have a detrimental effect on the production of unsaturated acids.

Therefore, other metals may also be included in the base catalyst of the above formula of the invention.

The catalyst of the present invention may be conveniently made by the method described in US Pat. No. 3,567,773.

The method of the present invention can be carried out in substantially the same manner as described in US Pat. No. 3,567,773.

Generally, the reaction is carried out in the gas phase.

The catalyst may be used in fixed bed or fluidized bed reactors.

The reactants are passed through the catalyst bed in a molar ratio of 0.5 to 4 moles of oxygen per mole of aldehyde and 1 to 20 moles of water per mole of aldehyde.

The reaction temperature is usually maintained at 150 to 450°C.

The preferred reaction temperature is within the range of 200 to 400°C.

The pressure can vary over a wide range, ranging from 0.5 to 10 atmospheres.

One particular advantage of the present invention is that acids can be obtained in high yields at low temperatures.

It also has a long catalyst life and can withstand significant changes in feedstock and reaction conditions without deleterious effects.

Further, the catalyst of the present invention can reduce or eliminate the production of acetic acid, an undesired by-product, when oxidizing acrolein to produce acrylic acid.

A preferred reaction of the present invention is a reaction that converts acrolein to acrylic acid.

Of course, other unsaturated aliphatic aldehydes can also be converted to the corresponding unsaturated fatty acids using the catalysts of the present invention and the techniques disclosed herein.

Production example of catalyst S b S n Production of VWMo-containing catalyst 62% S b
a S n 3 V3 W1 . 2 Mo 12 O
A catalyst having a composition of X and 38% SiO2 was produced as follows.

Sb203 (21.9 g) is digested in 350 cc of concentrated HNO and SnO2 (22.5 g) is added.

Decant the supernatant and wash the solids with water.

(NH4) 6・Mo7O24・4H2O (106g)
was dissolved in warm water and this solution was combined with tin, antimony, NH4VO3 (17.6 g) in 600 cc of water and 3
Add to a slurry consisting of 350 g of 0 wt% silica sol and (NH4)6W7O24.6H2O (16.2 g) suspended in hot water.

Adjust the pH of the mixture to 3 with nitric acid.

The mixture was slowly evaporated with stirring and dried in an oven at 130° C. for 24 hours.

Example I Preparation of Sn VWMo-containing catalyst 62% Sn
A catalyst with a composition of 6V3W1.2Mo12OX and 38% SiO2 was prepared using SnO2 (45.0 g) digested in 100 cc of concentrated nitric acid, rather than using a mixture of Sn and Sb oxides digested in nitric acid. Manufactured using

Comparative Example A Preparation and Use of VWMo Catalyst 62% W3W1 in a manner similar to Example 1 of U.S. Pat. .2Mo12
A catalyst consisting of OX and 38% SiO2 was produced.

A portion of the catalyst (20-35 mesh) was placed in a 4cc fixed bed reactor.

The reactor was brought to a temperature of 300°C under air circulation for 2 hours.
It was kept at 0°C.

A feedstock consisting of a ratio of 1 acrolein/6 air/H2O5 was fed into the catalyst bed at a rate resulting in a contact time of 1 second.

The reactor was operated with feed under reaction conditions for 15 minutes to precondition the catalyst.

After this pre-run, the reactor effluent was collected for 15 minutes.

This product was analyzed by gas chromatography.

The results of this experiment using the conditions of US Pat. No. 3,567,773 are shown in Table 1.

Example 2 Preparation of Acrylic Acid The catalyst prepared in Example 1 was used in the method described in Comparative Example A.

The first comparison of this experimental result and the result obtained in Comparative Example A is
Shown in the table.

It is clear from the above test results that the single pass yield is significantly improved using the catalyst of the present invention.

Furthermore, it was observed that the stability of the catalyst was also improved.

Example 3-18 and Comparative Examples B and C Various catalysts of the present invention were prepared as follows.

Completely dissolve appropriate amounts of ammonium salts of tungsten, molybdenum and panadium.

Next, add the promoter component.

Add copper, iron, manganese and cobalt as nitrates,
Tin and antimony were added as oxides.

Finally, Nalco Chemical Company (Nalco C
chemical Co. 40% ammonia-stabilized silica sol sold under the trade name 41D01 was added to obtain a catalyst having a composition of 62% active ingredients and 38% silica.

Evaporate the slurry to a thick paste and place it in the oven for 1 hour.
It was dried at 110°C overnight.

The catalyst was crushed and sieved.

A reactor (20 cc reaction zone) in which this catalyst (20 x 30 mesh) was assembled from stainless steel tubes with an inner diameter of 1.02 cm
I put it in.

Under a gentle flow of air, the catalyst was gradually heated to 400°C for 3 hours and held at 400°C for 2 hours.

Comparative Examples B and C demonstrate the activity of the base catalyst.

Table 2 shows the results obtained when acrolein was oxidized to acrylic acid using the catalyst of the present invention, together with the reaction conditions.

Methacrylic acid was produced from methacrolein using the catalyst of the present invention in the same manner as described in the examples above.

Also, using the same method as shown in the above example, the following formula Fe0
．． 5Sn6W3V1.2 Mo12Ox, MgCu3
Sn0.5W1.5V4Mo13Ox and Zn0.2
The corresponding unsaturated aliphatic carboxylic acids were prepared from unsaturated aliphatic aldehydes using a catalyst of Sn4WVMo10Ox.

Claims (1)

[Claims] 1 In a method for producing a corresponding unsaturated fatty acid by catalytically oxidizing an unsaturated aliphatic aldehyde with molecular oxygen or a molecular oxygen-containing gas at a temperature of 150 to 450°C, the oxidation reaction is expressed by the following formula (formula Inside, A is Fe, Ni,
Co, Zn, Mn, Mg, Cu or a mixture of these metals, a is a number from 0 to 10, and b is 0.
A number from 1 to 12, C is a number from 0.1 to 6, d is 0.
a number from 5 to 12, e is a number from 8 to 16, and X
is the number of oxygen atoms that satisfies the valence of the element in the catalyst.