CS226199B2 - Method of producing acrolein or methacrolein and acrylic or methacrylic acid - Google Patents

Description

A process for the oxidation of olefins with various multi-component catalysts is known. U.S. Pat. No. 3,642,930 discloses that certain complex catalysts may be used in olefin oxides to unsaturated aldehydes and acids. Indeed, these catalysts are very advantageous for oxidation reactions, but in the course of ongoing research other catalysts have been prepared which could improve the results obtained with the catalysts of the aforementioned US patent. The invention is the result of such research.

The present invention provides a process for producing acrolein or methacrolein and acrylic or methacrylic acid from vapor-phase propylene or isobutylene by oxidizing propylene or isobutylene with molecular oxygen at 200 to 600 ° C in the presence of one molybdenum, oxygen, bismuth, phosphorus, tungsten, nickel, cobalt and alkali metals, which is carried out using a catalyst of the formula I

Sb A _h DE Fe Bi Mo, 0 abcd fg 12 x (I), where A is an alkali metal, thallium or a mixture thereof,

D is nickel, cobalt, magnesium, manganese, zinc, cadmium, calcium, strontium or a mixture thereof E is phosphorus, arsenic, boron, tungsten or a mixture thereof, and is greater than 0 but less than 5, and bad are 0 to 4, c is 0.1 to 20, f and g are 0.1 to 10, and x is the number of oxygen atoms required to saturate the bonds of the other elements present.

The oxidation reaction provides particularly advantageous results at atmospheric or elevated pressure.

In particular, the use of a catalyst is a feature of the invention. As the catalyst, one of the catalysts defined by the above formula may be used. It is also preferable for the overall structure of the catalyst mixture if the catalysts contain potassium, rubidium, cesium or a mixture thereof and catalysts containing nickel, cobalt or a mixture thereof.

The catalysts of the invention can be used on a carrier or in a carrier-free form.

Suitable materials include silica, alumina, electrothermally produced corundum, titanium dioxide, zirconium dioxide, silicon carbide, and the like. Catalysts can also be used in various physical forms. The catalysts can be used in fixed bed and fluidized bed reactors.

The process of oxidizing propylene or isobutylene is well known in the art. Generally, the mixture of olefin and molecular oxygen, optionally in the presence of steam or other diluent, is contacted with the catalyst at an elevated temperature of 200 to 600 ° C for a time sufficient to convert the olefin to the corresponding unsaturated aldehyde and acid.

Usually the product of these reactions contains a very large proportion of aldehyde and a minor amount of unsaturated acid as a by-product. The contact time can vary widely from a few to a large number of seconds. The reaction may be carried out at atmospheric, elevated or reduced pressure, the elevated pressure normally being used in the industrial range.

A particular advantage of the catalysts of the present invention lies in their ability to withstand large amounts of olefin feed through the catalyst over a given period of time. This is normally measured in units of weight ratio of olefin feed to catalyst weight per hour (WWH). In other words, the catalysts can work efficiently with large amounts of olefin. Prior art catalysts tend to be less effective when large amounts of olefin are deployed over a given period of time.

Examples 1 to 8

Catalysts containing antimony

The various antimony-containing catalysts of the invention are prepared as follows. All catalysts contain 20% silica.

Example 1 ^Sb 0.5 ^K 0.1 ^Ni 2.5 ^Co 4.5 ^Fe 3 ^BiMO 12 ° x

Prepare a suspension of 63.56 g (ΝΗ ₄ ) Μθγ0 ₂₄ ; Η ₂₀ , 61.79 g of 34% silica sol (Nalco) and 2.19 g SbgOO and combine with a solution of 36.36 g Fe (NQ) ₃ ) _{3. 9} H ₂ O, 14.55 g.

• 5H ₂ O, 39.29 g Co (NO ₃ ) ₂ .6H ₂ 0, 21.80 g Ni (NO ₃ > ₂ .6H ₂ O and 3.03 g of 10% KNO ₃ solution) The mixture is evaporated, dried , heat treated at 290 ° C for 3 hours, at 425 ° C for 3 hours, and at 550 ° C for 16 hours.

Example 2 ^SbK 0.1 ^Cu 0.1 ^Ni 2.5 ^Co 4.5 ^Fe 3 ^BiMo 12 ° x

The catalyst is prepared in substantially the same manner as in Example 1, but the currency is added in the form of Cu (NO ₃ ) ₂ , 3H ₂ O,

Examples 3 and 5 ^Sb 0.5 ^Cs 0.5 ^Ni 2.5 ^Co 4.5 ^Fe 3 ^BiMo 12 ^O x

The catalyst was prepared in essentially the same manner as in Example 1 except that the potassium compound was replaced with CsNOy.

Examples ^{4a7 Sb} 1.0 ^Gs 0.5 ^S 0.25 ^Ki 2.5 ^Co 4.5 ^Fe 3 ^BiMo i 2 ° x

The catalyst is prepared in substantially the same manner as described above except that Cs 2 SO 4 is used to introduce sulfur into the catalyst.

Example 6 ^Sb 0.5 ^Cs 0.2 ^Ni 2.5 ^Co 4, ₅ ^Fe 3 ^BiMo 12 ° x

The catalyst was prepared in substantially the same manner as in Example 1 except that CsNO4 was used instead of potassium.

In a fixed bed reactor, which is made of a stainless steel tube with an inner diameter of 0.75 cm, 5 ml of each of the catalysts produced above are placed. The catalysts were tested at 371 ° C using a 1: 10: 4 isobutylene / air / steam feed at an actual contact time of 3.7 and 0.4 seconds.

The results shall be determined as follows:

i moles of product χ 100% yield in one pass moles of undiluted isobutylene moles of reacted isobutylene χ 100% conversion »———————————— - selectivity - .......

moles of reacted isobutylene

The results of these tests are shown in Table 1, where MA is methacrolein and MAA is methacrylic acid.

T a b u 1 k a 1

Oxidation of isobgtylene to methacrolein and methacrylic acid using catalyst of formula YNi _{2> 5} Co 4 ₁₅ Pe ₃ BiMo ₁₂ O _x

At- klad Catalyst Y = Results Yield in one pass ΜΑ MAA Total in% Conversion Selectivity 1 ^Sb 0.5 * 0.1 60.8 4.9 65.7 100.0 65.7 2 ^Sb 0.5 * 0.1 ^Cu 0.1 66.1 M 67.5 100.0 67.5 3 ^Sb 0.5 ^Cs 0.5 80.3 3.3 83.6 99.4 84.2 4 ^Sb 1.0 ^Cs O 5 ^S 0.25 74.1 ',O 75.1 82.1 91.4 5 ^{(a) (b) * * (e) Sb} 0.5 ^Cs 0.5 6.1, 1 8.5 69.6 98.8 70.5 6®> ^Sb 0, 5 ^Cs 0, 2 66.1 5.3 71.4 100.0 7 ', 4 ₇ b) ^{Sb 1.0 Cs} 0.5 ^S 0.25 77.2 1.6 78.8 92.8 85.0

^{(a) a} pressure of 0,084 MPa; ^{(b) a} pressure of 0,068 MPa

Example 8

Production of acrolein and acrylic acid

In the same manner as described in the above examples, the catalyst of formula is prepared Sbg jKq .mu.g Co ^ ^ ^ ^ BiMOj Fe ₂ 0 _χ and used for the oxidation of propylene. The catalyst is placed in a 5 ml reactor reaction zone made of a stainless steel tube. The reaction zone temperature is maintained at 380 ° C and the actual contact time is 3 seconds. Propylene, air and steam are used as the feed in a ratio of 1: 11: 4. Of the propylene used, 96.8% converges with a selectivity to acrelin and acrylic acid of 94.9%. The yield of acrolein in one pass is 78.1%. The yield of acrylic acid in one pass is 13.8% and the total yield of acrolein and acrylic acid in one pass is thus 91.9%.

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Claims (1)

SUBJECT OF THE INVENTION A process for producing acrolein or methacrolein and acrylic or methacrylic acid from vapor-phase pyrene or isobutylene by oxidizing propylene or isobutylene with molecular oxygen at a temperature of 200 to 600 ° C in the presence of one molybdenum, oxygen, bismuth, phosphorus, tungsten, nickel cobalt and alkali metals, characterized in that a catalyst of the formula I (I) is used. where A is an alkali metal, thallium or a mixture thereof, D is nickel, cobalt, magnesium, manganese, strontium, calcium, zinc, cadmium or a mixture thereof E is phosphorus, arsenic, boron, tungsten or a mixture thereof, and is greater than 0 but less than 5, and bad are 0 to 4, c is 0.1 to 20, f and g are 0.1 to 10, and x is the number of oxygen atoms required to saturate the bonds of the other elements present.