CS226158B2 - Method of preparing 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 the oxidation of olefins 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 of the U.S. Pat. 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 a temperature of 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

WdW12 ⁰ x ^(I >>

where

X is cerium, thorium, manganese, praseodymium, yttrium, zirconium, ruthenium, gallium, tin, indium, lanthene, mes, tantel, or a mixture thereof,

A is an alkali metal, thallium or a mixture thereof,

D is nickel, cobalt, magnesium, zinc, cadmium, calcium, strontium or a mixture thereof,

E is phosphorus, arsenic, boron, tungsten, sulfur, aluminum or a mixture thereof and a is greater than 0 but less than 5, b and d are 0 to 4, e, f and g are 0.1 to 2 and

X is the number of oxygen atoms needed to saturate the bonds of the other elements present.

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

The main feature of the invention is in particular the use of a catalyst. As the catalyst, one of the catalysts defined by the above formula may be used. In a preferred embodiment of the invention, each of the elements represented by X is introduced separately into the catalyst. This is usually achieved by independently adding component X in an amount proportional to the different elements. It is also preferable for the overall structure of the catalyst mixture if the catalysts contain potassium, rubidium, cesium or a mixture thereof with catalysts containing nickel, cobalt or a mixture thereof.

The catalysts of the invention can be prepared by a process well known in the art. This process involves the simultaneous precipitation of soluble salts. Specific information on the production of catalysts is provided in the Examples.

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, zirconia, 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 procedure for propylene or isobutylene oxide oxidation is well known in the art. Generally, a mixture of olefin and molecular oxygen, optionally in the presence of a feather 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 pad 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 from atmospheric, elevated or reduced pressure, the elevated pressure normally being used within 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 ratio of olefin weight to catalyst weight per hour (WH). 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

Oxidation of isobutylene at atmospheric pressure

Various catalysts of the present invention containing 20% silica are prepared as described below.

Example 1? 0.5 ^K 0.1 ^Ni 2.5 ^Co 4.5 ^Fe 3 ^BiMo 12 ° x

A suspension of 63.56 g (NH ₄ ) g Mo _{7 24 24 4} H ₂ O, 52.33 g 40% silica salt (NalCo) and 2.60 g PrOg was prepared. Separately, a solution of 36.36 g Fečko y9H ^ ₂ 0, 14.55 g of Bi (N0 _{3) 3} .5H ₂ O, 39.29 g of Co (NO _{3) 2} .6H ₂ O, 21.80 g Ni ( NOýg. 6H ₂ 0 and 3.03 g of 10 _»s solution KNO slurry and solution are combined and the liquid evaporated to a paste and the paste was dried at 120 ° C overnight. the catalyst was heat treated at 290 ° C for three hours at 425 ° C three hours e at 550 ° C for 16 hours.

Examples 2 to 5

The catalysts are prepared in the same manner as described above, except that appropriate amounts of manganese and thorium nitrate, germanium chloride and niobium oxide are added instead of praseodymium.

Example 6 ^Mn 0.5 ^Ce 0.5 ^K 0.5 ^Ni 2.5 ^Co 4.5 ^Pe 3 ^BiMo 12 ^O x

Solution 2.72 g CsNO 3, 1.19 g HKO 3, 20.33 g Ni (NO ₃ ) ₂ .6H ₂ O, 36.61 g Co (NO ₃ ) ₂ .6H ₂ O,

33.9 g Fe (NO ₃ ) ₃ .9H ₂ O, 13.6 g Bi (HO ₃ ) ₃ .5H ₂ O are added to the suspension 2.5 g Mn (HO ₃ ) ₂ , 59.2 g (KH) ₄ ) 6M ° 7 ⁰ 24 .4H ₂ 0 and 50 g of 40% silica salt (Nalco). The mixture was evaporated, dried and worked up by heating as in Example 1.

Examples 7 and 8

Catalysts are produced in the same manner except that manganese nitrate is used. 1.46 g GeO ₂ or 1.84 g Nb ₂ O 4 are added.

A fixed bed reactor, made of a stainless steel tube of 0.75 cm ID, was charged with 5 ml of each of the above catalysts. These catalysts were tested at a reaction temperature of 371 ° C using isobutylene, air and feather at a ratio of 1: 10: 4 and an actual contact time of 3.3 seconds. The results of these tests are shown in Table 1.

The results shall be determined as follows:

moles of product x 100% yield in one pass = ......................

moles of isobutylene feed moles of isobutylene feed x 100% conversion = moles of isobutylene feed moles moles of product x 100% selectivity = --— moles of isobutylene feed

In the tables, MA is methecrolein and MAA is methacrylic acid.

Table,

Oxidation of isobutylene to metecrolein and methacrylic acid at atmospheric pressure using a catalyst of the formula YNi ₂ ^ 0ο ₄ ^ Fe ^ 1Mo ^ O *

Results,%

Yield at

Example Catalyst, Y = one pass

MA MAA Total Conversion Selectivity 1 Pr _0, 5 ≤ 0.1 6,, 6 2.2 63.8 91.3 69.9 2 ^ 0.5 ^, 1 68.5 2.9 71.4 100.0 71.4 3 ^Ge 0.5 ^K 0.1 67.0 4,5 71.5 100.0 71.5 4 ^Nb 0.5 ^K 0.1 52.2 2.5 54.7 82.9 66.1 5 ijKq, 1 74.3 2.6 76.9 100.0 76.9

continuation of Table 1

Example Catalyst, Ϊ = Results,% Yield in one pass Conversion Selectivity MA HAA Total 6 ““ 0.5 ^Ce 0.5 ^K 0.5 68.3 3.4 71.7 100.0 71.7 7 ^0,5θ 0.5 ^Οβ 0.5 ^Κ 0.5 77.1 1.0 78.1 94.3 82.9 8 ^Nb 0.5 ^Cs 0.5 ^K 0.5 75.3 1,2 76.5 94.7 80.8

Examples 9 to 13

Oxidation of isobutylene under elevated pressure.

In the same manner as described above, the catalysts produced by the shear are used in reactions under elevated pressure. Catalysts ae are produced as follows:

EXAMPLE 9 ^Cr 0.5 ^Cs 0.5 ^III 2.5 ^Co 4.5 ^Fe 3 ⁰ x 12 ^BIMO

Prepare a solution of 1.1 g CsNO ^, 8.2 g Ni (NO _{3) 2} .6H ₂ O, 14.8 g Cs (NO _{3) 2} .6H ₂ O, 13.7 g Fa (MO _{3) 3} .5H ₂ O, 5.5 g of Bi (NO _{3) 3} .5H ₂ O and 2.3 g of Cr (NO _{3) 3} .9H ₂ O and the suspension 23.9 g (NH _{4) 7} 0 _a4 GMO. . 4H ₂ 0 and 20 g salt, 49% silica (Nelco). Catalyst ae was dried and heated to 430 ° C for four hours and 600 ° C for three hours.

Examples 10 to 13

Catalysts were prepared in the same manner as in Example 9 using the appropriate components as starting materials.

Unless otherwise stated, the procedure is performed at 0.08 MPe. The reaction temperature and results are shown in Table 2. The same mixture was used as described above. The actual contact time is 3.5 to 4.1 seconds and the weight ratio of the feed olefin to catalyst weight is 0.098 to 0.0159.

Table 2

Oxidation of isobutylene to methacrolein and methacrylic acid at elevated pressure using a catalyst of the formula TNig gCO ^ ^ Ρβ ^ ΒΙΜο ^ Οχ

Example Catalyst, 7 = Temperature Noc: 2 ° C Results, 56 Yield at 1pm pass Conversion Selectivity MA MAA Total 9 ^Cr 0.5 and ^Ca 0.5 371 58.9 2.9 61.8 81.7 75, 6 10 ^Ge 0.5 ^Cs 0.5 371 68.4 5.6 74.0 96.5 76.7 1 1 ^Mn 0.5 ^C ® 0.1 343 64.5 4.8 69.3 99.6 69.5 12 ^Th 0.5 ^Cs 0.5 343 61.5 3.5 65.0 89.0 73.0 13 ^Ce 0.5 ^Cs 0.2 363 70.3 6.4 76.7 98.9 77.6

Example 14

Production of acrolein

In the same manner as described in the examples above, acrolein and acrylic acid are prepared from propylene. 80% ΰβθ ^ Κθ, Nig 5®% 5ββ ΒΙΜο ^ θχ + + 20% SiO ₂ is used as the catalyst. The catalyst is heat treated at 550 ° C for 16 hours.

Use 5 ml of catalyst, a reaction temperature of 350 ° C and an actual contact time of 2.5 seconds.

The yield of acrolein in one pass is 84.8 56, the yield of acrylic acid in one pass is 5.2%. Conversion of propylene 93.0 56 and selectivity to acrolein and acrylic acid 96.8 56 are achieved.

Example 1 a d 15 to 21

Oxidation of propylene at atmospheric pressure

Catalysts were prepared in the same manner as described in Example 1, except that preseodymium oxide was not replaced by the following compounds in the following amounts:

X Compound Amount, %, 5 lanthanum nitrate 6.22 * 0.5 yttrium nitrate 5.48 ^Ru 0,5 ruthenium chloride 3.11 ^ 0.5 gallium nitrate 6.27 ^In 0,5 indium nitrate 5.86 ^Zr 0,5 zirconium chlorate 4.84

A fixed bed reactor made of a 0.75 cm stainless steel tube is not charged with 5 ml of each of the above catalysts. These catalysts were tested at a reaction temperature of 330 ° C using propylene, air and steam at a ratio of 1:10: 4 and a true contact time of 3.3 seconds. The results of these tests are shown in Table 3.

Tebulke3

Oxidation of propylene to acrolein and acrylic acid at atmospheric pressure using a catalyst of the formula.

Results , * Example Catalyst, X = Acrolein (ACR) ACR + AA Acrylic Acid (AA) Conversion 23 ^ 0.5 79.9 10.8 90.7 99.0 24 * 0.5 83.6 6.2 89.8 96.9 25 ^ 0.5 82.5 4.1 86.6 94.9 26 ^ 0.5 81.5 10.5 92.0 98.8 27 Mar: ^In 0,5 81.7 7.2 88.9 94.6 28 ^ 0.5 70.1 4.1 74.2 81.6

In the same manner as described above, these catalysts can be effectively used to oxidize isobutylene to methacrolein and methacrylic acid.

Claims (1)

Process for producing acrolein or methacrolein and acrylic or methacrylic acid from propylene or isobutylene in the vapor phase by oxidizing propylene or isobutylene with molecular oxygen at a temperature of 200 to 600 ° C in the presence of one molybdenum, oxygen, vizrnut, phosphorus, tungsten, nickel, cobalt and alkali metals, characterized in that ae uses a catalyst of the formula I VAWWx ^{! I)} where X is cerium, thorium, manganese, praseodymium, yttrium, zirconium, ruthenium, gallium, tin, indium, lanthanum, me3, tantalum or a mixture thereof; A is an alkali metal, thallium or a mixture thereof, D is nickel, cobalt, magnesium, zinc, cadmium, calcium, strontium or a mixture thereof, E is phosphorus, arsenic, boron, tungsten, sulfur, aluminum, a mixture thereof and a is greater than 0 but less than 5, and b is 0 to 4, c, f and g are 0.1 to 12 and x is the number of oxygen atoms needed to saturate the bonds of the other elements present.