DE2727195A1 - PROCESS FOR THE PRODUCTION OF METHACRYLIC ACID OR ACRYLIC ACID - Google Patents

Description

Process for the production of methacrylic acid or acrylic acid

The present invention relates to an improved process for the production of methacrylic acid or acrylic acid by oxidation of methacrolein or acrolein with molecular oxygen in the vapor phase in the presence of a catalyst the basis of the oxides of molybdenum, phosphorus, bismuth, copper, a halogen from the group of the elements chlorine, bromine and iodine and optionally at least one element from the group consisting of Fe, Cr, Ni, Mn, Sb, Te, Rh and Pd.

There are numerous known catalysts that are used in the oxidation of acrolein or methacrolein in acrylic acid or methacrylic acid are effective. The yields when using the However, catalysts in the production of methacrylic acid are low. The present invention is the result a search for more effective and desirable catalysts for the production of acrylic acid and methacrylic acid. In the vapor phase oxidation of acrolein or meth-

709882/0728

acrolein with molecular oxygen in the presence of the new catalysts according to the invention are surprisingly higher Yields of acrylic acid and methacrylic acid and higher selectivities for these products achieved.

The inventive method for producing acrylic acid and methacrylic acid by oxidation of acrolein or methacrolein with molecular oxygen in the vapor phase at a reaction temperature of about 200 ⁰ C to about 500 ⁰ C in the presence of an oxide catalyst and optionally in the presence of water vapor characterized in that as .oxidic catalyst a catalyst of the general formula

^Mo 12 ^P a ^Bi b ^Cu c ^M d ^X e ° f

is used, in which M at least one of the elements iron, chromium, nickel, manganese, tellurium, palladium, antimony and rhodium, X is chlorine, bromine or iodine, a, b and c are numbers in the range from 0.001 to 10, d is a number in the range from 0 to 10, e is a number of 5 or less and f is the number of oxygen atoms which saturate the valences of the other elements present necessary is.

The surprisingly advantageous catalysts according to the present invention Invention give improved yields of acrylic acid or methacrylic acid from acrolein or methacrolein in more effective, conveniently and economically at relatively low reaction temperatures. The heat output of the reaction is low so that the reaction can be easily controlled.

The most important aspect of the present invention is the catalyst employed. Anyone can do the catalyst any, identified by the above general formula

709882/0728

- 2T-

drew to be a catalyst. The catalysts used in the present invention can be used in various known ways, such as coprecipitation of soluble salts and calcining the product obtained.

The catalysts used according to the invention have preferred ranges with regard to their composition. Are preferred Catalysts in which a, b and c are numbers in the range from 0.01 to 5 and e is a number in the range from 0 to 1.0. More preferred are catalysts in which a is 1 to 1.5, and catalysts in which b is 0.1 to 5, further catalysts, where c is 0.1 to 1.0 and catalysts »where e is 0.01 to 0.5, Particularly preferred are catalysts of the general formula mentioned at the beginning, in which e is 0.01 to 2.0, as well as catalysts where d is 0. Catalysts in which X is chlorine are very particularly preferred. Catalysts of particular Of interest are those in which chlorine, bromine or iodine is present as an essential catalytic component. Are there particularly preferred catalysts in which chlorine is an essential catalytic component.

During the production of the catalyst, the various elements of the catalyst are combined and what is finally obtained Product calcined (calcined) with recovery of the catalysts. Numerous methods of association are known to those skilled in the art the catalyst elements and for annealing (calcining) the resulting product is known. Generally speaking, however the particular type of preparation of the catalysts used according to the invention is not critical.

However, there are methods of making the catalysts which have been found to be preferred. One of the preferred processes comprises the preparation of the catalysts in aqueous slurry with dissolution of the molybdenum and / or phosphorus

709882/0728

S '

ingredients containing phor and adding the remaining ingredients, Evaporation of this aqueous mixture and calcination, i.e. calcination of the catalysts obtained. Suitable molybdenum compounds, which can be used in the production of the catalysts indicated in this way include molybdenum trioxide, Phosphomolybdic acid, molybdic acid, ammonium unheptamolybdate and the like in the preparation of the catalysts according to the invention Usable phosphorus compounds include orthophosphoric acid, metaphosphoric acid, triphosphoric acid, phosphorus pentabromide, Phosphorus pentachloride and the like. The remaining catalyst components can in the form of their oxides, acetates, formates, sulfates, nitrates ,. Carbonates, hydroxyhalides or halides and the like. can be added.

The catalysts of the invention can preferably also by mixing the catalytic constituents in an aqueous Slurry or solution, heating the aqueous mixture to dryness and calcining, i.e. calcining the resulting products getting produced.

Excellent results are obtained by refluxing phosphoric acid and molybdenum trioxide in water for about 1.5 to 3 hours, although commercial phosphomolybdic acid can also be used with good results, adding the remaining constituents to the aqueous slurry and boiling them up to is heated to form a thick paste, at least one of the constituents being added in the form of a halide or oxyhalide, the product then being ^{air-dried at 110 to 120 °} C. and finally calcined. It is not yet fully understood where the halogen atom is in the catalyst product and its structure. Analysis by infrared and X-rays, however, shows that the catalyst consists largely of phosphomolybdate and that the halogen is in the form

709882/0728

a molybdenum oxyhalide is present.

Excellent results are obtained by using a coated one The catalyst used consists essentially of an inert support material with a particle diameter of at least 20 microns and an outer surface and a continuous coating of the catalyst active firmly adhered to the outer surface of the inert carrier material. The special coated catalyst consists of a core made of carrier material with an outer surface and a layer of active catalyst this outer surface.

The carrier material of the catalyst forms the inner core of the same. It is essentially an inert carrier material and can be essentially any particle size, but a diameter of at least 20 microns is preferred. Particularly preferred in connection with the present invention is the use in a large-scale reactor of those carrier materials which are spherical and have a diameter of about 0.2 to 2 cm. Suitable examples of essentially inert carrier materials are alundum, silicon dioxide, aluminum oxide, aluminum silicon oxide, silicon carbide, Titanium dioxide and zirconium oxide. Particularly preferred among these support materials are alundum, silicon dioxide, Alumina and alumina.

The catalysts according to the invention can support material and catalytically active product in essentially all weight ratios contained to each other. The limits of these proportions result only from the compatibility of the catalyst with the support material. Preferred catalysts contain from about 10 to about 100 percent by weight catalytically active material based on the weight of the

709882/0728

Carrier material

The coated catalysts can be produced in a number of ways. Basically the These catalysts are essentially produced by partially moistening the support material with a liquid. The carrier material must not be damp on the outer surface of the overall product. It should be prove to be dry to the touch. If the carrier material is moist, the active catalytic material bakes to separate Aggregates in the coating of the carrier material together. The partially moist carrier materials are then with brought into contact with a powder of the catalytically active material and the mixture stirred moderately vigorously until the has formed desired catalyst product. The moderately vigorous stirring is easily achieved by the fact that the partially moist Support material is placed in a rotating drum and the active catalyst product is added until nothing of this is absorbed by the carrier material. This production of the catalyst happens in very economical way.

The annealing of the catalyst the product is generally achieved by drying the catalyst components are heated to a temperature between about 300 and about 700 ⁰ C. The respective annealing temperature and duration to achieve the best results depends on the particular catalyst product used. The best annealing conditions for the catalysts according to the invention result from the exemplary embodiments.

The starting products in the process according to the invention for producing methacrylic acid are methacrolein and oxygen. In general, molecular oxygen is in the form of

709882/0728

Air is used, although oxygen gas can also be used. In general, from about 0.5 to about 4 moles of oxygen are employed per mole of aldehyde.

The reaction temperature used can vary depending on the catalyst used. Generally temperatures are used in the range of about 200 to about 500 ⁰ C, which temperatures are preferably from 250 to 37o C ^0.

The process according to the invention is expediently carried out in a fixed bed or fluidized bed reactor. The apparent Contact time can be as low as a fraction of a second and up to 20 seconds or more. The reaction can be carried out at atmospheric, superatmospheric or subatmospheric pressure, with absolute Pressures in the range of about 0.5 to about 4 atmospheres are preferred.

The catalyst used can be used either on a support material or without a support material. Suitable Carrier materials are alundum, silicon dioxide, aluminum oxide, boron phosphate, zirconium oxide, silicon carbide or titanium dioxide.

Are the catalysts described above according to the invention with acrolein or methacrolein in a fixed bed reactor used, the catalytically active components can be coated on an inert support material. on the other hand However, the catalytically active constituents can also be combined with one of the aforementioned support materials before their Layered on an inert carrier material have been mixed.

The present invention also includes the procedure that acrolein or methacrolein by a rapid

709682/0728

catalytic vapor phase reaction can be oxidized using the catalysts according to the invention with the proviso that a smaller amount of chlorine, iodine or bromine or an organic or organic halide is incorporated into the starting device.

By using the catalysts of the invention in the production of methacrylic acid or /. Acrylic acid gives excellent results in easily feasible reaction with low levels of by-products.

Examples 1 to 9

Various catalysts used in the present invention were prepared as follows:

example 1

^Mon 12 ^P 1 .32 ^Bi 0.5 ^Cu 0.25 ^C1 0.06 ° x Part A:

A slurry of 86.4 g (0.06 mol Mo) molybdenum trioxide and 7.6 g (0.067 mol P) 85% phosphoric acid in 500 ml distilled water was formed. The product was heated with stirring for 3 hours, so that phosphomolybdic acid of yellowish-green color was formed. To this slurry , 2.5 g (0.0125 mole Cu) of copper acetate was added. There was no change in the color of the reaction mixture. So then were 7.9 g (0.025 mol Bi) bismuthic, dissolved in 4.0 ml of concentrated hydrochloric acid was added. The Genisch was heated to boiling and evaporated to dryness in air at 110 ⁰ C overnight. The catalyst product was ground and the proportion of 20 to 30 US standard

709682/0728

-jr.

Mascherl (corresponding to 0.59 to 0.84 mm mesh width) screened and calcined for 3 hours at 400 ⁰ C and an air flow rate of 40 ml per minute.

Part B; '

A large batch of this catalyst was obtained by starting from 3500 ml of distilled water, 432 g of molybdenum trioxide, 38 g of phosphoric acid, 12.5 g of copper acetate, 39.5 g of bismuth chloride dissolved in 25 ml of concentrated hydrochloric acid. The mixture was heated overnight at 75 ⁰ C, evaporated to dryness in boiling temperature, dried overnight in an oven at 11O ⁰ C, ground and screened and calcined for 3 hours at 400 C and an air flow rate of 40 ml per minute.

Examples 2 to 9

The catalysts of these examples were calcined in the same manner as described in Example 1.

Example 2 ^Mo 12 ^P 1.32 ^Bl 0.5 ^Cu 0.25 ^Cl 0.04 ° x

This catalyst was prepared in the same manner as in Example

1 part B.

Example 3 ^Mo 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ^Cl 0.05 ° x

This catalyst was prepared in the same manner as in Example 1 except that the molybdenum trioxide and phosphoric acid were used were replaced by 118.3 g of commercially available phosphomolybdic acid and 1.84 g of 85% phosphoric acid.

709882/0728

-yi. AS

Example 4 ^Mo 12 ^P 1.32 ^Bl 0.5 ^Cu 0.25 ^Cl 0.055 ° x

This catalyst was used in the same manner as in the example 1 described, except that the hydrochloric acid by 15 ml of concentrated nitric acid was replaced.

Example 5

^Mo 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ^C1 0.06 ⁰ x

This catalyst was prepared in the same manner as in Example 1, except that bismuth chloride was used 5.8 g (0.025 mole Bi) of bismuth oxide was replaced.

Example 6

^Mo 12 ^P 1.32 ^Bl 0.5 ^Cu 0.25 ° x

This catalyst was prepared in the same manner as described in Example 1, except that no halogen was used in the preparation. The bismuth chloride was replaced with 5.8 g (0.025 mol Bi) bismuth oxide and no hydrochloric acid was used in the preparation.

Example 7

^Mo 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ° x

This catalyst was prepared in the same manner as described in Example 6, except that the bismuth oxide was replaced with 12.1 g of Bi (NOj) ₃ .5H ₂ O.

709882/0728

4 (ß

Example 8

^Mo 12 ^P 1:32 0:15 ^{Bl Cu} 0.3 ^Fe 0.1 ^Cr 0.1 0.1 ^{Nl Cl} 12:04 ⁰ x A slurry of 86.4 g (0.60 mole Mo) of molybdenum trioxide and 7.6 g (0.067 mol P) 85 # strength phosphoric acid made in 500 ml of distilled water. To this slurry were added 1.5 g (0.0075 mol Cu) copper acetate, 4.8 g (0.015 mol Bi) bismuth chloride, 5.0 ml concentrated hydrochloric acid, 1.4 g (0.005 Fe) iron - (- III) - chloride hydrate, 0.4 g (0.005 mol Cr) chromium oxide and 0.9 g (0.005 mol Ni) nickel acetate were added.

Example 9 ^Mo 12 ^P 1.32 ^Cu 0.2 ^Bl 0 _< 4 ^Sb 0.1 ^Nl 0.05 ^Cl 0.04 ° x

A slurry of 86.4 g (0.60 mol Mo) of molybdenum trioxide was obtained and 7.6 g (0.067 mol of P) 85 # phosphoric acid prepared in 500 ml of distilled water and refluxed for 3 hours heated to boiling. The color of the product obtained was yellowish green. To this slurry was added 0.7 g (0.005 moles Sb) of antimony oxide. The color changed to dark green and then 2.0 g (0.01 mol Cu) of copper acetate, 6.3 g (0.02 mol Bi) bismuth chloride, 3.5 ml concentrated hydrochloric acid and 0.4 g (0.0025 mol Ni) nickel acetate were added.

Examples 10 to 18

Production of methacrylic acid using various catalysts according to the invention.

The catalysts were prepared in the same manner as indicated above using appropriate amounts of the ingredients

709882/0728

manufactured.

A part of this Katalyaatorteilchen was in a 20 ecm
holding fixed bed reactor made of a ~ V2A steel pipe with 1.3
cm inner diameter and a 0.3 cm thick axial heat source. The reactor was heated to the reaction temperature under a stream of air and a starting mixture of methacrolein: air! Water vapor of 1: 6.2: 5.2 was over
passed the catalyst at an apparent contact time of h to 5 seconds. The reactor was operated under the reaction conditions for 1 to 5 hours and the reaction product was collected and analyzed. The reaction conditions and results of the experiments are given in Table I.
reproduced. The following definitions were used to measure
of the carbon atoms in the starting mixture and in the reaction product:

Moles of methacrylic % yield in a single pass = acid χ 100

Molo methacrolein in the starting chamber

Moles of total meth conversion = acrolein χ 100

Moles of methacrolein in the starting mixture

Yield at one time

Selectivity - slack; χ 100

Ge s'aratumwa'ndl ung

709882/0728

Tabel.lt? Z manufacture before. Methacrylic acid

CO T)

I. Reactive
tenp., ° C ³³⁷ 313 Results % yield
from Sssig-
acid at
unique
Sang Selectivi
tat -u meth
acrylic acid Sown
uawandiung applied
catalyst
manufacture at
game Catalyst j 316 316 yield
from meth
acrylic acid
at a-
Sang j
3.5 79.5 87.3 BiCl ₃ -THCl 10 ^Mo 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ^Cl 0, 06 ° fj ^Mo 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ^Cl 0.06 ° rj 313 330 69.4 6.6 74.6 94.5 BiCl ₃ -I-HCl
GroOaniatz 11 ^Mo 12 ^P 1.32 ^Bl 0.5 ^Cu 0.25 ^Cl 0.05 ° f \ 302 350 70.4 5.8 73.0 87.6 commercial
Phosphomolybdenum
acid-t-BiCl ₃ ^ -HCl 12th * ^to 12 ^P 1.32 ^Bi O, 5 ^Cu O, 25 ^C1 O, O55 ° f ^Ito 12 ^P 1.32 ^Cu 0.15 ^Bi 0.3 ^Fe 0.1 ^Cr 0.1 ^Ni 0.1 ^Cl 0.04 ° i 330 63.9 7.9 61.1 65.9 BiCl ₃ -I-HNO ₃ O 13
CO ^Mo 12 ^P 1.32 ^B1 0.5 ^Cu 0.25 ^C1 O, 06 ° f ^Mo 12 ^P 1.32 ^Cu 0.20 ^Bl 0.4 ^Sb 0.1 ^{Nl 0.05 Cl} 0.04 ° i 40.3 4.1 74.4 70.0 Bi ₂ O ₃₊ HCl OO,
co 1 ^{4 Ko} 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ° i 52.0 8.0 59.0 65.4 Bi ₂ O; no
halogen 0 ^{15 Ko} 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ° f 38.0 9.9 50.3 56.2 Bi (N0, V5H ₂ 0;
no halogen · * «!
»O 16
00 28.3 3.8 76.7 80.7 BiCl ₃ I-HCl 17th 61.9 4.4 79.5
ι ... ... -. 81.6 BiCl ₃ -THCl 18th 64.9

red t? d

VO

ου

K)

CD

Examples 19 to 21

Influence of the reaction temperature and the correct calcination of the catalyst in the production of methacrylic acid using the catalyst Mo ₁₂ P ₁ 3 ₂ ^Bi o 5 ^Cu O 25 ^C1 0 04 ° x *

Examples 19-20

The catalyst of Example 2 was calcined in the absence of the air stream for 3 hours at 400 ⁰ C and then reacted with methacrolein at 343 ⁰ C. In a second approach at 377 ⁰ C was implemented.

Example 21

The catalyst of Example 2 was reacted in the same manner as in Example 19 except that it was calcined in air and then reacted with methacrolein at 313 ° C.

The test results are shown in Table II below.

709882/0728

Table II

Influence of correct calcination and reaction temperature

when using the catalyst

32 ^Bi o 5 ^Cu O 25 ^C1 0

at
game Calcination Results, % Selek
activity total
conversion 19th
20th
21 without air
without air
in air yield
at a
malignant
Passage 60
80
73 13.1
17.5
91.5 7.9
14.1
66.7

From this it follows that the reaction temperature in connection with the correct calcination of the catalyst is essential for Obtaining the desired yields of methacrylic acid in the process according to the invention are.

Examples 22 to 28

Production of methacrylic acid using catalysts according to the invention:

Example 22

A catalyst of the formula 20 % 3 + 80 % Alundum was prepared as follows:

32 ^Bi o 5 ^Cu 0 25 ^C1 0 07 ° f ll

A solution consisting of 105.9 g of ammonium heptamolybdate (NH ₄ ) ₆ Mo _? 0 _{2 / f} .4H ₂ O (0.6 mol Mo) and 500 ml of distilled water were heated to the boil while stirring. 7.9 g of bismuth chloride BiCl, (0.025 mol of Bi) as a solution in

709882/0728

15 ml of concentrated hydrochloric acid were added. 2.5 g of copper acetate (0.0125 mol of Cu), 7.7 g of phosphoric acid (0.066 mol of P) and 2.5 g of hydrazine hydrate were added to this solution. The mixture was evaporated at the boil to dryness and dried overnight at 11O ⁰ C. The product was ground and sieved to a particle size of less than 80 US standard meshes (0.152 mm clear mesh size) and then layered on alundum balls with a diameter of 1/8 inch (= 3.175 mm) (product Norton SA 5223), by taking 50 g of alundum, moistening the alundum with 1.8 g of water and adding 16.7 g of the powdered catalyst material in 5 equal portions. During and after each addition, the alundum was rolled in a glass jar. The resulting product was then dried in an oven at 110 to 120 ° C overnight.

Example 23

20 96 Mo ₁₂ PJ 32 ^Bi 0 5 ^Cu 0 25 ^C1 0 I6 ° f ^{+ 80} ^ Alundum

This catalyst was prepared in the same manner as described above except that the hydrocine hydrate was omitted

became.

Example 24

15% Mo ₁₂ P ₁ .32 ^B i _O .5 ^Cu f o.25 ^C1 O.O6 ^O + ⁸³ * Alundum The catalyst component was 1 part A prepared in the same manner as in Example, ground and classified to a particle size of less than 50 US standard meshes (= 0.25 mm clear mesh size) sieved and then layered on alundum balls with a particle size of 3.175 mm (product Norton 5223) by taking 25 g of alundum, the alundum with 1.3

709882/0728

g of water moistened and then 4.17 g of the powdered catalyst product was admitted in a single time. The resulting product was then left in an oven overnight dried at 125 ° C.

Example 25

25th % Mo ₁₂ P ₁ .3 ₂ Bi _0t3 Cu _{0 <73} Cl _0t06 0 _f + 75 % Alundum

This catalyst was prepared in the same manner as described in Example 24 except that the alundum was 1.8 g Water was moistened and 6.94 g of the powdered catalyst material was added in two equal portions.

Example 26

40 % Mo ₁₂ P ₁ 32 ^Bi o 5 ^Cu O 25 ^C1 0 06 ° f ⁺ ^ ⁰ ^ Alundum This catalyst was prepared in the same way as described in Example 24, except that the alundum was moistened with 2.1 g of water and 11 , 1 g of the powdered catalyst material was added in three equal portions. The catalyst was then dried in an oven at 11O ⁰ C.

Example 27

25% Mo ₁₂ P ₁ .32 ^Bi Q.5 ^Cu 12:25 00:06 ° ^{C 1} x * ⁷⁵ * Alundum The active catalyst was prepared in the same manner as described in Example 1 part B, and ground to a particle size of less than 50 US Standard meshes (corresponding to 3.175 mm clear mesh size) sieved and then on alundum particles (product Norton SA 5223) of the fraction

709882/0728

tion of 10 to 30 US standard meshes (corresponding to 0.59 to 1.95 mm clear mesh size) by using 50 g of Alundum of this particle size, this product was moistened with 4 g of water and 16.7 g of the powdered Catalyst material was added in three portions, each weighing 3 g, and a 6.7 g portion. The resulting material was dried at 110 to 120 ⁰ C.

Example 28

35 % Μο ₁₂ ^ρ 1.32 ^Β1 0.5 ^0ια 0.25 ⁰¹ 0.06 ⁰ χ + ⁶ ^ * Alundum This catalyst was prepared in the same way as described in Example 27, except that the alundum was moistened with 2.2 g of water and 26.9 g of the powdered catalyst material with a particle size of less than 80 US standard mesh (corresponding to 0.175 mesh size) was added in 4 equal proportions.

Examples 29 to 48

Production of methacrylic acid using various coated catalysts according to the present invention.

The catalysts were prepared in the same manner as described above using the appropriate amounts of the ingredients. The resulting products were ^{calcined for 3 hours at 400 °} C. in air to form the active catalyst product, which consisted of the alundum support material with a continuous, strongly adhering layer of the active catalyst product.

709682/0728

ik '

Each catalyst prepared according to Examples 22-28 was used in the reactor described in Examples 10-18 given. The reactor was heated to reaction temperature in a stream of air and then a starting mixture of Methacrolein: air / water vapor: nitrogen from 1: 5.3: 5.6: 4.6 passed over the catalyst with an apparent contact time of 2.5 to 2.7 seconds. The reaction conditions and Test results are given in Table III below.

709682/0728

Table III Results of Coated Catalysts in the Production of Methacrylic Acid

: 3example

catalyst

Reaction

tenp., C

Results, %

Methacrylic acid

acetic acid

29
reduced

30th
31
32

co; unredusier ¹
CD)

CO
K)

34
35
35

2CS4

^FiO 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ^Cl 0.07 ° f ^{+ 80% A} ^ ndum ^Ko 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ^Cl 0.07 ° f ^{+ 80%} Alundum ^Mo 12 ^P 1.32 ^Bi 0.5 ^Cu 0.25 ^Cl 0.07 ° f ^{+ 80} * Alundun

40.6 64.0 68.3 68.0

1.5 3.6 4.6 5.9

_2O5i Mo ₁₂ P _{1> 32} Bi ₀ , 5 ^Cu 0.25 ^C1 0, i6 ⁰ f ^{+ 30} * ^Alundun j ^ 02

2Ο5ί Ko ₁₂ P _{1> 32} Bi _{o> 5} Cu _{o> 25} Cl _{Of i6} 0 _f ♦ 8056 Alundun j 327

20Ji Mo ₁₂ ? ^ 35 ³ⁱ Q c- ^ Q 25 ^C ^ 0 I6 ° f ^{+ 8} ^ ³ & lva.aam \ 338

2C56 Mo ₁₂ P ₁ , ₃ 2 ³ⁱ 0.5 ^Cu 0.25 ^C1 0.16 ° f ^{+ 80} % Alundun; ₃₅ 2

37

Beis-3. 1
Part A

36
39

15% "O ₁₂ P _{1 '32} ³ⁱ o 5 ^Cu o 25 ^C1 0 Ο6 ^Ο · ρ ^{+ 75} ^ Alundun

15% Ko ₁₂ P ₁ ^ ₃ 2 ^Bi 0.5 ^Cu 0.25 ^C1 0.06 ° f ^{+ 75%} Alundun 2555 Mo. _O P. · -, 3i _o ,, Cu _n --Cl _{n ηΑ} 0 ^ + 7556 Alundua

40
. 1

Part A

- ^Ho 12 ^? 1.32 ³ⁱ 0.5 ^Cu 0.25 ^Cl 0.06 ⁰ i 38.0 60.0 66.0 69.4

Seed change

48.0 78.0 86.7 90.8

30.8 48.3 55.7

49.5

3.9

selectivity

84.0 82.0 79.0 75.0

CO

■ σ m O

Table III - Continuation of Sr.Tgbr.isse sit 'stratified catalysts at the manufacturer 1 ur .. <? of methacrylic acid

example

41

42

, 25 ^C1 0.06 ° f

^85%

C /.

acid

acid

40% Ko ₁₂ P ₁ 32 ^Bi 0 5 ^Cu 0 25 ^C1 0 06 ⁰ ^ ^{+ 6θ5ί Alunduc} j

40% M.

₁₂ P _1t3 2 ^sl 0 _t 5 ^Cu 0 _t 25 ^C JO, 0 6 ° f ⁺

36.5
49.2
63.2

1.9 2.6 5.8

44 j Ex. 1; 25%

Tsil B 45

, 32 ^Bi 0.5 ^Cu 0.25 ^C1 0.06 ° f ^{+ 15%} Alundual

3eisp. ? Tail B

25% Ko ₁₂ P ₁ , 3 ₂ Bi ₀ , 5 ^Cu 0.25 ^C1 O, O6 ^O f ^{+ 7} ^ ^AlunduD !

46 j 25% Ko ₁₂ P _1f52 3i _0f5 Cu _0t25 Cl _0f06 0 _f + 75% alundum; 60.9
64.0
63.2

35% Kc

48 j 35% Mo ₁₂ P ₁ ^ ₃₂ Bi ₀ ^ ₅ Cu _{0> 25} C1 _O ^ _o6 O _f + 65% AlundUBi;

; 63.0

j '60.8

1.7 5.6 4.6

4.8 8.1

Gssanit— conversion

43.0 60.4 85.3

68.6 90.0 89.0

78.0 85.0

vity

84.0 81.0 74.0

89.0!

! 71.0

71.0

80.0 ! , t 71.5

Example 49

In the same way as described in Examples 10 to 18, acrylic acid was obtained from acrolein using the catalyst of Example 1 Part A (Mo ₁₂ ^p -i 3? ^Bi o 5 ^Cu 0 25 Cl ₀ QgOf) ^ηβΓ 6 ^βδΐ β11 * · The Results of this experiment show a single pass conversion to acrylic acid of 75.1 % _t, a total conversion of 85.3 % and a selectivity of 88.0 % at a reaction temperature of 317 ^° C.

709882/0728

Claims (35)

Patent claims: \ "Ti process for the production of acrylic acid or methacrylic acid ^ V by oxidation of acrolein or methacrolein with molecular oxygen in the vapor phase at a reaction temperature in the range of about 200 to about 500 ⁰ C.
in the presence of an oxidic catalyst and, if appropriate, in the presence of steam, characterized in that the oxidic catalyst is one of the general formula is used where M is at least one of the elements
Iron, chromium, nickel, manganese, tellurium, palladium, antimony and rhodium, X chlorine, bromine or iodine, a, b and c numbers in the range from 0.001 to 10, d a number from 0 to 10, e a number from 0 to 5 and f is the number of oxygen atoms that are used to saturate the free valences of the other im
Catalyst elements present are necessary. 2. The method according to claim 1, characterized in that
the catalyst at a temperature in the range of 525
has been calcined in air up to 45O ⁰ C. 3. The method according to claim 1 or 2, characterized in that the reaction temperature is ^{250 to 370 0 C,} 4. Process according to Claims 1 to 3, characterized in that e is 0. 709882/0728 ORIGINAL INSPECTED 5. The method according to claims 1 to 3, characterized in that a, b and c numbers in the range from 0.01 to 5 and e one Number is from 0 to 1.0. 6. Process according to Claims 1 to 5, characterized in that a is a number from 1 to 1.5. 7. Process according to Claims 1 to 6, characterized in that b is a number from 0.1 to 0.5. 8. The method according to claims 1 to 7, characterized in that c is a number from 0.1 to 1.0. 9. The method according to claims 1 to 3 and 5 to 8, characterized in that e is a number from 0.1 to 0.2, 10. The method according to claims 1 to 3 and 5 to 8, characterized in that e is a number from 0.01 to 0.5. 11. The method according to claim 10, characterized in that M is at least one element selected from the group consisting of Fe, Cr and Ni. 12. The method according to claims 10 and 11, characterized in that X is chlorine. 13. The method according to claims 10 to 12, characterized in that the catalyst of the formula Mo ₁₂ ^Bi n 5 ^P 1 3? ^Cu O ^9C 5 CIq o6 ° f ^en-t speaks. 14. The method according to claims 1 to 13, characterized in that that the catalyst is coated on an inert support material. 709882/0728 15. The method according to claim 14, characterized in that the catalyst consists essentially of an inert support material having a particle diameter of at least 20 microns and an outer surface and on the support material a continuous layer of the solid adhering to the outer surface of the substrate having active carrier material. 16. The method according to claims 14 and 15, characterized in that that the content of active catalyst is from about 10 to about 100 percent by weight of the inert support material. 17. The method according to claims 14 to 16, characterized in that the carrier material is silicon dioxide, aluminum oxide, Alundum, aluminum silicon oxide, silicon carbide, titanium dioxide or zirconium oxide is used. 18. The method according to claims 14 to 17, characterized in that the particle size of the inert carrier material 0.2 to 2 cm. 19. Catalyst product of the general formula ^Mo 12 ^P a ^Bi b ^Cu c ^M d ^X e ° f where M at least one of the elements iron, chromium, nickel, manganese, tellurium, palladium, antimony and rhodium, X chlorine, Is bromine or iodine, a, b and c are numbers in the range from 0.01 to 10, d is a number from 0 to 10, e is a number from 5 or less and f is the number of oxygen atoms which saturate the valences of the others in the catalyst present elements is necessary. 20. Catalyst according to claim 19, characterized in that it is at a temperature in the range from 325 to 450 ° C is calcined in air. 709882/0728 21. Catalyst according to claim 19 or 20, characterized in that that a, b and c are numbers in the range from 0.01 to 5 and e is a number of 1.0 or less. 22. Catalyst according to claims 19 to 21, characterized in that that a is 1 to 1.5. 23. Catalyst according to claims 19 to 22, characterized in that that b is 0.1 to 0.5. 24. Catalyst according to claims 19 to 23, characterized in that that c is 0.1 to 1.0. 25. Catalyst according to claims 19 to 24, characterized in that that e is 0.01 to 0.5. 26. Catalyst according to claims 19 to 24, characterized in that that e is 0.01 to 0.2. 27. Catalyst product according to claims 19 to 26, characterized in that d is 0. 28. Catalyst according to claims 19 to 26, characterized in that M is nickel in combination with at least one of the elements chromium, manganese, tellurium, palladium, antimony
and is rhodium. 29. Catalyst according to claims 19 to 27, characterized in that that M is a mixture of iron, nickel and chromium " 30. Catalyst according to claims 19 to 29, characterized in that that X is chlorine. 31. Catalyst according to claims 19 to 30, characterized in that it is coated on an inert support material. _709882/0728 32. Catalyst according to claim 31, characterized in that it consists essentially of an inert support material having a particle diameter of at least 20 microns and having one outer surface and one on the outer Layer of this carrier material firmly adhering continuous layer consists of the active carrier material. 33. Catalyst according to claim 31 and 32, characterized in that the active catalyst ingredient is about 10 to about 100 percent by weight of the inert carrier material. 3 ^. Catalyst product according to claims 31 to 33, characterized characterized in that the carrier material is made of silicon dioxide, aluminum oxide, alundum, aluminum silicon oxide, silicon carbide, Titanium oxide or zirconium oxide is made. 35. Catalyst product according to claims 31 to 3 '+, characterized characterized in that the particle size of the inert support material is 0.2 to 2.0 cm. 709882/0728