DE2752223A1 - METHOD FOR THE SIMULTANEOUS PREPARATION OF METHACRYLIC ACID AND A METHACRYLATE OR OF ACRYLIC ACID AND AN ACRYLATE - Google Patents

Description

The invention relates to a method for simultaneous production from methacrylic acid and a methacrylate or from acrylic acid and an acrylate; it relates in particular to a method for simultaneous production of methacrylic acid and a methacrylate or of acrylic acid and an acrylate by reacting methacrolein or acrolein with an aliphatic alcohol and Molecular oxygen in the gas phase using a catalyst which consists of or contains (1) palladium, (2) Phosphorus, (3) antimony, (4) X and (5) oxygen, where X is at least means an element that is selected from the group consisting of potassium, sodium, lithium, rubidium, cerium, beryllium, lead, magnesium, Calcium, strontium, zinc, barium, thorium, bismuth, chromium, iron,

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21b222J

Nickel, cobalt, vanadium, manganese, tin, uranium and rhenium.

According to a further preferred embodiment, the method comprises of the invention the introduction of a phosphoric acid or a phosphorus compound produced by chemical conversion during the Reaction can form a phosphoric acid in the reaction system.

For the synthesis of methacrylic acid by the oxidation of methacrolein A number of catalysts have already been proposed in the gas phase. Almost all of these catalysts show, however a low activity on · In addition, if the reaction is carried out at elevated temperature to the Conversion (sales) to increase, large amounts of undesirable By-products such as carbon monoxide, carbon dioxide, acetic acid and the like. So that the yield of methacrylic acid per pass is very high is low.

The catalysts described in Japanese Patent Laid-Open Nos. 67 216/1973 and 61 416/1973, which have improved catalytic activity and selectivity, contain, as a main component, phosphomolybdic acid or its salts. However, catalysts based on phosphomolybdic acid have the disadvantage that the catalyst life is short. Once they have lost their activity, it cannot be restored by a simple treatment such as reclamation. If the temperature of the reaction or calcination exceeds 450 ° C, their catalytic activity suddenly decreases. They are thermally unstable and are not always available for large-scale use. aside from that

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ORIGINAL INSPECTED

conventional phosphomolybdic acid based catalysts have a remarkably short catalyst life when the Implementation carried out at a particularly high space velocity will.

In Japanese Patent Laid-Open No. 30826/1975, a method for producing methyl methacrylate is described, at which is a gas mixture of methacrolein, methanol, oxygen, water vapor and nitrogen in the gas phase in the presence of a catalyst the molybdenum-vanadium-tungsten series is reacted. The process is far from being technically satisfactory to be because the yield of methyl methacrylate is very low.

In Japanese Patent Laid-Open No. 37719/1975, a Described catalyst containing palladium, phosphorus and oxygen. Methacrylic acid is produced by the oxidation of Methacrolein with molecular oxygen in the presence of this catalyst. The desired product, methacrylic acid, becomes Formed in higher yield and with higher selectivity, but a comparatively large amount of steam is required for this. However, the larger the charge, the larger the apparatus, which is important for carrying out the process on an industrial scale and undesirable from an economic point of view is. Since this process is only aimed at the production of methacrylic acid, it is of course impossible to use it at the same time to make an ester.

Extensive research has now been carried out to find the

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to eliminate the disadvantages described above, and these investigations have led to the present invention.

According to the present invention, methacrolein or acrolein can be oxidized at low temperature, e.g. at 160 to 350 ° C, whereby nan receives methacrylic acid and a methacrylate or acrylic acid and an acrylate in high yields at the same time. It will the formation of by-products such as acetic acid, carbon monoxide and carbon dioxide, which is a consequence of the degradation, is well suppressed. The amount of hydrogen to be supplied during the reaction can be very large be small, which is one of the important features of the invention. In addition, the catalyst used in the present invention is thermal stable and therefore has a much longer useful life (service life), especially when the implementation is at high space velocities. The inventive Process is not only economically advantageous, but also industrially epoch-making.

The catalyst used according to the invention consists of or contains (1) palladium, (2) phosphorus, (3) antimony, (4) X and (5) oxygen, where X is at least one element selected from the group consisting of potassium, sodium, lithium, rubidium, Cerium, beryllium, lead, magnesium, calcium, strontium, zinc, barium, thorium, bismuth, chromium, iron, nickel, cobalt, Vanadium, Manganese, Tin, Uranium and Rhenium, and it has a long useful life (life) that of the known ones Phosphomolybdic Acid Based Catalysts Is Clearly Superior · It was surprisingly found that the catalyst at is resistant to elevated temperatures, e.g. at 600 C.

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However, it has been shown that this catalyst as such is not yet completely satisfactory because part of the Phosphorus, which is one of the essential components of the catalyst, is the catalyst system during the conversion, albeit in a very small amount, leaves. As a result, the semi-permanent required for commercial catalysts Lifespan cannot always be achieved.

It has now been found that when the reaction is carried out in the presence of the catalyst, the catalyst stabilizes and its useful life (lifespan) can be further extended if you operate continuously or intermittently Phosphorus replenished in an appropriate amount corresponding to the amount of phosphorus leaving the catalyst system.

The inventive method is epoch-making and of great value for industrial use, since methacrylic acid and a methacrylate or acrylic acid and an acrylate can be selectively produced over long periods of time in high yields,

The expression "a phosphoric acid or a phosphorus compound which can form a phosphoric acid during the reaction by a chemical conversion ¹ * (hereinafter referred to as a phosphorus-containing compound), which is to be fed to the reaction system according to the invention, is used here to include any phosphoric acids and phosphorus compounds, which can form a phosphoric acid through a chemical reaction, such as hydrolysis, oxidation and the like, such as orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphoric acid.

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Acid, hypophosphorous acid, phosphine, organic phosphoric acids, solid phosphoric acid and the like.

The phosphorus-containing compound can de «reaction system be supplied in any suitable manner. For example, if the phosphorus-containing compound is water-soluble, it can for use in the reaction can be dissolved in water uniformly so that they can enter the reaction system together with the water is fed. If the phosphorus-containing compound is solid, such as a solid phosphoric acid, this solid material can be introduced before the catalyst layer. When water vapor is introduced and comes into contact with the filled material, A phosphoric acid is formed from the latter, which is transported to the catalyst layer together with the water vapor. If the Phosphorus-containing compound is gaseous, a gas mixture of the same and air can be fed to the catalyst layer.

The amount of phosphorus-containing compound that will be supplied should vary within a wide range. In general, the phosphorus-containing compound is used in a supplied in such an amount that the amount of that contained in the compound Phosphorus preferably 5 to 1 χ 10, in particular

0.5 to 1 χ 10 percent by weight, based on the total amount of water and an aliphatic alcohol added during the reaction will be.

The catalyst preferably used in the present invention has the following Composition;

Pd P. Sb X .0 whether ede

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* 27b2Z23

wherein X is at least one member selected from Group potassium, sodium, lithium, rubidium, cerium, beryllium, lead, magnesium, calcium, strontium, zinc, barium, thorium, Bismuth, chromium, iron, nickel, cobalt, vanadium, manganese, tin, uranium and rhenium ^ and the indices a, b, c, d and e the number of Pd, P, Sb, X and O atoms mean, where a = 1, bsi to 42, c = 0.1 to 15, d = 0.1 to 15 and e represents a number, which is determined by the valences of the other elements and is usually 3.75 to 150.5.

A particularly preferred catalyst has a composition of the formula given above, the ratio being between the indices a, b, c, d and e is within the following range: a: b: c: d: e = 1: (1 to 28) :( 0.2 to 10) :( 0.1 to 10) : (6.4 to 101).

The catalyst according to the invention can be based on conventional ones known per se Manner, for example using the methods described below.

In one case, compounds of the respective constituent elements and the carrier, if a carrier is used, mixed together. The mixture obtained thereby becomes dry evaporated and then the dried product is calcined.

In another case, a solid support is impregnated with compounds of each constituent element. This impregnated The carrier is evaporated to dryness and then calcined.

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In another case, a solid support is impregnated with compounds of some constituent elements and then subjected to a heat treatment, preferably at a temperature of 200 to 700 ° C. The partially impregnated carrier is made with compounds the other constituent elements are further impregnated. This carrier, impregnated twice, is evaporated to dryness and then calcined.

In each of the processes described above, the calcination temperature is preferably within the range from 300 to 700, in particular within the range from 400 to 550 ° C. Galcination or heat treatment can be used if necessary in an atmosphere of a reducing agent such as hydrogen, hydrocarbon and the like.

Examples of connections of each component element are given below specified.

Examples of the palladium compound include palladium chloride, Palladium nitrate, palladium sulfate, palladium black and the like.

Examples of the phosphorus compound include orthophosphoric acid, Phosphorous acid, hypophosphorous acid, pyrophosphoric acid, Metaphosphoric acid, polyphosphoric acids, their salts and the like.

Examples of the antimony compound include oxides, hydroxides and chlorides of antimony, such as anti Mondi chloride, antimony pentachloride, antimony trioxide and the like.

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Examples of the compound of component X include nitrates, Hydrochlorides, phosphates, sulfates, oxides, hydroxides of the component X and the like.

More specific processes for preparing the catalyst of the invention are explained in more detail below:

To an ammonia solution of a suitable palladium salt such as palladium chloride, orthophosphoric acid (as 85% aqueous Solution), phosphorous acid, (de-phosphorous acid or any other phosphoric acid or a salt thereof is added, whereby a clear solution is obtained. For this clear solution there is also a Metal salt or an oxide of antimony (e.g. antimony trioxide) and a metal salt or an oxide of component X are added, with nan receives an aqueous solution. A suitable carrier is impregnated with this aqueous solution, evaporated to dryness and then calcined in air at 300 to 700 ° C., preferably at 400 to 550 ° C., for 5 or more hours.

The carrier, which is first impregnated with a palladium salt and heat-treated at a temperature of preferably 200 to 700.degree can be impregnated with phosphoric acid, antimony trioxide and the X compound and then calcined. It can but also the carrier, which has been impregnated with antimony trioxide and the X compound and treated with heat treatment, with palladium chloride, dissolved in ammonia water, impregnated and then calcined in air and in a reducing atmosphere, such as hydrogen, be warned. The substance obtained is nit

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impregnated with the phosphorus compound and then calcined.

In any case, the activity of the catalyst is not adversely affected. The catalyst can have a carrier in order to reduce the catalyst concentration, to increase the catalyst strength or to improve the economy of the catalyst 2U . A suitable amount of a carrier can be impregnated with a small amount of the catalyst. A large amount of a carrier can also be used.

Inert substances such as silica sol, silica gel, Silicon carbide, a-aluminum oxide, alundum, celite, boiling stones, Aluminum powder, silica hydrogel and the like can be used. The catalyst can be in the form of spherical granules, pellets, Particles crushed to an appropriate size, tablets and the like can be used.

The aliphatic alcohol used here is, for example, methanol, ethanol, propanol and the like.

The molecular oxygen used here is usually air. The oxygen can be mixed with an inert gas, which does not adversely affect the reaction such as nitrogen, carbon dioxide and the like., Are diluted.

Methacrolein or acrolein and oxygen are added to the reaction system fed in the form of a gaseous feed mixture in proportions such that the molar ratio of methacrolein or acrolein to oxygen preferably l: (0.5 to 30),

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in particular 1: (1 to 8 ^.

When methacrolein or acrolein in the presence of the invention Catalyst and is oxidized by oxygen in the absence of an aliphatic alcohol to produce methacrylic acid or acrylic acid, the presence of water vapor is essential. In the absence of water vapor, oxidation occurs from methacrolein or acrolein to methacrylic acid or acrylic acid only to a very small extent. Since when performing the invention If an aliphatic alcohol is present, the desired products can be methacrylic acid and methacrylate or acrylic acid and acrylate can also be obtained in high yields in the absence of steam. The selectivity for methacrylic acid and methacrylate or acrylic acid and acrylate is very high. By introducing a small amount of water vapor can however, the conversion of methacrolein or acrolein can be further accelerated and the yield of methacrylic acid and methacrylate or acrylic acid and acrylate is further increased.

The steam is added to the gaseous feed mixture in proportions such that the amount of steam is preferred 0.1 to 28 mol, in particular 0.5 to 10 mol per mol of methacrolein or acrolein.

The aliphatic alcohol is preferably used in an amount of 0.1 to 25 moles, particularly 0.3 to 10 moles, per mole of methacrolein or acrolein was introduced.

The temperature for carrying out the reaction is not so critical. The reaction can preferably be carried out at a temperature of 180 to

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-Jf-

370 ° C, in particular at 200 to 330 ° C, can be carried out.

The reaction can be carried out at atmospheric pressure or at lower or higher pressures. In general it is advisable to carry out the reaction at atmospheric pressure. A preferred pressure range is 0.3 to 15 at.

The gaseous feed mixture can be introduced at any desired space velocity, preferably it is introduced at a space velocity of from 300 to 15,000 liters of gas / liter of catalyst hour, more preferably from 700 to 8000 liters of gas / liter of catalyst hour. _m

According to the invention, satisfactory results are obtained even if the reaction with space velocities of up to 2000 to 8000 1 gas / l catalyst χ hour is carried out. In addition, the useful life of the catalytic converter is maintained for a long period of time under such conditions.

The catalyst of the invention can be in any form, e.g.

in the form of a fixed bed, a fluid bed and a moving bed

Bettes, can be applied.

The catalyst according to the invention and the process according to the invention are explained in more detail by the following examples, but without being restricted thereto. The ones in the examples the expressions used "conversion (conversion) of methacrolein or acrolein", "selectivity for methacrylic acid or acrylic acid",

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"Selectivity for a methacrylate or an acrylate", "Yield of methacrylic acid or acrylic acid", "Yield of methacrylate or acrylate "and" space velocity "are defined as follows:

Conversion (conversion) of methacrolein or acrolein = Moles of converted methacrolein or acrolein .-_ ^ Moles of the supplied methacrolein or

Acroleins

Selectivity for methacrylic acid or acrylic acid =

Moles of methacrylic acid or acrylic acid formed , __ ^ moles of methacrolein or acrolein converted

Selectivity for a methacrylate or an acrylate = Moles of methacrylate or acrylate formed .-_ ^ Moles of converted methacrolein or

Acrolein

Yield of methacrylic acid or acrylic acid =

Mole of methacrylic acid or acrylic acid formed ._. ^ Moles of methacrolein or acrolein added

Yield of methacrylate or acrylate =

Moles of methacrylate or acrylate formed - - Moles of methacrolein or acrolein added

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-JMT-

Space velocity (SV) Flow rate ^ of a gaseous feed

mixture (1 Gas / shock)

Volume of the filled catalyst (1 catalyst)

* calculated on the basis of normal temperature and normal pressure. example 1

While 16.0 g of Aerosil (SiO ₂ ) were heated and stirred, 0.4 g of antimony trioxide and 0.17 g of magnesium phosphate (III) were added. The mixture was concentrated by heating, then evaporated to dryness and then dried at 100 ° C. for 8 hours. The dried mixture was impregnated with an aqueous ammonia solution containing 0.44 g of palladium chloride, evaporated to dryness, then washed repeatedly with 10 l of distilled water and dried. * The dried product was subjected to a heat treatment in the air at 450 ° C. for 5 hours and then it was heat-treated in a hydrogen atmosphere at 450 ° C. for 5 hours. The product was impregnated with 6.5 g of un teip hos ρ hearing acid (30 jCig) and evaporated to dryness. The dried product was then calcined in air at 450 ° C. for 5 hours. The product obtained, hereinafter referred to as catalyst A, had a composition corresponding to the following formula

^Pd 1.0 ^P 12.3 ^Sb 1.0 ^Mfl 0.5 ° 33.75

A stainless steel reaction tube with an inside diameter

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of 20 mm was filled with 10 ml of the catalyst A and in a Bath ou * immersed in a molten nitrate. Using this reaction tube, which was filled with catalyst A, the oxidation of methacrolein was carried out for 120 days. Trimethyl phosphate was used as the phosphorus-containing compound in In the form of a 0.1% solution (i.e. in the form of a methanol-water solution) used. This solution was introduced in an amount of 5 ecm per hour.

A gaseous feed mixture contained methacrolein, methanol, oxygen, water vapor, nitrogen and phosphorus in

-3

a relative molar ratio of 1: 1: 2: 5.5: 18.1: 1.8x10.

The gaseous feed mixture was moving at space velocity (SV) of 1565 1 gas / l catalyst supplied χ hour. The products obtained were determined by gas chromatography. The results obtained are shown in Table I below.

Table I.

Reacti- Temp.des Methacrole- Selectivity Methacryl- Methylmethonszeit Nitratba- in-Conversion for methacrylic acid-ausacrylat-Aus (days) des ( ⁰ C) {%) acid + methyl- loot {%) loot (%)

methacrylate)

At first
step 285 74.5 89.3 40.0 26.5 40 285 74.7 89.2 40.3 26.3 120 285 74.7 89.2 40.1 26.5

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In the production of methacrylic acid and methyl methacrylate from methacrolein and methanol, small amounts of by-products were obtained, namely 1.0 % acrylic acid, 0.5 % acetic acid, 2.5 % carbon dioxide and 4.0 % carbon monoxide.

Example 2

Example 1 was repeated, this time metaphosphoric acid in the form of a 0.1 solution (i.e. in the form of a methanol-water solution) was used as a phosphorus-containing compound in place of trimethyl phosphate. The remaining reaction conditions were the same as in Example 1. The results obtained are shown in Table II below.

Table II

Reacti- Temp. Des Methacrole- Selectivity Methacrylate- Methylmethonszeit Nitrate ba- in conversion for methacrylic acid-ausacrylate-Aus (days) des (° C) (%) acid + methyl booty {%) booty {%)

methacrylate)

At first
step 285 74.3 88.6 39 8th 26.0 40 285 74.4 88.6 39 8th 26.1 120 285 74.5 88.5 39 9 26.0

In the production of methacrylic acid and methyl methacrylate from methacrolein and methanol, small amounts of by-products were obtained, namely 1.5 % acrylic acid, 0.7 % acetic acid, 2.0 % carbon dioxide and 4.3 % carbon monoxide. '

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AT-

40

Example 3

In a manner similar to Example 1, a catalyst having the same composition as in Example 1 was prepared, wherein this time, however, the un teip hos ρ hearing acid by phosphorous acid was replaced. Using the catalyst, the reaction was carried out in a manner similar to Example 1. the The results obtained are given in Table III below,

Table III Reokti- Temp. Des Methacrole- Selectivity Methacryl- Methylmeth-

on-time nitrate ba-in conversion for methacrylic acid ausacrylate Aus ·

(Days) des (° C) {%) acid + methyl prey (%) prey (%)

inethacrylate (? O

At first
step 281 75.1 88.5 40.2 26.3 40 281 75.0 88.8 40.5 26.1 120 281 75.1 88.3 40.3 26.0

In the production of methacrylic acid and methyl methacrylate from methacrolein and methanol, small amounts of by-products were obtained, namely 1.6 % acrylic acid, 0.4 % acetic acid, 2.3 % carbon dioxide and 4.3 % carbon monoxide.

Example 4

The reaction described in Example 1 was repeated, but this time using acrolein instead of methacrolein. The results obtained are given in Table IV below.

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Tobelle IV

Reokti- Temp. Des acrolein- Selectivity Acrylic acid- Methylacrylatonszeit Nitrotbo- Umwond- for Acrylic acid- Yield Yield {%) (days) des (° C) treatment (jC) re + Methylacry- {%)

lot (%)

At first-
step 280 98.2 95.7 66 5 27.5 40 280 98.3 95.7 66 8th 27.3 120 280 98.1 95.6 66 3 27.5

In the production of acrylic acid and methyl acrylate from acrolein and methanol, small amounts of by-products were obtained, namely 1.0 % acetic acid, 1.5 % carbon monoxide, 1.2 % carbon dioxide and 0.5% acetone.

Example 5

The implementation was carried out under the same conditions as in example 1, but this time not containing any phosphorus Connection was supplied. The results obtained are given in the following table.

Example 6

The implementation was carried out under the same conditions as in example 4 carried out, this time no phosphorus-containing compound was fed. The results obtained are shown in the following table · V.

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ZZ

Table V

Ex. Reaction Temp ) Methacrolein 74.7 Selecti Meth methyl No. Time nitrate conversion 70.1 vity for acrylic- met h- (Days) baths (° C) 00 Acrolein Methacrylic acid- acrylate conversion acid + methyl- Exertion Exertion methacrylate (^) te (%) te (%) At first 5 step 287 88.8 40.0 26.3 10 287 90.2 39.1 24.1 Ex. Reaction Temp 98.0 Selecti acrylic Methyl- No. Time nitrate 92.0 vity for acid- acrylate (Days) bath ( ⁰ C) Acrylic acid + Exertion Exertion Methyl acryl te (%) te (%) lat (%) At first 6th step 281 94.5 66.2 26.4 10 281 93.7 63.1 23.1 Examples 7 to 8 (

In a manner similar to Example 1, catalysts with the compositions given in Table VI below were prepared, if necessary using salts of the X component, ammonium metavanadate and rhenium chloride and the like Using these catalysts, the reactions were carried out under the same conditions as in Example 1, wherein this time, however, no phosphorus-containing compound was added. The results obtained are in the following table VI indicated.

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Tobelle VI

oat ο co αο no κ>

Ex.
No. Catalyst »« amen set-
tongue Temp
Nitrate-
baths (° C) Methacro
lein-um-
change
(*) Methacryl
acid-off
prey {%) Methylneth
acrylate
yield
(50 - selectivity
for methacrylic
acid + methyl ~
methacrylate) 7th ^Pd l ^P l ^M 90.5 ^Sb l ° 5.5 270 75.5 35.1 13.8 64.8 8th Pd ₁ P ₅ Mg ₁ Sb ₁ O ₁₆ 273 75.6 35.5 14.0 65.5 9 Pd ₁ P ₉ Mg ₂ Sb ₁ O ₂₇ 276 75.1 40.7 23.7 83.7 10 Pd ₁ P ₁₆ Mg ₅ Sb ₇ O _{56 # 5} 279 70.5 40.2 20.8 86.5 11 ^Pd l ^P 27 ^M 5l0 ^Sb 10 ° 93.5 288 71.0 38.5 20.4 83.0 12th ^Pd l ^P 8 ^M 9 ₀ .l ^Sb 0.2 ° 21.4 276 74.0 35.7 15.9 70.0 13th Pd ₁ P ₁₂ B ₅ L SlJ 9 ₃₅ 276 72.5 38.5 24.5 86.9 14th ^Pd l ^P 6 ^Ba 0.5 ^Sb 2 ° 19.5 272 75.5 35.7 18.6 71.9 15th Pd ₁ P ₁₉ Ba ₃ Sb ₁ O ₅₃ 286 72.7 37.5 23.2 83.5 16 Pd ₁ P ₂₃ Ba ₁ Sb ₃ O ₆₄ 296 73.5 36.5 20.7 77.8 17th Pd ₁ P ₁₂ Ca ₁ Sb ₁ O _{33 # 5} 279 74.5 39.1 22.8 83.1 18th Pd ₁ P ₂₁ Ca ₁ Sb ₂ O _{57> 5} 281 73.5 40.5 20.3 82.7
to 19th Pd ₁ P ₅ Ca _{0 a} 5 Sb ₁ O _{15 # 5} 271 75.7 35.6 21.1 20th Pd ₁ P ₂₇ Ca ₆ Sb ₇ O ₈₅ 295 72.5 34.5 18.9

Table VI (1st continuation)

lisp.
No. Catalyst composition
tongue Temp
Nitrate-
baths (° C) mm \ ~
Methacro
lein-um-
change
00 Methacrylic
acid-based
prey {%) Methylmeth-
acrylate
yield
00 selectivity
for methacrylic
acid + methyl-
methacrylate (/ 0 21 Pd ₁ P ₁₂ K ₁ Sb ₁ O ₃₃ 272 73.5 40.1 21.3 83.5 22nd Pd ₁ P ₁₆ K ₃ Sb ₂ O ₄₅ ^ ₅ 274 72.5 38.5 20.5 81.4 23 Pd ₁ P ₂₃ K ₁ Sb ₃ O _{63 # 5} 285 70.5 35.7 18.5 76.9 24 ^Μ ΐ ¥ θ.3 ^81> 0.5 ⁰ 9.4 270 76.6 33.6 19.4 69.2 25th Pd ₁ P ₁₂ Na ₁ Sb ₁ O ₃₃ 270 74.5 38.5 23.1 82.7 ^, 26th Pd ₁ P ₂₂ Na ₂ Sb ₂ O ₆₀ 280 73.3 40.1 22.7 85.7 27 Pd ₁ P ₃ Na ₅ Sb ₇ O ₂₁₅ 268 74.7 35.4 15.7 68.4 28 Pd ₁ P ₁₃ Rb ₁ Sb ₁ O _{35 mS} 273 75.3 41.1 23.5 85.8 29 Pd ₁ P ₂₀ Rb ₃ Sb ₂ O ₅₅ ^ ₅ 286 73.5 39.7 21.4 83.1 30th ^Pd l ^P 6 ^Rb 0.2 ^Sb 0.5 ° 16.9 270 74.7 35.5 17.3 70.7 31 ^Pd l ^P 12 ^Sn 0.5 ^Sb l ° 33.3 276 75.6 40.7 23.8 85.3 32 Pd ₁ P ₂₂ Sn ₂ Sb ₃ O _{59 # 5} 290 72.5 39.7 20.5 83.0 ^ o 33 ^Pd l ^P 3 ^Sn 0.2 ^Sb 4 ° 14.8 271 74.5 36.7 17.7 73.0 cn N.

Tob !! VI (2nd continuation)

O CO OO

Btitp. Kote! YMtoRMMM «n» «t · Twp.d ·· fettwero · H.thocryl- M # thyl ^ th- S«! «Ktlvtta« Χχ · cung Nitrat- ltin-U · - · βοΓ · -Αϋ · - ocrylot - for M # thaeryl »

bad * »rc) conversion b« it · (jO yield · taur ^ ethyl- (%) (%) »« Thocrvlot «)

34 Pd ₁ P ₁₁ Zn ₁ Sb ₁ O ₃₁ 273 74.7 39.9 24.1 85.7 Vf —J
CH 35 Pd ₁ P ₂₁ Zn ₄ Sb ₂ O _{60 5} 288 73.5 38.5 23.3 84.1 N- 36 ^Pa i ^P 4 ^Zn 0.6 ^Sb 0.2 ° U.9 269 75.6 35.7 18.2 71.3 37 Pd ₁ P ₁₂ Ce ₁ Sb ₁ O ₃₃ 277 76.5 39.7 23.5 82.6 38 Pd ₁ P ₂₄ Ce ₃ Sb ₂ O _{65 # 5} 291 74.5 37.8 22.3 80.7 39 Pd ₁ P ₃ Ce ₆ Sb ₈ O ₂₃ ^ ₅ 267 76.4 34.7 20.3 72.0 40 Pd ₁ P ₁₃ Th ₁ Sb ₁ O ₃₇ 273 74.5 40.0 19.5 79.9 41 ' Pd ₁ P ₂₃ Th ₄ Sb ₄ O ₇₂₅ 287 73.3 39.7 17.5 78.0 42 ^Pd l ^P 2 ^Th 0.1 ^Sb 3 ° 10.7 266 76.9 34.5 18.8 69.3 43 Pd ₁ P ₁₂ Sr ₁ Sb ₁ O _{33 # 5} 271 74.5 40.5 20.7 82.1 44 Pd ₁ P ₂₃ Sr ₃ Sb ₂ O _{64 t 5} 289 72.5 38.9 19.5 80.6 45 ^Μ 1 ^Ρ 5 ⁸ * 0.3 ⁸¹ > 1 ^Ο 15.3 262 73.5 35.8 19.2 74.8 46 Pd ₁ P ₁₃ Bi ₂ Sb ₂ O _{39 <5} 277 74.8 39.7 24.5 85.8 47 Pd ₁ P ₂₂ Bi ₃ Sb ₁ O ₆₂ 292 73.5 37.5 21.3 80.0

Tob !! Vl (3rd continuation)

•• V Tesi

sung

OO
CD
CO
QO

48 49 50 51 52 53 54 55 56 57 58 59 60 61

^Pd l ^P 6 ^Bi 0.5 ^Sb 6 ° 25.8

Pd ₁ P ₂₄ Ni ₂ Sb ₄ O ₆₉

^Pd l ^P 6 ^Ni 0.7 ^Sb 0.2 ° 17

^Pd l ^P 13 ^Fe l ^Sb O.5 ° 35.8 Pd ₁ P ₂₀ Fe ₂ Sb ₄ O ₆₀

Pd ₁ P ₂₇ Fe ₄ Sb ₈ O ₈₆₀₅

^Pd l ^P 2 ^CO 0.3 ^Sb l ° 7.8 Pd ₁ P ₁₂ Cr ₁ Sb ₁ O ₃₄

Pd ₁ P ₂₁ Cr ₂ Sb ₂ O ₃₉ ^

^Pd l ^P 4 ^Cr 0.7 ^Sb l ° 13.6

272 273 286 265 271 285 300 276 281 261 273 294 263 269

wmdlung b "ut"

75.5
75.5
74.4
76.5
74.6
73.5
75.5
75.2
73.6
76.7
76.5
75.3
76.7
75.8

35.0
39.9
39.8
35.7
40.0
38.7
39.9
39.6
37.5
34.3
41.3
40.0
35.7
43.1

• erylate » Autbcvt

17.9 19.9 19.0 16.1 21.5 20.3 17.1 22.5 21.7 19.3 23.0 18.5 17.8 18.7

MUl MthaervlaifO

70.1 79.2 79.0 67.7 82.4 80.3 75.5 82.6 80.4 69.9 84.0 77.7 69.8 81.5

Tob !! VI (4th continuation)

co O CO OO Ν »

With · »· KotalytoterzutaaMiit« t · Teap.d ·· Methocro- Mtthocryl- Methylaeth * selectivity
No. Tung Nitrate-Lein-Ue iöure-Au-ocrylcft- for Hethaeryl

bad ( ⁰ C) conversion yield (%) aut yield tBure + diethyl- (%) (%) Methacrylatefc)

62 Pd ₁ P ₁₉ Mn ₃ Sb ₄ O _57a5 273 75.1 40.0 63 ^Pd l ^P 3 ^Mn 0.5 ^Sb l ° 10.5 259 74.5 38.5 64 Pd ₁ P ₁₃ U ₁ Sb ₁ O ₃₇ 273 73.1 39.7 65 ^Pd l ^P 25 ^ü 3 ^Sb 2 ° 72.5 299 72.5 38.5 66 ^Pd l ^P 2 ^ü 0.5 ^Sb 6 ° 16 265 75.5 37.9 67 Pd ₁ P ₁₂ Re ₁ Sb ₁ O _{34 5} 265 75.7 41.5 68 Pd ₁ P ₂₁ Re ₃ Sb ₂ O _{62 m 5} 268 74.3 39.7 69 ' ^Pd l ^P 5 ^Re l ^Sb 0.5 ° 16.3 251 73.8 39.0 70 ^Pd l ^P 12 ^Be 0.5 ^Sb l ° 33 273 74.5 38.5 71 ^Pd l ^P 22 ^Be 2 ^Sb l ° 59.5 296 73.7 37.0 • 72 267 75.7 36.3 73 275 75.1 40.0 74 Pd ₁ P ₂₁ Pb ₂ Sb ₂ O _58β5 287 75.2 39.5 75 Pd ₁ P ^ Pb _n ., Sb _n .O ₁₄ ,
1 5 0.3 0.5 14.ο 270 75.3 37.0

16.2
15.6
20.5
18.7
16.5
23.5
22.7
18.5
23.1
21.5
17.5
23.6
22.9
18.5

74.8 72.6 82.4 78.9 72.1 85.9 84.0 77.9 82.7 79.4 71.1 84.7 83.0 73.7

Tobtll »VI (5th continuation)

roro

Btitp «No *

77 78 79 80

Catalysis* sung

76 ^Pd 'l ^P 12 ^V l ^Sb l ° 35

Pd ₁ P ₁₉ V ₂ Sb ₃ O ₅₈ Teep.d ·· Methocro- Methocryl- fethyLwth · Selectivity Nitrat- lein-U · - «aur» -Au ·· ocryldt- for MethocryJU bad · »( ⁰ C) conversion beut« (%) Expansion litter ethyl - (<) (%) -thoervlotfc)

273
285
291
273
280

76.1 39.0

74.5 38.7

73.1 36.6

74.7 40.0

73.5 39.9

23.3 21.5 17.6 23.1 21.3

81.9 80.8 74.1 84.5 83.3

Examples 81-102

Reactions were carried out under the same conditions as in Example 1 carried out using the catalysts of the examples given above. The results obtained are given in the following table VII

809822 / om

Table VII

Ex.
No. Example No.
of the use
deten kata
lysators Reacti
on time
(Days) Tenp.d.
Nitrate ba
des ( ⁰ C) Methacrole
to-convert
1υη ₉ (*) Methac
rylsäu
re-au s-
bootyOO Methylmeth-
acrylate
yield
(%) selectivity
for methacry1-
sBure + methyl-
methacrylate (jC) 81 13th 0
40
120 276
276
276 72.5
72.6
72.5 38.5
38.4
38.3 24.5
24.5
24.4 86.9
86.6
86.5

O CO OO

82 17th O
40
120 279
279
279 74.5
74.3
74.6 39.1
39.0
39.2 22.8
22.5
22.6 83.1
82.8
82.8 83 21 0
40
120 272
272
272 73.5
73.5
73.5 40.1
40.0
40.2 21.3
21.4
21.2 83.5
83.5
83.5 84 25th 0
40
120 270
270
270 74.5
74.4
74.7 38.5
38.3
38.3 23.1
23.3
23.3 82.7
82.8
82.5 85 28 0
40
120 273
273
273 75.3
75.2
75.2 41.1
40.9
41.0 23.5
23.6
23.7 85.8
85.8
86.0 86 31 0
40
120 276
276
276 75.6
75.5
75.5 40.7
40.5
40.6 23.8
23.6
23.9 85.3
84.9
85.4 87 34 0
40
120 273
273
273 74.7
74.6
74.7 39.9
39.9
39.9 24.1
24.1
24.2 85.71
85.8 '
85.8

VXX (ι. Continuation)

Btlsp.

No.

88

Β · ί · Μ * »clock!« D ·· ν · Γ * · β · on time d «t« i Koto- (Tog ·) lysotors

T «ap.d.
Nltrotbo-

40 120

Methocrol · - Htthse-IfetbylMtb-S «lt * tlvitat

in-UmaneV rylsög- acrylot- for Hathocryl

! (%) r «-aus- expansion · stluwMethyl-

Uu t (%) (%) BethocrylatOC)

277
277
277

76.5
76.3
76.5

39.7
39.8
39.8

23.5 23.6 23.6

82.6 83.1 82.9

89 40 0
40
120 273
273
273 74.5
74.5
74.4 40.0
39.7
39.7 19.5
20.5
20.6 79.9
80.8
81.0 90 43 0
40
120 271
271
271 74.5
74.3
74.6 40.5
40.2
40.4 20.7
20.7
20.8 82.1
82.0
82.0 91 46 0
40
120 277
277
277 74.8
74.6
74.7 39.7
39.7
39.7 24.5
24.2
24.2 85.8
85.7
85.5 92 49 0
40
120 273
273
273 75.5
75.6
75.6 39.9
40.0
40.0 19.9
19.9
20.0 79.2
79.2
79.4 93 52 0
40
120 271
271
271 74.6
74.5
74.4 40.0
39.9
40.0 21.5
21.6
21.4 82.4
82.6
82.5 94 55 0
40
120 276
276
276 75.2
75.1
75.3 39.6
40.0
39.8 22.5
22.1
22.2 82.6
82.7
82.3

NJ NJ NJ

ToUlU VH (2nd continuation)

B «i · p.
No.

95

BeUp.Nr. Reoktidet viivM- on · »it deten Koto- (days) lyotor ·

40 120

Teep.dt

Nltretbadt ,. ( ⁰ C)

273 273 273

Methocrole- Hethoc- Hethylerkh- selectivity in-demand rylsOu- οcrylot- for Hethacryl · adjustment (jC) re-Au · - · Autbeut täure + methyl · yield (%) (%) eethocrvlgtOO

76.5
76.5
76.5

41.3
41.4
41.3

23.0 23.1 23.1

84.0 84.3 84.2

96 61 0
40
120 269
269
269 75.8
75.7
75.7 43.1
43.0
43.0 18.7
18.8
18.8 81.5
81.6
81.6 97 64 0
40
120 273
273
273 73.1
73.0
73.1 39.7
39.7
39.8 20.5
20.7
20.5 82.4
82.7
82.5 98 67 0
40
120 265
265
265 75.7
75.5
75.7 41.5
41.5
41.6 23.5
23.4
23.4 85.9
86.0
85.9 99 70 0
40
120 273
273
273 74.5
74.4
74.6 38.5
38.6
38.5 23.1
23.0
23.1 82.7
82.8
82.6 100 73 0
40
120 275
275
275 75.1
75.0
74.9 40.0
40.2
40.0 23.6
23.5
23.4 84.7
84.9
84.6 101 76 0
40
120 273
273
273 76.1
76.0
76.0 39.0
39.1
39.1 23.3
23.4
23.3 81.9 ι
82.2 '
82.1

2752 ^ 3

33

in oo σ \

• · · «r 51 · ν 00 CO 00

mom OJ (N CM

O O O

t »· in in

m ro «n I ^s r ^ r ^ CN CM (N

ο ο ο

cn

809822/0774

3 *

Examples 103-104

In a manner similar to Examples 7 to 80, catalysts were prepared with those given in Table VIII below
Compositions made. Using these catalysts, the reactions were carried out under the same conditions
carried out as in Example 1. The results obtained are shown in Table VIII below.

809822/0774

Tobelle VIII

Example: KotolysatorzusoMMnset- reaction »- Temp.d. Methacro- Methacryl- Methylieth- Selectivity ^Nr · * "** J · ". ^Νί * ^Γ ° ^ - lein-Umseure-Aus aerylet- for methacryl-

CTage; des (C) conversion booty (jC) yield acid + methyl-

'" ^X (%) wethocrvlot«)

103

Pd ₁ P

Sb

.Rb

275 275 275

70.6 70.1 70.5

40.1 40.0 40.0

19.9 19.6 19.9

85.0 85.0 85.0

104

Pd ₁ P ₁ -Sb _n -V _n -K _n -0 ,, _A 1 12 0.7 0.5 0.2 33.4

272 272 272

75.5 75.4 75.4

39.0 39.1 39.1

21.0 20.8 20.9

79.5 79.4 79.6

2752/23 - ar-

Examples 105 - T26

The reactions described in Example 4 were repeated, this time using catalysts with the in the following Table IX specified compositions, prepared in the same manner as in Examples 7 to 80, were used, and it no phosphorus-containing compound was added «The The results obtained are shown in Table IX below.

809827/0774

Table IX Etoisp. Kotalysatorzusatzung Temp.d. Acrolein- Acryl · du- Methylacry Selectivity for Nr * nitrate bath ·· conversion r «-Au« beulat-Au «b« u- Acryletfure + Methyl-

( ⁰ C) (%) t « (%) U (%) ocrvlot (%)

105 Pd ₁ P ₁₂ Ba ₁ Sb ₁ O _{33 #}

106 Pd ₁ P ₁₂ Ca ₁ Sb ₁ O _{33 #}

107 Pd ₁ P ₁₆ K ₃ Sb ₂ O _{45 # 5}

108 Pd ₁ P ₂₂ Na ₂ Sb ₂ O ₆₀

109 Pd ₁ P ₁₃ RbISb ₁ O ₃₅ ^

110 Pd ₁ P ₁₂ Sn _0β 5Sb ₁ O ₃

111 Pd ₁ P ₁₁ Zn ₁ Sb ₁ O ₃₁

112 Pd ₁ P ₁₂ Ce ₁ Sb ₁ O ₃₃

113

114 Pd ₁ P ₂₃ Sr ₃ Sb ₂ O ₆₄ ^

115 Pd ₁ P ₁₃ Bi ₂ Sb ₂ O _{39 #}

116 Pd ₁ P ₁₂ Ni ₁ Sb ₁ O _{33 m}

117 Pd ₁ P ₁₃ Fe ₁ Sb ₀₅ O ₃

281 279 286 276 283 274 280 282 285 275 286 277 281

97.7 66.3 26.1 96.1 65.2 25.4 92.3 63.1 23.3 92.5 64.3 23.1 98.2 66.3 26.2 91.3 61.1 22.6 95.7 64.9 25.3 93.7 64.5 24.2 98.0 65.3 25.7 92.1 64.6 24.1 93.7 64.7 25.1 95.1 65.1 24.6 94.1 62.3 25.1

94.5 94.3 93.6 94.5 94.2 91.7 94.3 94.7 92.9 96.3 95.8 94.3 92.9)

Tobell IX (Forteetrung)

Β · 1 · ρ · Kotoly * atorzusaMwns «tsung Teap.d · Acrolein · Aerylsau · M» thylaery »S« l «ktivittlt for
Nr * nitrate bath ·· conversion r * -ausbmi · lat-Au «b» ü- Acryl * öur »+ M» thyl ·
( ⁰ C) (%) U (%) U (%) ocrvlot (%)

CO
O
CD
OO

118 Pd ₁ P ₁₂ CO ₂ Sb ₁ O _{34 m}

119 Pd ₁ P ₁₂ Cr ₁ Sb ₁ O ₃₄

120 Pd ₁ P ₁₉ Mn ₃ Sb ₄ O ₅₇ ^

121 Pd ₁ P ₁₃ U ₁ Sb ₁ O ₃₇

122 Pd ₁ P ₁₂ Re ₁ Sb ₁ O _34e

123 Pd ₁ P ₁₂ Be _0e 5Sb ₁ O ₃

124 Pd ₁ P ₁₂ Pb ₁ Sb ₁ O ₃₃ ^

125 Pd ₁ P ₁₂ Vi ⁵¹⁵ I ⁰ SS

126 Pd ₁ P ₁ -Li ₁ Sb _n , 0 ,, _A 112 1 0.632.4

282 95.2 63.3 24.7 92.4 278 92.7 61.5 24.3 92.6 271 95.5 62.1 23.7 99.8 277 93.1 60.7 24.1 91.1 272 98.3 67.3 26.0 94.9 278 95.7 61.5 24.5 89.9 274 96.1 66.8 24.9 95.4 273 97.0 65.9 23.9 92.6 277 92.1 61.3 24.0 92.7

Example 127

The reactions described in Example 4 were carried out for 120 days using the same catalysts as in Examples 105 to 126. The results obtained after 120 days were almost the same as those obtained in FIG Initial stage were obtained. The yields of acrylic acid and methyl acrylate did not decrease within the 120 days.

Example 128

Examples 1 and 4 were repeated, this time as phosphorus containing compound instead of trimethyl phosphate solid phosphoric acid (Celite / ^ hosphor = 50/50) was used, which in 550 ° C was heat treated.

On top of the catalyst layer made up of 10 ml of catalyst A, 5 ml of the solid phosphoric acid was applied. The results obtained were almost the same as those of Examples 1 and 4.

Example 129

Examples 81 to 104 and 127 were repeated, this time using the phosphorus-containing compound instead of trimethyl phosphate orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid and solid phosphoric acid were used in each case. It was found that the results were almost the same as those of Examples 81-104 and 127.

809822/0774

Example 130

Examples 1 and 4 were repeated, this time the The amount of the supplied phosphorus-containing compound was changed. The amount of phosphorus in the compound has been changed to be within the range of 0.5

-3
Wt -.% To 1 χ 10 wt -.%, Based on the total amount of supplied water and methanol, was. The results were almost the same as those of Examples 1 and 4.

Example 131 Using the procedure given in Example 1,

a catalyst produced, but this time in the order

the impregnation with palladium and phosphorus has been changed.

Using this catalyst the same reactions occurred

carried out as in Examples 1 and 4. The results obtained

were almost the same as those of Examples 1 and 2

Example 132

A catalyst was prepared using the procedure outlined in Example 1, this time the impregnation was carried out with palladium and phosphorus at the same time. Using this catalyst, the reactions on the carried out in the same manner as in Examples 1 and 4. The results obtained were almost the same as those of Examples 1 and 4.

Example 133

16.0 g Aerosil, 0.4 g antimony trioxide, 0.17 g magnesium phosphate, 6.5 g hypophosphorous acid and 10 nl of an aqueous ammonia solution, containing 0.44 g of palladium chloride were mixed together. The mixture was evaporated to dryness. The dried one Product was calcined in air at 450 ° C for 5 hours. The catalyst thus obtained had a composition according to the following formula:

Using this catalyst the same reactions occurred carried out as in Examples 1 and 4. The results obtained were almost the same as in Examples 1 and 4.

Example 134

Example 1 was repeated, this time using the gaseous feed mixture with a space velocity (SV) of 400 liters Gas / l catalyst was supplied for χ hour. The results obtained are given in Table X below.

Tobelle X

Rection temp. Methacro- selectivi- methacryl- methylmeth- »With nitrate linse conversion for methic acid aus acrylot- (days) bath (C) lung (jC) acrylic acid + booty (jC) yields)

Methyl methaeroite (%) initial stage · 296 67.7 W, 5 40 296 67.6 89.3 120 296 67.6 89.4

809827/0774

37.2 23.4 37.4 23.0 37.4 23.0

-TfT-

135

Example 4 was repeated, this time the gaseous feed mixture having a space velocity (SV) of 4000 l gas / l catalyst χ hour was fed. The received Results are given in Table XI below.

Table XI

Reokti- Reaction- Methacrolein- Selectivity MethacryI- Methy1-onszeit temp.d. Ni conversion for methacrylic acid from methacrylate (days) step baths (%) acid + methyl spoil (%) lat from ( ⁰ C) methocrylate (? S) spoil (%)

At first-
ttufe 287 91 , 6 93.6 62, 1 23.6 40 287 91 , 4 93.7 62, 3 23.3 120 287 91 , 3 93.9 62, 4th 23.3 Examples 136-139

The reaction given in Example 1 was carried out in the presence of the catalyst A with a varying molar ratio between the reagents repeated in a gaseous feed mixture. The results obtained are given in Table XII below.

In Table XII, the gaseous feed mixtures B-E had the following relative molar ratios:

809822/0774

gaseous meth-feed acrolein mixture B C Ο

Methanol: Sour
material : water
steam: Stick
fabric I phosphorus 1 2 0 18.1 1.8x1 θ ' ³ 2 4th 5.5 13.6 1.8x1θ " ³ 1 3 8.0 15.9 3.6x1 θ " ³ 4th 8th 13.0 25.0 1.8x1θ " ³ Tabel XII

Example gasforei- Tenp.d. Methacro-Selective- Methacryl- Methy1-Nr. ge loading nitrate linseed for acid ex- methacrykungsaigung bath conversion methacryl- loot {%) lat- leaching · (° C) {%) acid + me- te {%)

thylnethacrylotOQ

136 B. 300 66.5 88 7th 37.5 21.5 137 C. 276 76.5 83, 1 35.2 28.4 138 D. 277 77.6 80, 2 40.0 22.2 139 E. 273 63.5 87 8th 39.6 16.2 Examples 140-143

The reaction of Example 4 was repeated in the presence of Catalyst A with varying molar ratios between the Reagents in the gaseous feed mixture · The obtained Results are given in Table XIII below.

Table XIII shows the gaseous feed mixtures F-I have the relative molar ratios given below:

809822/0774

Sour water stick

gaseous
Loading
mixture
F. Acrolein
1 : Methanol:
1.5 Tabel material
2 : steam
0 : material
18.1 G 1 2 4th 7.5 13.6 H 1 1 8th 12.5 21.6 I. 1 4th 5 3 12.3 XIII

1.8x10

3.6x10

1.8x10
5.4x10

Example gaseous temp. Acrolein Selective Acrylic Methy1

No. of charge nitrate conversion act for acrylic acid acrylate baths {%) acid + methyl yield yield

schung Cc) 94.8 acrylate (%) 00 te 00 140 F. 287 98.8 91.7 58.1 28.8 141 G 272 98.7 93.0 64.9 27.0 142 H 270 95.1 90.2 67.3 21.7 143 I. 282 92.7 60.1 28.1

Claims (9)

1. Process for the simultaneous production of methacrylic acid and a methacrylate or acrylic acid and an acrylate by reaction of methacrolein or acrolein with an aliphatic Using alcohol and molecular oxygen in the gas phase of a catalyst, characterized in that nan uses a catalyst which consists of or contains (1) palladium, (2) Phosphorus, (3) antinone, (4) X and (5) oxygen, where X is at least one element selected from the group potassium, Sodium, lithium, rubidiun, cerium, beryllium, lead, magnesium, calcium, Strontium, zinc, barium, thorium, bismuth, chromium, iron, nickel, cobalt, vanadium, manganese, tin, uranium and rhenium. 2. The method according to claim 1, characterized in that the reaction system at the same time a phosphoric acid or a Phosphorus compound, which can form a phosphoric acid by chemical conversion during the reaction, supplies. 3. Process for the simultaneous production of methacrylic acid and a methacrylic lots or acrylic acid and an acrylate by substituting methacrolein or acrolein with an aliphatic 809822/0774 ORIGINAL INSPECTED Using alcohol and molecular oxygen in the gas phase of a catalyst, characterized in that a catalyst of the following composition is used Pd P. Sb X .0 ab ede wherein X is at least one element selected from the group Potassium, sodium, lithium, rubidium, cerium, beryllium, lead, magnesium, Calcium, strontium, zinc, barium, thorium, bismuth, chromium, iron, nickel, cobalt, vanadium, manganese, tin, and uranium Rhenium and the indices α, b, c, d and e mean the number of Pd, P, Sb, X and O atoms, where a = 1, b = 1 to 42, c = 0.1 to 15, d = 0.1 to 15 and e represents a number which is determined by the valences of the other elements in which Usually a number from 3.75 to 150.5. 4. The method according to claim 3, characterized in that in the general formula a = 1, b = 1 to 28, c = 0.2 to 10, d = 0.1 to 10 and e = 6.4 to 101. 5. Process according to claims 1 to 4, characterized in that that methanol is used as the aliphatic alcohol. 6. The method according to claims 2 to 5, characterized in that that nan uses orthophosphoric acid, pyrophosphoric acid or metaphosphoric acid as phosphoric acid. 7. The method according to claims 2 to 5, characterized in that that one as a phosphorus compound produced by chemical conversion 809822 / 077Ä during the reaction a phosphoric acid can form, solid Phosphoric acid or an organic phosphoric acid is used. 8. The method according to claims 1 to 7, characterized in that that methacrolein is used as a reagent. 9. The method according to claims 1 to 7, characterized in that that acrolein is used as a reagent. Π98 ?? / 077 k ORIGINAL INSPECTED