DE2203710A1 - Process for the oxidation of olefins to aldehydes and acids - Google Patents

Description

Applicant: The Standard Oil Company-Midland. Building, Cleveland, Ohio 44115 / USA

Process for the oxidation of olefins to aldehydes and acids

The invention relates to a process for the catalytic oxidation of olefins to useful oxygen-containing hydrocarbon compounds} it relates in particular to a process for the conversion of oC-olefins of low molecular weight, such as B. propylene and isobutylene, into the corresponding unsaturated aldehydes and unsaturated Carboxylic acids, acrolein, methacrolein, acrylic acid or methacrylic acid.

The process according to the invention is characterized in that a gaseous mixture of olefin and oxygen is used in the gas phase

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With an oxide of iron, bismuth, luolybdenum, and at least one iilement from Group II of the Periodic Table of Elements contacted as essential components and optionally oxides of phosphorus arsenic and an alkali metal-containing solid catalyst.

The catalyst according to the invention has a number of advantages the effective and economical implementation of the invention Contribute considerably to the procedure. The catalyst is excellent under the reaction conditions of the process Redox resistance. In addition, the catalyst has high activity and selectivity for converting olefins into Usable oxygenated products with a low bismuth content on; therefore, the cost of the essential components of the catalyst is low. This low cost of catalytic Ingredients in connection with the ease of manufacture of the catalytic converter make this catalytic converter : From a point of view very attractive.

The high activity of this catalyst with a low bismuth content is surprising in view of the US Pat 2 941 007, in which a process for the production of unsaturated Aide iyde and ketones from α-olefins in the presence of one from: / ismutmolyblat or phosphorinolybdate existing catalyst. > en, and in US Pat. No. 3,171,359, in which a method for the production of unsaturated aldehydes in ', actually one Catalytic converters containing oxides of iron, bismuth, phosphorus and molybdenum

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lysators is described, the specified degrees of conversion. Another The advantage that is achieved with the process according to the invention is that it is possible with this process to produce olefins to convert directly into unsaturated aliphatic acids. Under under suitable conditions, high yields of unsaturated aliphatic acids can be obtained directly by oxidation of olefins and the investment costs for the plant in an industrial one-step process for converting, for example, propylene into Acrylic acid are considerably less than in the two-step process.

The reactants that are used to produce the unsaturated according to the invention Aldehydes and unsaturated carboxylic acids are used, are oxygen and a lower alkene, such as. B. propylene or isobutylene and mixtures thereof. The olefins can be mixed with paraffinic hydrocarbons, for example ethane, propane, butane and pentane, for example the starting material can be a propylene / propane mixture. This makes it possible using ordinary refining streams without special preparation. Thinners, such as Nitrogen and the carbon oxides, may be present in the reaction mixture.

According to a preferred aspect, the method according to the invention is characterized in that a mixture consisting of propylene or isobutylene and oxygen with the catalyst at a elevated temperature and at atmospheric pressure or at one pressure

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- 4 contacted near atmospheric pressure.

Any source of oxygen can be used in the process of the invention be used. For economic reasons, however, air is preferably used as the oxygen source. From the purely technical From a standpoint, relatively pure molecular oxygen gives equivalent results. The molar ratio of Oxygen to olefin in the feedstock (feed) in the reaction kettle should be within the range of 5: 1 to 0.5: 1 and a ratio of about 1: 1 to 3: 1 is preferred.

It has been found that, in some cases, water in the mixture introduced into the reaction vessel can reduce the selectivity of the Reaction and the yield of unsaturated aldehydes and / or acids can be improved. However, water is not essential since water is formed in the course of the reaction. In general, the molar ratio of added water to olefin is when Water is added within the range of about 0.25 to 20: 1. Ratios on the order of 1: 1 to 4; 1 are special expedient.

The reaction is carried out at a temperature within the range of about 260 to about 482 ° C (500-90O ⁰ F). The preferred temperature range is from about 288 to about 399 ⁰ C (550 ⁰ F 75O). The pressure at which the reaction is carried out has a certain influence on the conversion and the reaction should be at about atmospheric pressure or at a pressure slightly above

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Atmospheric pressure (2 to 5 atmospheres). the Apparent contact time is not critical and there can be contact times can be used within the range of about 0.1 to about 50 seconds. Of course, the optimal contact time varies depending on the person after the converted olefin, however, there is generally a continuous time from 1 second to 15 seconds preferred.

The yield of unsaturated carboxylic acids is increased by higher reaction temperatures, favors higher oxygen to olefin ratios and longer contact times and the reverse is true for the yields of unsaturated aldehydes. If a maximum yield of unsaturated acids is desired, it is advantageous to use the Unsaturated aldehyde formed again via the erfindungsgeraässen To recycle catalysts. The recycling of the converted Aldehyde can be used with the recycling of the process water vapor and / or the unreacted olefin are combined.

In general, <jur> . Implementation of the method according to the invention any device can be used, which for the Suitable for carrying out oxidation reactions in the vapor phase is. The method according to the invention can be carried out either continuously or intermittently. By the catalyst bed it can be a fixed bed, if using a particulate or pelletized large particle catalyst, or alternatively a so-called "fluidized bed" act. The fluid reactor can be loaded from an open column

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or the reactor can have a plurality of perforated, horizontally stacked one on top of the other over the entire length of the column Contain soils as described in US Pat. No. 3,230,246. The reactor can be before or after the introduction of the starting reaction mixture brought to the reaction temperature. In a large-scale procedure, however, it is preferred to operate the process continuously and in such a system the circulation of the unreacted olefin is provided. Although the catalyst is redox-resistant, it can, if necessary, be regenerated or reactivated by using the Bringing the catalyst into contact with air at an elevated temperature.

The reaction products can be prepared by any known method be won. One such method is that the effluent gases from the reactor with cold water or a suitable one Solvent washes to remove the reaction products therefrom. The final extraction of the products can be based on conventional methods Way to be carried out. The effectiveness of the washing process can be improved when using water as a detergent if a suitable wetting agent is added to the water. If molecular oxygen in the process according to the invention is used as an oxidizing agent, after removal of the carbonyl and carboxylic acid compounds; lagging resulting product mixture for removing carbon dioxide and water with the remainder of the unreacted olefin and oxygen containing mixture are treated and recycled into the reactor. In the event that instead of molecular oxygen

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■ - 7 -

If air is used as the oxidizing agent, this can be done after the separation remaining product and the other carbonyl products with a non-polar solvent such as a hydrocarbon to f fraction, washed to recover unreacted olefin and in this case the remaining gases can be discarded. It can also include the addition of a suitable one Inhibitors may be provided to prevent the polymerization of the unsaturated products during the recovery stages.

In the case of the catalyst used in the process according to the invention it is a mixture, a complex or a compound from the oxides of iron, bismuth, molybdenum and at least one element from Group II of the Periodic Table of the Elements and optionally the oxides of phosphorus and / or arsenic and an alkali metal. The composition can expediently through the following molecular formula can be expressed:

^A a ^B b ^C c ^Fe d ^Bi e ^Mo f ⁰ X

wherein: A is an alkali metal, B phosphorus or arsenic or both and C is at least one element from group II A and from of Group II B of the Periodic Table of the Elements and in which (a) denotes a number from 0 to less than 0.1, (b) a number from 0 to 3, (c) a number from 0.1 to 10, (d) and (e) each Number from 0.1 to 6, (f) a number from 8 to 16 and (x) a number, by the valence requirements of the other elements present> estinii: it is.

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A preferred catalyst composition is one in which A is potassium, C is a metal from Group II A of the Periodic Table of the Elements and the atomic ratios of the elements in the above empirical formula are within the range in which (a) is a number from 0 to 0.09, (b) a number from 0 to 1, (c) a number from 0.1 to 7, [d) and (e) each a number from 1 to 4, and (£) the number 12. Most a catalyst composition in which the metal of Group II A of the Periodic Table of the Elements is magnesium is preferred.

The catalyst of the present invention can be any of a number of Processes for preparing catalysts known to those skilled in the art can be prepared. For example, the Catalyst can be produced by co-precipitating the various constituents that can be co-precipitated then dried and ground to a suitable size. Alternatively, the jointly precipitated material can be slurried and be spray-dried by customary methods. The catalyst can be extruded into pellets in oil or in a conventional manner can be deformed into spheres. Alternatively, the catalyst components mixed with the carrier in the form of the slurry and then dried, or silica or any other carriers can be impregnated with it. A particularly abrasion-resistant form of the catalyst can be produced by Adding the support material to the catalyst in two stages, first adding a mixture of the active catalyst components and 0 to 60% by weight of the total carrier material and

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heat-treated and then the remainder of the support material is added to the powdered form of the heat-treated catalyst. A more detailed description of the preparation of an attrition-resistant catalyst is given in the examples below.

The alkali metal can be in the form of an oxide or any salt, that gives the oxide during calcination. Preferred salts are the nitrates, which are readily available and easily soluble are. Bismuth can be introduced in the form of an oxide or in the form of any salt which, when calcined, provides the oxide. Most preferred are water-soluble salts which are easily dispersible within the catalyst and which are used in the Heat treatment to form stable oxides. The most preferred salt for introducing bismuth is bismuth nitrate. For the introduction of the iron component in the catalyst, any iron compound can be used which provides the oxides upon calcination. As with the other elements, the water-soluble salts are preferred because of the ease with which they are uniform within of the catalyst can be dispersed. Most preferred is iron (III) nitrate. The metals of group II of the periodic Systems of elements can be introduced in a similar manner. However, the metals of Group II of the Periodic System of the elements also in the form of the insoluble carbonates or hydroxides are introduced into the catalyst, which at the oxides result from the heat treatment. To introduce the molybdenum component, any molybdenum oxide, for example the dioxide,

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Trioxide, pentoxide or sesquioxide, is preferred a hydrolyzable or decomposable molybdenum salt such as eg molybdenum halide is used. A preferred starting material is the ammonium heptamolybdate. The arsenic can be introduced in the form of ortho-arsenic acid. The phosphorus can be in the form of a Alkali metal, alkaline earth metal or ammonium salt are introduced, but it is preferably introduced in the form of phosphoric acid. The other elements can be introduced starting from the metal, the metal with an oxidizing acid, such as B. nitric acid, oxidized and then incorporated the nitrate into the catalyst. In general, however, the nitrates are light available and make a very convenient starting material.

Other variations in the starting materials will be apparent to those skilled in the art, especially if those mentioned above are preferred Starting materials are unsuitable for reasons of economy in large-scale production. In general Any compounds containing the desired catalyst components can be used provided that they when heated to a temperature within the range given below, the oxides for the catalyst according to the invention result.

The catalyst can be used without a carrier and has excellent activity. The catalyst can also use be combined with a carrier and preferably it is at least 10 up to about 90 wt .-%, based on the total composition

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composition, a carrier compound combined. It can all known Support materials, such as. B, silicon dioxide, aluminum oxyc zirconium oxide, titanium oxide, alundum, silicon carbide, aluminum oxide-silicon dioxide, inorganic phosphates, such as. B. aluminum phosphate, silicates, aluminates, borates, carbonates and materials such as z. B. pumice stone, montmorillonite and the like. Which are among the in the Use of the catalyst occurring reaction conditions are stable, can be used.

The catalytic activity of the system is increased by heating to an elevated temperature. In general, the catalyst mixture is dried and heated to a temperature of about 260-982 ⁰ C (500-180O ⁰ F), preferably from about 482 to about 704 ⁰ C (900-1300 ⁰ I about 1 to about 24 hours or more. If the activity is insufficient, the catalyst can be heated further to a temperature above about 538 ^° C. (1000 ^° F.), but below a temperature which is detrimental to the catalyst.Generally, the activation of the catalyst will occur at the higher temperatures Whether the activation is sufficient under given conditions is determined by spot testing a sample of the material for catalytic activity Activation is best carried out in an open chamber with air or oxygen circulating, see above that the consumed oxygen can be replaced. In addition, a pretreatment or activation of the catalyst prior to its use with a Reducing agent in the presence of a limited amount of air at a temperature within the range 260-538 ⁰ C (500-1000 F ⁰⁾ low. A loading

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vorzugtes process for the preparation of the catalyst according to the invention and a detailed description of the process of the invention are given in the _s following examples.

Except for the production of unsaturated aldehydes and carboxylic acids the catalyst of the invention is also useful for Conversion of olefins, such as. B. propylene and isobutylene, mixed with ammonia, into the corresponding unsaturated nitriles

Examples 1 to 4

The catalysts of these examples were prepared according to those described in US Pat 2,941,007 and US Pat. No. 3,171,859, respectively.

Examples 5, 7 to 9 and Π to 14

The catalysts used in these examples were prepared substantially by the same method, as described below, materials using the appropriate output. ¹ A catalyst having the composition 80 wt .- * K _{0 07} Mg ₄ 5Fe ₄ Bi _{2 0} 5 P ^M o ₁₂ ° 5i / ²⁰ wt .- * SiO ₂ was prepared by dissolving 70.6 g CNH ₄₎ Jmo ₇ O ₂₄ .4H ₇ O in water with minimal heating. To this, 1.9 g of K ₃ PO ₄ (85% strength by weight) and 76.7 g of colloidal silicon dioxide sol (DuPont Ludox AS, 30% strength by weight) were added in succession with stirring. The solution was stirred at room temperature for 15 minutes. 53.7 g of Fe (NO ₃ ) 2 · 9Η ₂ Ο, dissolved in water, were added to this solution and were then added

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successively 38.5 g Mg (Np ₃ ) ₂ · 6K ₂ O, 0.23 g KNO ₃ and 32.4 g Bi (NO ₃ ) 2 "5H ₂ O, dissolved in water, the 8 cm concentrated HNO ₃ (68 wt .-% strength) was added. The slurry was ernitzt with constant stirring until gel formation occurred. The gel was then dried at about 132 ⁰ C (27O ⁰ F). The resulting catalyst was 5 hours at 316 ⁰ C (600 ⁰ F) and 20 hours heat treated at 549 ⁰ C (1020 ⁰ F) and then brought to a particle size of 0.84-0.42 mm (20-35 Tyler mesh screen) ge ·?.

Example 6

A non-supported catalyst of the composition Mg. ₅ Fe.Bi ₂ P ^ 5 ^ ⁰ I ₂ ⁰ SJ ^was prepared by dissolving 70.6 g (NH ₄ ] L Mo-O ₂ -.4H ₂ O in water with minimal heating, to which was added 1.9 g Κ ₃ ^ΡΟ 4 (85 wt .-% strength). The Lösun _ü was stirred for 15 minutes at room temperature. to this solution, 53.7 g of Fe (NO _{3) 3} ' 9H ₂ O, dissolved in water, was added, then 38.5 g of Mg (NO ₃ ) ₂ · 6K ₂ O and 32.4 g of Bi (NO ₃ ) y 5K ₂ O, dissolved in water, which was 6 cm concentrated, were added one after the other containing HNO ₃ (68 wt .- ig!) was added. The slurry was heated with continuous stirring until gel formation occurred. The gel was then dried at about 132 ⁰ C (27O ⁰ F). The resulting catalyst was 5 hours Heat-treated at 316 ⁰ C (60.0 ⁰ F) and for 20 hours at 549 ⁰ C (1020 ⁰ F) and then brought to a size of 0.84-0.42 mn (20-35 Tyler screen mesh).

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Example 10

An abrasion-resistant catalyst of the composition 60 wt .-% Mg ₄ , .Fe ₄ Bi ₂ P _{0 5} Mo ₁ 2 ° ^{51/40 wt} «- ^? " ^Si0 2 ^wu *" de produced by dissolving 706 g (NiI ₄ ) ^ k) ₇ O ₂₄ .4K ₂ O in 5 70 cm ^{3 of} water with minimal heating and then wiping with 19 g of 85% H ₃ PO ₄ 767 g of 30 "g of silicon dioxide sol (DuPont AS Ludox) were added to this solution, followed by 537 g of Fe (UO,).,. 9H ₉ O

3
in aqueous solution containing 250 cm of water and an aqueous solution containing 385 g of Mg (NO ^) ₂ .6K ₂ O in 190 cm V / water are added. A solution consisting of 324 g of Bi (NOj) ₃ .5H ₂ O, 30 cm ^{3 of} 66% HMO ₃ and 380 cm ^{3 of} water was added to this strongly curled solution. The slurry was heated with stirring until a non-fluid cake was obtained. The solid was then treated at a temperature of 316 ⁰ C (600 ⁰ F) for 5 hours. After mechanically pulverizing the dry solid, 1000 g of powder was mixed with 1125 g of 30% silica sol (DuPont AS Ludox) and a sufficient amount of water to obtain a slurry with 40% by weight solids. The i-Iischung was lan ground _ö in a porcelain ball mill for 20 minutes. The resulting slurry was then (4 foot 1/2) in a Bowen Eprühtrockner with a Durcnmesser of 135 cm with an inlet temperature of 288 C (550 F) and a Auslaiitemperatur of 177 ⁰ C (35O ⁰ F) spray-dried. The microspherical product obtained in the spray dryer was placed in an oven at 138 ° C (20 ° F). The temperature was raised to a temperature of 316 C (000 F) again and 3 Ii tun- over a period of 1 hour.

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kept at this temperature for a long time. Before discharging the material In the fluidized bed reactor for testing, the catalyst was subjected to a 15 hour final calcination at 593 ° C (1100 ° F).

Example 1 6

A catalyst with the composition 30% by weight IC ₀ Q ₇ Hg ₄ 5Fe ₄ Bi ₂ P _{0 5} Mo ₁₂ 0 ₅₁ /20% by weight SiO _{2 was} prepared as follows:

212 g (NH ₄₎ / IiO ₇ O ₂₄ .4H ₂ O were dissolved with minimal heating in water then were added sequentially with stirring 5.7 g of H ₃ PO ₄ (35 wt oig ^p) and 230 g of colloidal silica sol (DuPont Ludox AS, 30% strength by weight) was added. 161 g of Fe (NO ₃ ) _{3 were added to this solution}

9H ₂ O, dissolved in water, was added and then 115.5 g of Ug (NO ₃ ) _2. -6H ₂ O and 0.69 g of IQTO ₃ , dissolved in water, were added in succession. 97.2 g of Bi (MO ₃ ), 5H ₂ O, dissolved in water containing 9 cm of concentrated HNO ₃ (68% strength by weight) were added to the vigorously stirred slurry. The slurry was stirred continuously for about 15 minutes. Then, the slurry was spray dried and the powder obtained in the spray dryer was further dried for 16 hours in an oven at 11O ⁰ C (23O ⁰ F). The resulting dry powder was mixed well with 1% by weight graphite and compacted into 0.109 cm χ 0.327 cm (1/16 χ 3/16 inch) pellets using a conventional pelletizer. The pellets were heated for 5 hours at 232 ⁰ C (45O ⁰ F) to decompose the nitrates and then \ vurden it for 20 hours at 549 C

(1020 ⁰ F) calcined.

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The method used to carry out the oxidation reactions in Examples 1 The reactor used to 15 was a standard reactor with a fixed catalyst bed. xThe catalyst volume was about 5 cm and the Catalyst particle size was 0.84-0.42 mm (20-35 Tyler screen mesh). The gases were metered into the reactor with rotameters. The reaction products were made by washing the effluent gases of the reactor obtained with water and then analyzed by gas chromatography.

The percentage conversions given in the examples in the unsaturated are compounds containing oxygen defined as follows:

Conversion into an unsaturated aldehyde or into an unsaturated " Carboxylic acid in mol-I per pass =

Moles of aldehyde or acid obtained _x - \ qq moles of olefin used

The oxidation reactions that occur with the catalyst compositions according to the invention using propylene and isobutylene as the hydrocarbon feedstock are disclosed in US Pat summarized in the following Tables I and II. These dates are compared to the conversions obtained with the catalyst compositions described in US Pat. Nos. 2,941,007 and 3,171,859 which are given in Examples 1 to 4 of Table I and Example 14 of Table II. The data in these Tables show that with the catalysts of the invention

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Conversions (conversions) into acrolein, methacrolein, obtained per pass, Acrylic acid and methacrylic acid were significantly higher than those obtained with the known catalysts. The catalysts according to the invention gave comparable yields of unsaturated aldehydes and unsaturated acids both in fixed bed reactors and in fluidized bed reactors when used of pelletized catalysts or catalysts from fluid Type. *

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T a b e 1 1 e I 0
leader s 15 minutes Passage in
Acrylic acid Conversion of running time β 30 minutes 2.9, Mole ratio Contact
time in
Seconds Mon 1-%
Conversion per
Acrolein 3.5 » Catalyst volume β 5 _C m ^ Propylene in acrolein and acrylic acid 2.5 22.8 3.9 Particle size of the catalyst of the starting material: C ^s / air / H ₂ 0 = 1/11/4 5.0 35.6 6.8 example
No. Catalyst composition 2.5 22.0 10.6 1 50% Bi ₀ PKk) ₁ OOr, / 501 SiO ₉ ^s 0.84- - 0.42 mm
Γ2Ο-35 meshl 5.0 48.5 2 It Il Reaction
temperature
in oC ( ⁰ F) 5.0 64.4 5.7. 3 50% Fe _{4 5} Bi ₄ 5PMo ₁₂ O ₅₂ / 5O4 SiO 360 (680) 7.8
O
17.2 CO 4th ti 360 (680) 5.0 78.3 20.6 - * 5 80% Mg _n [.Fe-Bi ₁ P _n -Mo ₁₉ O. _Q / ₂₃₁₉ (605) 2.5
2.5 67.3
54.3 20% SiO ₂ 360 (680) 5.0 51, 2 6th 100% Mg _{4 5} Fe ₄ Bi ₂ P _{0 5} Μο ^ ₂ ° 51 360 (680) 7th
δ SOI Mg _4f5 Fe ₄ Bi ₂ P _{0> 5} Mo ₁₂ 0 ₅₁ /
20% SiO ₂
ti 9 80% Mg _4fS Fe ₄ Bi ₂ P _0fS Mo ₁₂ 0 _5i /
20% SiO ₂ 360 (680) 319 (605)
360 (680) 360 (680)

• bo VO bo ^, • ft CM - 19 - to 2203710 ρ « ft Ä ^ ^- ft 3 co J O LO N CM O ft to • σ » + J ft ο I. ft ft Q) ^ · νθ OO Ln Vi VO Ο νθ vD -μ Ln O ft LO ! ι O ΙΛ ft O CM CM CM Q> oo O* / "■" »
O » Ι O νθ co co VO : 6 <- » O VO VO σ> ^ Λ VO O O rH τ— bo ίο to VO VO to Ö (U to IO (U
r-l τ-Κ
O) 'CM CM O O O O tH oo •H • Η •HI CO CO (D O r— E- * LO Ln <$$ * CM dp O O O O CM CM •H ^ j- ta ₁ - CO • Η O τ— τ—. * τ3 Ln t ^ approx Ln PJ Ln O O O : cÖ ft CM CM CM O ~> » to CM JO O (U CM LO •H "in O 'In ^ PQ CM • I (U ^ · O τ— O • Η (U tn cw } - ( (M in CM ~ tM • Η CtJ •H ■ rl pq bO (U Ο) U * Ph Ά LO O CM Ln LO * "O • k ft Ο-Η «Φ ^) - M CO W) O O dp CO CM O O OO QO CM to

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- 20 Table II

Conversion of isobutylene into methacrolein and methacrylic acid

Reaction temperature - 36O ° C (680 ⁰ F) KontaktvZeit "2.5 seconds

Molar ratio iC ₄ ^s / air / H ₂ Ot / tj / 4

MoI-I conversion per sample run into

No. Catalyst Composition Methacrolein Methacrylic

acid

14 50% Fe ₁ --Bi ₄ CPiMo ₁ , 0 __ / 28.6 4.0 50% SiO ₂

15 100% Mg _{4 s} Fe ₄ Bi ₂ P ₀ 5 Mo ₁₂ O ₅₁ 48.5 4.8

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Claims (14)

- 21 claims . ^ Process for converting an olefin from the group of propylene, isobutylene and mixtures thereof into the corresponding unsaturated aldehydes and unsaturated carboxylic acid ^ characterized in that the olefin is at a temperature of about 260 to about 482 ⁰ C (500-90O ⁰ F) and reacting at a pressure of about 0.5 to about 5 atmospheres with a gas phase containing molecular oxygen in the presence of a catalyst of the empirical formula ^A a ^B b ^C c ^Fe d ^Bi e ^Mo f ° x wherein A is an alkali metal, B phosphorus or arsane or both and C at least one element from group II A and II B of the Periodic Table of the Elements and in which are (a) a number from 0 to less than 0.1, (b) a number from 0 to 3, (c) a number from 0.1 to 10, (d) and (e) each one Number from 0.1 to 6, (f) a number from 8 to 16 and (x) one Number determined by the valence of the other elements present. 2. The method according to claim 1, characterized in that air is used as the molecular oxygen-containing gas. 209834/1210 3. The method according to claim 1 or 2, characterized in that propylene is used as the olefin. 4. The method according to claim 1 or 2, characterized in that isobutylene is used as the olefin. 5. The method according to claim 3, characterized in that a molar ratio of olefin to oxygen is within the range from 1: 0.5 to 1: 5 is used. 6. The method according to claim 5, characterized in that it is carried out xtfird in the presence of steam. 7. The method according to claim 1, characterized in that a catalyst is used which is applied to a support material is. 8. The method according to claim 7, characterized in that a Catalyst is used, which is applied to a support material in amounts of about 10 to about 95 wt .-%, based on the catalyst applied to the support. 9. The method according to claim 8, characterized in. » the existence Catalyst that has been produced is used 2ιΠ *; Κ / 1 21 0 (a) by activating a mixture of the catalyst with 0 to 60 wt .-% of the total support material at a temperature of about 538 to about 1093 ⁰ C (1000-2000 ⁰ F) in an oxidizing atmosphere and comminution of the catalyst obtained to a fine powder and (b) Mixing the powder obtained in step (a) with an aqueous slurry of the remaining carrier material, drying and heat-treating the mixture obtained at a temperature of about 399 to about 1093 ⁰ C (750-200O ⁰ F) 10. The method according to claim 1, characterized in that a Catalyst is used, in whose molecular formula C an element of group II 'A of the Periodic Table of the Elements means" 11. The method according to claim 10, characterized in that a catalyst is used as the element of group II A of the Periodic Table of the Elements contains magnesium. 12. The method according to claim 1, characterized in that it is in the presence of a pelletized catalyst in a fixed bed reactor and optionally carried out in the presence of steam. 13. The method according to claim 1, characterized in that it is in 2 0 9 8 3 4/1210 Presence of a fluidized catalyst in a fluidized bed Reactor and optionally in the presence of steam is carried out. 14. The method according to claim 1, characterized in that as
Oxygen-containing gas uses molecular oxygen
and that the process is carried out in the presence of process steam. 209834/1210