CA1094098A - Simultaneous production of methacrylic acid and a methacrylate or acrylic acid and an acrylate - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:
A process for simultaneously producing methacrylic acid and a methacrylate or acrylic acid and an acrylate by reacting methacrolein or acrolein with an aliphatic alcohol and molecular oxygen in the vapor phase by using a catalyst comprising (1) palladium, (2) phosphorous, (3) antimony, (4) X and (5) oxygen wherein X denotes 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.

Description

li 1094098 ¦ DETAILED DESCRIPTION OF THE INVE~TION:
This invention relates to a process for producing methacrylic acid and a methacrylate or acrylic acid and an acryla`te at the same time.
- More particularly, this invention relates to a process for simultaneously producing methacrylic acid and a methacrylate or acrylic acid and an acrylate by reacting methacrolein or acrolein with an aliphatic alcohol and molecular oxygen in the vapor phase by using a catalyst comprising (1) palladium, (2) phasphorus, ~3~ antimony, t4) X and (5) oxygen wherein X denotes at least one element selected from the group consisting of potassium, sodium, lithium, rubidium, cerium, beryllium, lead, magnesium, calcium, strontium, zinc, barium, l thorium, bismuth, chromium, iron, nickel, cobalt, vanadium, 15 ~ manganese, tin, uranium and rhenium.
The process of the invention may further comprise supplying into the reaction system a phosphoric acid or a phosphorus compound capable of forming a phosphoric acid through a chemical change during the reaction.
For the synthesis of methacrylic acid by oxidizing methacrolein in a vapor phase a number of catalysts have hitherio been proposed.
Almost all of these catalysts, however, have low l activities. Further, if the reaction is carried out at an elevated temperature in order to increase the conversion, ., I

09409~ j large amounts of undesirable by-products such as carbon monoxide, carbon dioxide, acetic acid etc. are produced so that the per-pass yield of methacrylic acid is very low.
~ The catalysts as disclosed in the Japanese Patent ¦ Laid-Open Publication Nos. 67216/1973 and 61416/1973, which are improved in their catalytic activity and selectivity, I comprise phosphomolybdic acid or its salts as the main ingredient, Phosphomolybdic acid-based catalysts have a dis-advantage that the catalyst lifetime is short. Once they lose activity, it cannot be restored by means of a simple treatment such as re-calcination, for example. When the temperature of reaction or calcination exceeds 450C, they are abruptly degraded in catalytic activity. Thus, they are thermally unstable and they are not always available for commercial use.
Further, conventional phosphomolybdic acid-based catalysts offer a notably short catalytic lifetime when the reaction is carried out at a particularly high space velocity.
Japanese Patent Laid-Open Publication No. 30,826/1975 2Q discloses a process for producing methyl methacrylate which !¦ comprises subjecting a gas mixture of methacrolein, methanol, ¦¦ oxy~en, steam and nitrogen to the reaction in the vapor phase ¦¦ in the presence of a molybdenum-vanadium-tungsten series catalyst.
¦ The process is far from commercially satisfactory because the yield of methyl methacrylate is very low.

, `` 1094098 Another disclosure relating to a catalyst containing palladium, phosphorus and oxygen is described in Japanese Patent Laid-Open Publication No. 37,719/1975. Methacrylic acid is prepared by oxidizing methacrolein with molecular oxygen in the presence of the above catalyst. The destined product, methacrylic acid is produced in higher yield and selectivity, while a comparatively large amount of steam is required. The larger the feed, the larger the equipment, which is undesirable on an industrial scale and economically disadvantageous. Since the process of the above application is only directed to the preparation of methacrylic acid, it is, of course, impossible to prepare an ester at the same time.
The present invention is directed at overcoming the aforementioned disadvantages and according to the process of the present invention, methacrolein or acrolein is oxidised at low temperature such as 160 to 350C and methacrylic acid and a methacrylate or acrylic acid and an acrylate are produced in high yields at the same time. Further the formation of by-products such as acetic acid, carbon monoxide and carbon dioxide owing to the degradation is well suppressed. The amount of steam to be fed during the reaction may be very small, which is one of the important characteristics of the invention.
In addition the catalyst according to the present invention is I ~094098 I

thermally stable and therefore has a substantially longer service life, particularly even when the reaction is carried out at high space velocities.
~ The process of the invention is not only economically advantageous, but also industrially epoch-making.
The catalyst to be used in the present invention comprises (1) palladium, (2) phosphorus, (3) antimony, (4) X and (5) oxygen wherein X denotes at least one element selected from the group consisting of potassium, sodium, lithium, rubidium, cerium, beryllium, lead, magnesium, calcium, strontium, zinc, ~arium, thorium, bismuth, chromium, iron, nickel, cobalt, vanadium, manganese, tin, uranium, and rhenium and has a long service life which is significantly superior to those of the prior phosphomolybdic acid-based catalysts.
It has surprisingly been found that the catalyst is stable at elevated temperatures, for example, at 600C.
However, this catalyst as such is not completely satisfactory, because a part of phosphorus which is one of the essential components of the catalyst, though in a very small amount, leaves the catalyst system during the reaction.
Consequently, the semipermanent life required for commercial catalysts can not be attained.
The inventors have found that when the reaction is l carried out in the presence of the catalyst, the catalyst can be st~bilized and its servi~e life can iurther be prol~nged l - 5 -i! ~

by continuously or intermittently supplementing phosphorus in an appropriate amount corresponding to that of the phos-phorus which leaves the catalyst system.
¦ The process of the present invention is epoch-¦ making and of great value for commercial use since methacrylic acid and a methacrylate or acrylic acid and an acrylate can be selectively produced in high yields for long periods of time.
The term "a phosphoric acid or a phosphorus compound capable of forming a phosphoric acid through a chemical change during the reaction "(hereinafter to be referred to as a phosphorus-containing compound~ which is to be supplied to the reaction system in accordance with the present invention means any of phosphoric acids and phosphorus compounds capable of forming a phosphoric acld through a chemical reaction such as hydrolysis, oxidation, etc., including orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, phosphine, organic phosphoric acids, solid phosphoric acids, etc.
To the reaction system the phosphorus-containing 20 I compound may be supplied in any suitable manner.
For example, if the phosphorus-containing compound is water-soluble, it may uniformly be dissolved in water to be used for the reaction so that it is carried to the reaction system along with water.
If the phosphorus-containing compound is solid, for , l li l , . , ' 6 1 i 1.

¦ example, a solid phosphoric acid, this solid material may be charged in front of the catalyst layer. As steam is fed and made contact with the charged material, the latter generates ~ a phosphoric acid, which is carried to the catalyst layer , along with steam.
~urtheremore, if the phosphorus-containing compound is gaseous, a gaseous mixture of the same and air may be fed to the catalyst layer.
The amount of the phosphorus~containing compound to be supplied may vary over a wide range. In general, the phosphorus-containing compound is supplied so that the amount of phosphorus contained in the compound is preferably 5 to 1 x 10 4 wt%, more particularly 0.5 to 1 x 10 3 wt% on the l basis of a total amount of water and an aliphatic alcohol fed 1 during the reaction.
!l A preferred catalyst according to the present invention has the following composition: ¦
PdaPbSbCXdOe l wherein X denotes at least one element selected from the group I consisting of potassium, sodium, lithium, rubidium, cerium, !l beryllium, lead, magnesium, calcium, strontium, zinc, barium, ¦ thorium, bismuth, chromium, iron, nickel, cobalt, vanadium, manganese, tin, uranium, and rhenium, the subscripts a, b, c, ! d and e denote the number of the Pd, P, Sb, X and O atoms, " and wherein a is 1, b is 1 to 42, c is 0.1 to 15, d is 0.1 to 15 . , l 10~4098 i ¦ and e is a number determined by the valences of other elements ¦ and usually from 3.75 to 150.5.
Ii A more preferred catalyst is a composition represented ¦j the ab~ve formula in which the ratio among a, b, _, d and e ~' lies in the following range: a:b:c:d:e = 1:(1-28~:(0.2-10):
l ~0.1-10~:C6.4-101~.

! The catalyst according to the present invention can be prepared in a conventional manner well known in the art, I - for example, by the following procedures.
1 In one casej compounds of respective constituent elements and the carrier, if a carrier is used, are mixed.
The resultant mixture is evaporated to dryness and then the dried product is calcined.
ll In another case, a solid carrier is impregnated with ¦ compounds of each constituent element. This impregnated Il carrier is evaporated to dryness and then calcined.
I In still another case, a solid carrier is impregnated with compounds of some constituent elements and then subjected to a heat treatment, preferably at a temperature of 200- 700C.
¦ The partly impregnated carrier is further impregnated with compounds of the other constituent elements. This twice impregnated carrier is evaporated to dryness and then calcined.
In any of the aboYe-described procedures the calcina-~ tion temperature lies preferably in a range of 300-700C, 2S more preferably in a range of 400~ - 550C.

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~i , ¦ If necessary, the calcination or the heat treatment may be carried out in an atmosphere of reducing agent such as hydrogen, hydrocarbon etc.
, Examples of the compound of each constituent element i are listed below.

! Examples of palladium compound include palladium I chloride, palladium nitrate, pallad~um sulfate, palladium black and the l~ke.
I Examples of phosphorus compound include orthophos-1 phoric acid, phosphorous acid, hypophosphorous acid, pyro-phosphoric acid, metaphosphoric acid, polyphosphoric acids, their salts, and the like.
Examples of antimony compound include oxides, hydroxides and chlorides of antimony, such as antimony 1 dichloride, antimony pentachloride, antimony trioxide, and the like.
Examples of compound of the X constituent include nitrates, hydrochlorides, phosphates, sulfates, oxides, 1~ hydroxides of the X constituent, and the like.
I More concrete procedures for the preparation of the catalyst of this invention are explained as follows:
To an ammonia solution of any suita~le palladium , salt, for example palladium chloride, is added ortho-~ phosphoric acid (as 85% aqueous solution~,phosphorous acid,

2~ hypophosphorous acid or any other phosphoric acid or salt _ g _ .

Il lO9A098 Il I

! thereof, yielding a clear solution. To this clear solution I are further added a metal salt or oxide of antimony (such! as antimony trioxide) and a metal salt or oxide of the X
constituent, yielding an aqueous solution. Any suitable carrier ¦ is i~mpregnated with such aqueous solution, evaporated to dryness and then calcined in air at 300- 700C, preferably 400 - 550C for five or more hours.
The carrier which has been impregnated first with a palladium salt and thermally treated at a temperature of preferably 200- 700C may ~e impregnated with phosphoric acid, antimony trioxide and X compound and then calcined.
Or, the carrier which has been impregnated with antimony trioxide and X compound and thermally treated m~y be ~ impregnated with palladium chloride dissolved in ammonia water I and then calcined in air and thermally treated in an atmosphere ¦ of reducing agent such as hydrogen. The resultant substance ¦¦ is impregnated with phosphorus compound and then calcined.
¦ In either case the activity of the catalyst is not I¦ adversely affected.
'l The catalyst can include a carrier to lower the catalyst concentration, increase the catalyst strength or to enhance 1~ the economy of the catalyst. A suitable amount of a carrier l! may be impregnated with a small amount of the catalyst. Even I¦ a large amount of a carrier may be used.
1, As the carrier, may be employed inert substances such , ., , 1~ , l as silica sol, silica gel, silicon carbide, a-alumina, Alundum, celite, boiling bubble stone, aluminum powder, silicahydro gel and the like.
l ` The catalyst may be used in the form of spherical ~ granules, pellets, particles crushed to suitable size, tablets etc.
The aliphatic alcohol used herein is, for example, methanol, ethanol, propanol and the like.
l The molecular oxygen used herein is usually air.
lQ ¦ The oxygen may be diluted with an inert gas which does not adversely affect the reaction, such as nitrogen, carbon dioxide and the like.
To the reaction system methacrolein or acrolein and oxy~en are fed as a gaseous feed mixture in such proportions ! that the molar ratio of methacrolein or acrolein to oxygen is preferably 1:(0.5-30), more preferably 1:(1-8).
When methacroiein or acrolein is oxidized by oxygen in the presence of the catalyst of the invention and in the ~ absence of an aliphatic alcohol to produce methacrylic acid 1 or acrylic acid, the presence of steam is indispensable. If steam is absent, the oxidation of methacrolein or acrolein to 1i¦ methacrylic acid or acrylic acid takes place almost to the il least extent. Since an aliphatic alcohol is present according I¦ to the process of the inventionr the destined products, 1, methacrylic acid and methacrylate or acrylic acid and acrylate, !

I

can be obtained in high yields even in the absence of steam.
The selectivity of methacrylic acid and methacrylate or acrylic acid and acrylate is very high. However, by introducing ¦
a smali amount of steam the conversion of methacrolein or acrolein is further accelerated and the yield of methacrylic acid and methacrylate or acrylic acid and acrylate is further increased.
The steam is added in the gaseous feed mixture in such proportions that the amount of steam is preferably 0.1 to 28 moles, more preferably 0.5 to 10 moles per mole of methacrolein or acrolein.
The aliphat~c alcohol is preferably fed in an amount from 0.1 to 25 moles, especially 0.3 to 10 moles per mole of methacrolein or acrolein.
The temperature for carrying out the reaction is not so critical. The reaction may preferably be carried out at a temperature of 180 to 370C, especially 200to 330C.
The reaction can be carried out at atmospheric pressure or at lower or higher pressures. In general it is ¦ convenient to carry out the reaction at atmospheric pressure.
¦ ~ preferable range of pressure is 0.3 to 15 atm.
ll The gaseous feed mixture can be introduced at ¦¦ any desirable space velocity, preferably at a space velocity ~ of 300 to 15,000 Q-gas/Q-cat.hr, especially 700 to 8,000 ' Q-gas/Q~cat.hr.
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1094098 1.
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1, ' , ¦¦ According to the present invention satisfactory results ¦¦ are obtained even when the reaction is carried out at space velocities as high as 2,000 to 8,000 Q-gas/~-cat.hr. Further the service life of the catalyst is maintained for a long period ¦ of time under such conditions.

i The catalyst of the present in~ention may be applied in any form selected from a fixed bed, a fluidized bed and a moving bed.
The following examples are illustrative of the catalyst ¦
and the process of the present invention. In the examples, the terms "conversion of methacrolein or acrolein", "selectivity of methacrylic or acrylic acid", "selectivity of a methacrylate ! or acrylate", "yield of methacrylic or acrylic acid", "yield l of a methacrylate or acrylate", and "space velocity" are ¦ defined as follows:
Conversion of methacrolein or acrolein Moles of methacrolein or acrolein reacted 100 Moles of methacrolein or acrolein fed x Selectivity of methacrylic or acrylic acid l = Moles of methacrylic or acrylic acid produced x 100 % ¦
j Moles of methacrolein or acrolein reacted , Selectivity of a methacrylate or acrylate _ Moles of methacrylate or acrylate produced x 100 %
l Moles of methacroleln or acrolein reacted `' Yield of methacrylic or acrylic acid Moles of methacrylic or acrylic acid produced I Moles of methacrolein or acrolein fed x 100 ! `~

, . , l - 13 -1, ~

¦I Yleld of a methacrylate or acrylate ¦ _ Moles of methacrylate or acrylate produced x 100 Moles of methacrolein or acrolein fed l Space Velocity (SV) The flow rate* of a geseous feed mixture (Q-gas/hr.) The volume of a charged catalyst ~Q-cat.~
*calculated on a basis at the normal temperature and pressure Example 1:
While 16.0 g of Aerosil (SiO2) was heated and agitated, 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 thereafter, dried at 100C for eight hours. The dried mixture was impregnated with an aqueous 15 1 ammonia solution containing 0.44 g of palladium chloride, evaporated to dryness, thereafter repeatedly washed with 10 liters of distilled water and dried. The dried product was subjected to a heat treatment in the air at 450C for five hours and then thermally treated in an atmosphere of hydrogen 20 ¦ at 450C for five hours. The product was impregnated with 6.5 g of hypophosphorous acid ~30 %), evaporated to dryness.
Thereafter, the dried product was calcined in the air at 450~C
for five hours. The thus obtained product is named Catalyst A, I¦ the composition of which is represented by the formula:
25Pdl,OPl2,3sbl.OMgO-5o33-75 1' * trade mark - 14 - ;
., 10~4098 1~ s l! ' A reaction tube of stainless steel having an inner ¦¦ diameter of 20 mm was filled with 10 mQ of the Catalyst A
Il and dipped in a bath of molten nitrate. With the use of this ¦¦ reaction tube filled with Catalyst A the oxidation of methacrolei~
was carried out for 120 days.
As the phosphorus-containing compound was used trimethyl phosphate in the form of a 0.1 % solution (i.e.
methanol-water solution). This solution was fed in an amount l of 5 cc per hour.
A gaseous feed mixture contained methacrolein, methanol,j oxygen, steam, nitrogen and phosphorus in a relative molar ratio of 1:1:2:5.5:18.1:1.8xlO 3.
The gaseous feed mixture was supplied at a SV of 1565 Q-gas/Q-cat.hr.
,¦ The thus obtained products were determined by gas chromatography. The results are shown in Table 1.
Table Reaction Tempera- Conversion Selectivity Yield of Yield of time ture of of meth- of meth- meth- methyl ~day) the ni- acrolein acrylic acid acrylic meth-trate (%~ + methyl acid acrylate ll bath (~C) methacrylate (~
I I (% ) 1'Initial 285 74.5 89.3 40.0 26.5 ! 40 285 74.7 8g.2 40.3 26.3 120 285 74.7 8g.2 40.1 26.5 ~' i ., .

i 1094098 On the production of methacrylic acid and methyl methacrylate from methacrolein and methanol small amounts of by-products were derived, including 1.0 %
l of acrylic acid, 0.5 % of acetic acid, 2.5 % of carbon dioxide 5 i and 4.0 % of carbon monoxide.
Exam~le 2:
Example 1 was repeated except that metaphosphoric acid in the form of a 0.1 % solution (i.e. methanol-water solutionl was used as the phosphorus-containing compound in place of trimethyl phosphate.
Other reaction conditions were the same as those of . Example 1. The results are shown in Table 2.
Table 2 Reaction Tempera- Con~ersion Selectivity Yield of Yield of time ture of of meth- of meth- methacry- methyl (day) the ni- acrolein acrylic lic acid meth-trate ~%) acid + meth- (%) acrylate bath (C~ yl methacry- (%) late (%) 2Q stage 285 74.3 88.6 39.826.0 285 74.4 88.6 39.826.1 120 285 74.5 88.5 39.926.0 I . _ .
! On the production of methacrylic acid and methyl ~I methacrylate from methacrolein and methanol small amounts of 1¦ by-products were deri~ed, including 1.5 ~ of ,~l acrylic acid, 0.7 % of acetic acid, 2.0 % of carbon dioxide 'i l - 16 -., , " :

il ¦1 and 4.3 % of carbon monoxide.
,¦ Example 3:
I
A catalyst having the same composition with that of ¦ Example 1 was prepared in a similar way to that of Example 1, 5 l¦ except that hypophosphorous acid was replaced by phosphorous acid.
With the use of the catalyst the reaction was carried out in a similar manner as described in Example 1. The results l are shown in Table 3.
¦ Table 3 Reaction Tempera- Converslon Selectivity Yield of Yield of I time ture of of meth- of meth- meth- methyl l (day) the ni- acrolein acrylic acrylic methacry- !
i trate (%) acid + meth- acid late 1 bath (C) yl meth- (%) (%) , acrylate (%) ¦¦Initial 281 75.1 - 88.5 40.2 26.3 ~¦stage 281 75.0 88.8 40.5 26.1 120 281 75.1 88.3 40.3 26.0 ¦ On the production of methacrylic acid and methyl ¦¦ methacrylate from methacrolein and methanol small amounts of by-products were derived, including 1.6 % of ¦¦ acrylic acid, 0.4 % of acetic acid, 2.3 % of carbon dioxide and 4.3 % of carbon monoxide.
~5 ' Example 4:
1 l ,, The reaction described in Example 1 was repeated ~, . ~ .

; 17 -Il 1094098 ¦l except that acrolein was used in place of methacrolein.

The results are shown in Table 4.

Table 4 l Reaction Tempera- Conv~rsion Selectivity Yield of Yield of ¦ time ture of of acro- of acrylic acrylic methyl (day) the ni- lein acid + acid acrylate trate (%~ methyl acry- (%~
bath ~C) latè (%) stage 280 98.2 95.7 66.5 27.5 280 98.3 95.7 66.8 27.3 120 280 98.1 95.6 66.3 27.
On the production of acrylic acid and methyl acrylate l from acrolein and methanol small amounts of by-products were I derived, including 1.0 % of acetic acid, 1.5 % of carbon ¦~ monoxide, I.2 ~ of carbon dioxide and 0.5 ~ of acetone.

¦¦ Example 5:
The reaction was carried out under the same conditions as those of Example 1, except that the phosphorus-containing 1 compound was not fed at all. The results are shown in Table 5.
l Example 6:

I The reaction was carried out under the same conditions ¦¦ as those of Example 4, except that the phosphorus-containing compound was not fed at all. The results are shown in Table 5.

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l Table 5 I .
Exam- Reaction Tempera- Conversion Selectivity Yield of Yield of ple time ture of of meth- of meth- meth- methyl No. (dayl the ni- acrolein acrylic acrylic methacry~
trate (%) acid + me- acid late ! bath (C) thyl meth- (%) (~) l acrylate . .... ~_ 5 stage 287 74.7 88.8 40.0 26.3 287 70.1 90.2 39.1 24.1 Exam- Reaction Tempera- Conversion Selectivity Yield of Yield of ple time ture of of acro- of acrylic acrylic methyl No. (~ay) the ni- lein acid + acid acrylate trate (~) methyl (%) (%) bath (C) acrylate 6 stage 281 98.0 94.5 66.2 26.4 l 10 281 92.0 93.7 63.1 23.1 Examples 7 - 80:
The catalysts having the compositions shown in Table 6 were prepared in a manner similar to that described in Example 1, if necessary, using salts of the X constituent, ammonium Il metavanadate and rhenium chloride etc. With use of these ! catalysts the reactions were carried out under the same condi-I, tions as those of Example 1, except that the phosphorus-contain-¦~ ing compound was not fed at all. The results are shown in Table 6.
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1: .
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¦¦ Examples 81 - 102:
Reactions using the catalysts of the said Examples were carried out under the same conditions as those of Example 1. ~he result- re b~wn in Table 7 ~_ !

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,, ` 1094098 li Examples 103 - 104:
The catalysts having the compositions shown in Table 8 were prepared in a manner similar as in Examples 7 - 80.
With use of these catalysts the reactions were carried out , under the same conditions as those of Example 1. The result are shown in Ta~le 8.
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- 32 ', . 1094098 i, , ,i Examples 105 - 126:
Reactions described in Example 4 were repeated Il except that catalysts having the compositions shown in Table ,i 9 prepared in the same manner as in Examples 7 - 80 were used .1 and the phosphorus-containing compound was not fed at all.
The results are shown in Ta~le 9.

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li , ! Example 127:
il The reactions described in Example 4 were carried l~ out for 120 days using the same catalysts as in Examples ! 105 - 126. The results obtained after 120 days were nearly 1 the same as those obtained at the initial stage. The yields of acrylic acid and methyl acrylate were not decreased for 12Q days.
Example 128:
l Examples 1 and 4 were repeated except that solid l phosphoric acid (celite/phosphorus = 50/50~ heat treated at 550C was used as the phosphorus-containing compound in place i of trimethyl phosphate.
On the upper side of the catalyst layer consisting l of 10 m~ of Catalyst A was placed 5 ml of the solid phosphoric ¦ acid.
The results were nearly the same as those of Examples 1 and 4.
Example 129;
l Examples 81 - 104 and 127 were repeated except that 1 orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid and solid phosphoric acid were used as the phosphorus-containing compound in place of trimethyl phosphate, respectively, ¦ in each case. It has been found that the results are nearly ,~ the same as those of Examples 81 - 104 and 127.
,! !

i 1094098 ,, Example 130: 1 Examples 1 and 4 were repeated except that the amount of the phosphorus-containing compound supplied was changed.
l The amount of phosphorus contained in the compound was changed 1 in the range of 0.5 wt% to 1 x 10`3 wt% based on total amount of water and methanol fed. The results were nearly the same as those of Examples 1 and 4.
Example 131:
A catalyst was prepared by following the procedure noted in Example 1, except that the impregnation order of palladium and phosphorus was changed. Using this catalyst the reactions were carried out in the same manner as in Examples 1 and 4. The results were nearly the same as those of Examples 1 and 4.
Example 132:
A catalyst was prepared by following the procedure noted in Example 1, except that palladium and phosphorus were impregnated at the same time. Using this catalyst the reactions were carried out in the same manner as in Examples 1 and 4.
The results were nearly the same as those of Examples 1 and 4.

i Example 133:
16.0 g of Aerosil, 0.4 g of antimony trioxide, 0.17 g 'I of magnesium phosphate, 6.5 g of hypophosphorous acid and 10 cc ¦¦ of an aqueous ammonia solution containing 0.44 g of palladium I chloride were mixed together. The mixture was evaporated .
37 ~, . .

i! .
!l i ¦ to dryness. The dried product was calcined in the air at 450C
for five hours. The catalyst thus obtained had a composition ~, represented by the formula: ¦
I PdlP12 3SblMgo~sO33~75 ¦¦ Using this catalyst the reactions were carried out in the same manner as Examples 1 and 4. The results were nearly the same as those of Examples 1 and 4.
Example 134:
Example 1 was repeated except that the gaseous feed mixture was supplied at a SV of 4000 Q-gas~Q-cat. hr. The ¦ results are shown in Table 10.
Table 10 i Reaction Tempera- Conversion Selectivity Yield of Yield of l time ture of of meth- of meth- meth- methyl l (day~ the ni- acrolein acrylic acrylic meth-I trate (%) acid ~ acidacrylate bath ~C~ methyl (%) (%) methacry-I
iInitial 296 67.7 89.5 37.223.4 stage 296 67.6 89.3 37.423.0 120 296 67.6 ag.4 37.423.0 .
. .

ll 1094098 ¦ Example 135:
¦ Example 4 was repeated except that the gaseous feed mixture was supplied at a SV of 4000 Q-gas/Q-cat. hr.
The results are shown in Table 11.

~ Table 11 Reac- Tempera- Conversion Selectivity Yield of Yield of tion ture of of meth- of meth- methacry- methyl time the ni- acrolein acrylic acid lic acid methacry-(day) trate (~) ~ methyl (~) late bath (C) methacrylate (~) Initial 287 91.6 93.6 62.1 23.6 stage 287 91.4 93.7 62.3 23.3 120 287 91.3 93.9 62.4 23.3 Example 136-139:
The reaction described in Example 1 was repeated in the presence of Catalyst A with a varying molar ratio between reagents in a gaseous feed mixture. The results are shown in Table 12.

¦ _ 39 _ ,, 1, , "

¦l In Table 12, gaseous feed mixtures B - E have the ¦¦ following relative molar ratio:

feed acertOhlein : methanol : oxygen : stea~ : nitrogen : phhOrus il B 1 1 2 0 18.1 1.8xlO
C 1 2 4 5.5 13.6 1.8xlO-~
D 1 1 3 8.0 15.9 3.6xlO I
E 1 4 8 13.0 25.0 1.8xlO 1 Table 12 i Exam- Gaseous Tempera- Conversion Selectivity Yield of Yield of ple feed ture of of meth- of meth- meth- methyl No. mixture the ni- acrolein acrylic acrylic methacry-trate (%) acid ~ acid late bath (C) methyl (%) (%) methacry-late 1%) 136 B 300 66.5 88.7 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 87.8 39.6 16.2 _ Example 140 - 143:

i The reaction described in Example 4 was repeated in l~~ the presence of Catalyst A with a ~arying molar ratio be.ween Il' reagents in the gaseous feed mixture. The results are shown in li Table 13.
Il In Table 13, gaseous feed mixtures F - I have the 1. 1 "

~094098 ¦ following relative molar ratio:

feed acrolein : amnOhl : oxygen : steam : genr : phhOorus 1 F 1 1.5 2 0 18.1 1.8x10-3 G 1 2 4 7.5 13.6 3.6xlO 3 H 1 1 8 12.5 21.6 1.8xlO 3 I 1 4 5 3 12.3 5.4xlO

Table 13 Exam- Gaseous Tempera- Conversion Selectivity Yield of Yield of ple feed ture of of acro- of acrylic acrylic methyl No. mixture the ni- lein acid + acid acrylate trate (%) methyl (%) (~) bath (C) acrylate 140 F 287 94.8 91.7 58.1 28.8 141 G 272 98.8 93.0 64.9 27.0 142 H 270 98.7 90.2 67.3 21.7 143 I 282 95.1 92.7 60.1 28.1 .
I

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.

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- 41 - !

Claims (9)

WHAT IS CLAIMED IS:

1. A process for simultaneously producing methacrylic acid and a methacrylate or acrylic acid and an acrylate by reacting methacrolein or acrolein with an aliphatic alcohol and molecular oxygen in the vapor phase by using a catalyst comprising (1) palladium, (2) phosphorus, (3) antimony, (4) X and (.5) oxygen wherein X denotes 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.

2. The process according to Claim 1 wherein a phosphoric acid or a phosphorus compound capable of forming a phosphoric acid through chemical change during the reaction is concurrently supplied to the reaction system.

3. A process for simultaneously producing methacrylic acid and a methacrylate or acrylic acid and an acrylate by reacting methacrolein or acrolein with an aliphatic alcohol and molecular oxygen in the vapor phase by using a catalyst having the following composition:

PdaPbSbCXdOe wherein X denotes 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 rhemium, the subcripts a, b, c, d and e denote the number of the Pd, P, Sb, X and O atoms, and wherein a is 1, b is 1 to 42, c is 0.1 to 15, d is 0.1 to 15 and e is a number determined by the valences of other elements and usually from 3.75 to 150.5.

4. The process according to Claim 3 wherein a is 1, b is 1 to 28, c is 0.2 to 10, d is 0.1 to 10 and e is 6.4 to 101.

5. The process according to Claim 1 wherein said aliphatic alcohol is methanol.

6. The process according to Claim 2 wherein said phosphoric acid is orthophosphoric acid, pyrophosphoric acid or metaphosphoric acid.

7. The process according to Claim 2 wherein said phosphorus compound capable of forming a phosphoric acid through chemical change during the reaction is solid phosphoric acid or organic phosphoric acid.

8. The process according to Claim 1 wherein a reagent is methacrolein.

9. The process according to Claim 1 wherein a reagent is acrolein.