CA1099250A - Process for the preparation of unsaturated acids from unsaturated aldehydes - Google Patents

Abstract

PROCESS FOR THE PREPARATION OF
UNSATURATED ACIDS FROM UNSATURATED ALDEHYDES

ABSTRACT OF THE DISCLOSURE
Methacrylic acid or acrylic acid are produced by the oxidation of methacrolein or acrolein, respectively, with molecular oxygen in the vapor phase in the presence of a catalytic oxide of molybdenum, phosphorus, arsenic, oxygen and the following components delineated in Groups I to III: (I) a rare earth element or mixture thereof, and optionally, at least one of Ag, Tl, Rh, Pd, Ru, Pt, Cd, Al, Au, Cu, alkaline earth metal, Cl and NH4; or (II) at least one element selected from the group consisting of U, Ti, Nb, Re, Pb, Zn and Ga, and optionally, at least one of Cu, a rare earth element, Ag, Ta, In, Th, Cd, Tl, alkaline earth metal, NH4, Cl, Ni, Al, and Ge; or (III) at least one element selected from the group consisting of Ag, Rh, Ru and Au, and optionally, at least one of Cd, Pt, Tl, Pd, Al, Ge, Cu, Ni, alkaline earth metal, NH4 and Cl.

Description

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BACKGROUND OF THE INVE~TION
A number Or catalysts are known to be effective for the oxidation of acrolein or methacrolein to acrylic acid or methacrylic acid, respectively. However, the y~elds obta~ned using the ca~alysts for the preparation o~
metahcrylic acid are low. West German Provisional Patent No. 2,048,620 discloses catalysts containing the oxides of molybdenum, phosphorus, and arsenic for the oxidation of methacrolein and acrolein to methacrylic acid and acrylic acid, respectively. U. S. Patent Mo. 3,761,516 discloses catalysts containing oxides of molybdenum, arsenic and phosphorus on a support, especially A12O3, having external macropores and a surface not greate~ than 2 m2/g.

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The present invention is a result of a se~rch for more efficient and desirable catalysts for the production of acrylic acid and methacrylic acid. Unexpectedly higher yields of and selectivities to acrylic acid and methacrylic acid are obtained by the vapor phase oxidation of acrolein and methacrolein, respectively, with molecular oxygen in the presence of the new and useful catalysts of the present invention.

SUMMARY OF THE INVENTION
It has been disclovered according to the present invention in the process for the preparation of acrylic acid or methacrylic acid by the oxidation of acrolein or meth-acrolein, respectively, with molecular oxygen in the vapor phase at a reaction temperature of about 200C to about 500C in the presence of an oxide catalyst, and optionally in the presence of steam, the improvement comprising using as a catalyst a catalyst described by the formula xayb~lTol2pcAsdox wherein X is a rare earth element or a mixture thereof;
Y is at least one of Ag, Tl, Rh, Pd, RU, Pt, Cd, Al, Au, Cu, al~aline earth metal~ Cl and NH4;
wherein a is 0.001 to 10;
b is O to 10;
c is 0.~1 ~o 5;
d is 0.01 to 5;
x is the number of oxygens required to satisfy the valence states of the okher elements present; or (4958) (4959) ~ ing as a catalyst a catalyst described by the formula ~aYbMl2PcAsdox ; wherein X is at least one element selected from the group consisting of U, ~rl, Nb, Re, Pb, Zn and Ga;

Y is Cu, a rare earth element, Ag, Ta, In, Th, Cd, Tl, an alkaline earth metal, NH4, Cl~ Ni, Al and Ge~
and wherein a is 0.001 to 10;
b is O to 10;
c is 0.01 to 5;
d is 0.01 to 5-x is the number of oxygens required tosatisfy the valence states of the other elements present; or uslng as a cakalyst a catalyst describe~ by the ;~ formula xaYbMI2PcASdOx wherein X is at least one element selected from the group consisting of Ag, Rh~ Ru and Au;
Y is at least one of Cd, Tl, Pd7 Al, Ge, Cu, Pt, Ni, alkaline earth metal, NH4, and Cl;
and wherein a is 0.001 to 10;
b is O to 10;
c is 0.01 to 5 d is 0.01 to 5;
x is the number of oxygens required to satisfy the valence states of the other elements present.
The surprisingly advarltageous catalysts of this invention give im~roved yields of acrylic acid and methacrylic acid from acrolein and methacrolein, res~ectively, in an efficient, convenient, and economical manner at a relatively low temperature. ~he exotherm of the reaction is low, thereby allowing easy reaction control.

(4957) ~ (4958) The most si~nificant aspect of the present inven tion is the catalyst employed. The catalyst may be any of the catalysts delineated by ~ormulae I to III. The cat-alysts can be prepared by a number of different techniques described in the art, such as coprecipitation of soluble salts and calcination of the resulting product. The cat-alysts of the invention have preferred limitations on their composition.
When catalysts within formula I are employed, pre-ferred are catalysts wherein a is 0.001 to 3, catalysts wherein b is OoOOl to 3, and catalysts wherein b is zero.
Especially preferred are catalysts wherein X represents cerium, erbium, or a mixture of rare earth elements con-sisting essentially of Ce, La, Nd and Pr. Catalysts of particular interest are described wherein Y is silver, thallium or copper.
When catalysts within formula II are employed, preferred are catalysts wherein a is 0.001 to 3, catalysts wherein b is 0.001 to 3j and catalysts wherein b is zero.
Especially preferred are cata].ysts wherein each of the elements described by X is separately incorporated into the catalyst. This is conveniently accomplished by setting X
independently equal to the various elements. Catalysts of particular ~.nterest are described wherein Y is at least one element selected from the group consisting Or a rare earth element, Al, Ag and Cu.
When catalysts within formula III are employed, preferred are catalysts wherein a is 0.001 to 3, catalysts wherein b is 0.001 to 3, and catalysts wherein b is zero.
Especially preferred are catalysts wherein each of the elements described by X is separately incorporated into the

2~ ~ (4958) (4959) catalyst. Thls is conveniently accomplished by settln~ X
independently equal to the various elements. Also preferred are catalysts wherein Y is at least one of Cd, Tl, Cu, NH
and Cl.
In the catalyst preparations, the various elements oP the catalyst are combined, and the ~inal product is calcined to obtain the catalyst. A number of methods of combining the elements of the catalyst and calcining the resultant product are known to those of sklll in the art.
In the ~road concept of the invention, the particular method of preparing the catalysts is not critical.
There are, however, methods of preparing the catalysts that have been found to be preferred. One preferred preparation involves the preparation of the catalysts in an aqueous slurry or solution of molybdenum, arsenic, and/or phosphorus containing components, and adding the remaining components; evaporation of this aqueous mix~ure; and calcination o~ the resulting catalysts. Suitable molybdenum compounds that may be employed in the preparation of the catalysts delineated by the above formula include molybdenum trioxide, phosphomolybdic acid, molybdic acld, ammonium heptamolybdate and the like. Suitable phosphorus compounds that may be employed in ~he preparation of the catalysts include ortho-phosphoric acidg metaphosphoric acid, tri-phosphoric acid, and phosphorus halides or oxyhalides.
The remaining components of the catalysts may be added as oxlde, acetate, formate, sulfate, nitrate, carbonate, oxyhalide, or halide and the like.

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Excellent results are obtained by refluxing phosphoric acld, an arsenic containing compound, and molyb-denum trioxide, or ammonium heptamolybdate in water for about one-half hour to 3 hours, howe~er, commercial phospho molybdic acid may be effectively utilized; adding the remain-ing components to the aqueous slurry and boiling to a thick paste; drying at 110C to 120C in air; and calclning the resulting catalysts.
The calcination of the catalyst usually is accom-plished by heating the dry catalytic components at a tempera- -ture of about 200C to about 700C. The preferred procedure of the invention is wherein the catalyst is calcined at a temperature of 325C to 425C.
The reactants of the reaction of the invention are methacrolein or acrolein and oxygen. Molecular oxygen is normally supplied to the reaction in the form of air, but oxygen gas could also be employed. About 0.5 to about 4 moles of oxygen are normally added per mole of methacrolein.
The reaction temperature may vary as different catalysts are employed. Normally, temperature of about ~00C to about 500C are employed with temperature of 250C
to 370C being preferred.
The catalyst may be used alone or a support could be employed. Suitable supports include silica, alumina, Alundum~, silicon carbide, boron phosphate, zirconia and titania. The catalysts are conveniently used in a fixed-bed reactor using tablets, pellets or the like or in a fluid-bed reactor using a catalyst ha~ing a particle size of less than about 300 microns. When a fluid-bed reactor is employed, preferred catalysts are in the form of microspheroidal particles.

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(4957) 5 ~ (~958) The contact time may be as low as a fraction of a second or as high as 20 seconds or more. The reaction may be conducted at atmospheric, superatmospheric or subatmospheric pressure, wlth absolute pressures of about 0.5 to about 4 atmospheres being preferred.
Excellent results are obtained using a coated catalyst consisting essentially of an inert support material having a diameter of at leas~ 20 microns and an outer surface and a continuous coating of said active ca~alyst on said inert support strongly adhering to the outer surface of said support. The special coated ca~alyst cons~sts of an inner support material having an outside surface and a coating of the active catalytic material on this outside surface.
These catalysts can be prepared by a number of different methods.
The support material for the catalyst forms the inner core of the catalyst. This is an essentially inert support and may have substantially any particle size although a diameter of greater than 20 microns is preferred. Especially preferred in the present invention for use in a commercial reactor are those supports which are spherical and which have a diameter of about 0.2 cm. to about 2 cm. Suitable examples o~ essentially inert support materials lnclude:
Alundum, silica, alumina, alumina-silica, slIicon carbide, titania and zirconia. Especially preferred among these supports are Alundum~ sllica, alumina and alumlna silica.

(4957) ~ 2~ ~ (4~958) The catalysts may contaln essentially any proportions of support and catalytically active material. The limits of this relationship are only set by the relative abillty of the catalyst and support material to accommodate each other.
Preferred catalysts contain about 10 to about 100 percent by wei~ht o~ catalytically active material based on the weight of the support.
The preparation of these coated catalysts can be accomplished by various techniques. The baslc method of preparing these catalysts is by partially wetting the support material with a liquid and then contacting the support material w~ith a powder of the catalytically active material and gently agitating the mixture until the catalyst is formed. The gentle agltation is most conveniently accomplished by placing the partially wet support in a rotating drum or ~ar and adding the powdered active catalytic material.
Using the catalysts of the invention in the preparation of methacrylic acid or acrylic acid, excellent yields are obtained in a convenient reactlon with low amounts of byproducts.

s~r~ I~OD~ S

Compara ive Exam~les A to D and Examples_l to 80:
Comparison of catalysts containing promoters of invention with base catlyst in the preparation of methacrylic acid.

A 20 cc. fixed-bed reactor was constructed of a 1.3 cm. stainless steel tubing. Catalysts prepared as described below were charged to the reactor and heated to the reaction temperature under a flow of air and a feed of (4958) (4959) methacrolein/air/nitrogen/steam of 1/5.7/4.6/8.7 w~s ~ed over the catalyst at an a~parent contact time of 2 to 4 seconds. The reactor was run under the reaction conditions for 1 to 6 hours and the product was collected and analyzed.

Comparative Example A

5% l2PlAso.sox + 75% Alundum A solution was prepared consisting o~ 211.88 grams of ammonium heptamolybdate, (NH4)6Mo7024.4H20, (1.2 mole Mo), 500 mls. distilled water at 60C and 7.94 grams of ammonium arsenate NH4H2AsO4, (0.05 mole As) as solution in 25 mls. distilled water. A white precipitate formed which was heate~ to about 100C for two hours. To this mixture was added 11.53 grams of 85% solution phosphoric acid (0.10 mole P). One-half hour later 5.0 grams of hydrazine hydra-te was added. The slurry was evaporated to a thick paste, dried overnight in an oven at 110 to 120C, and ground and screened to less than 80 mesh. This powder was coated on Norton 1/8" SA 5223 Alundum balls by taking 50 grams of Alundum, partially wetting the Alundum wlth 1.8 grams of water and adding 16.7 grams of active catalyst prepared above in five equal portions. During and after each addition, the Alundum was rolled in a glass ~ar. The powder was evenly coated onto the surface of the Alundum and the flnal product was dried. A hard unl~orm material was obtained that consisted of an inner core of the Alundum support with the continuous, strongly adhering coat of the powder on the outside surface of the support. The material was then calcined ~or 1 hour at 370C in 40 ml/min. air to form the active catalyst.

(4957) ~ (4959) Examples 1 to 9 Various c~talysts within formula I were prepared as follows:

25% (Rare earth mlx~ure)o.25Mol2plAso-5ox 75% Al . . .. . _ . .
A solution was prepared consisting of 105.9 grams of ammonium heptamolybdate, (NH4)6Mo7O24.4H2O~ (0-6 mole Mo), 700 mls. o~ distilled water at 60C and 4.~ grams of ammonium arsenate NH4H2As04, (O~025 mole As) as solution in 25 mls. of water. A white precipitate formed which was heated at 100C about one-half hour. To this mixture was added 4.4 grams of Moly Corp. rare earth chloride mlxture (Product Code No. 4700) consisting of 48% CeO2, 33% La2O3, 13% Nd2O3, 4.5% Pr6Ol and 1.5% other rare earth elements calculated as oxides. ~o this solution was added 5.8 grams of 85% solution phosphoric acid, H3PO4 (0.05 mole P). One-half hour later 2.5 grams of hydrazine hydrate were added.
The slurry was evaporated to a thick paste, dried overnight in an oven at 110 to 120C, and ground and screened to less than 80 mesh size. The catalyst was then coated to a 25%
active level on 1/8't SA 5223 Alundum balls. Calci~ation was the same as in Comparative Example A.

Examples 2 to 7 Preparation of the Catalysts 5% XaybMol2plAso~sGx + 75% Alundum Various catalysts of the invention were prepared.
The catalysts were prepared according to the procedure of ~10~

(4957) ( 4958 ) a~ ( 4 9 5 9 ) Example 1, using 105. 9 grams of ammon~um molybdate, 700 mls.
of 60C. distilled water and 4 . O grams of ammonium arsenate in so~ution o~ 25 mls. of water. The catalytic components ~delineated by X and/or Y were added immediately preceding the addition o~ 5.8 grams of 85% phosphoric acid and 2.5 grams of hydrazlne hydrate. To prepare the catalystsg the ........
following compounds and amounts were used:

Example Element Compound Amount ? g.

2 CeO.25 cerium acetate 4.31

- 3 CeO 1 cerium acetate 1.72

4 ErO.25 erblum acetate 5.21 Rare Rare earth chloride 1.77 earth mixture (Moly Corp.
mixtu~el No. 4700) ' CU0.25 copper ~cetate 2.48 6 Rare Rare earth chloride 4.43 earth mixture mixture 0.25 T10.05 thallium acetate o.66 7 CeO.15 cerium acetate 2.59 Ago.l silver acetate o.85 E_ample 8 25% Rare earth miXtUreO 25cuo~o5Mol2plAso.5ox 75 __ _ __ This catalyst was prepared ln the same manner described in Example 1~ except 34.25 grams of ammonium heptamolybdate, 1.28 grams of ammonium arsenate~ 1.43 grams of rare earth chloride mixture, 0.161 grams of copper acetate, 1.88 grams of 85% phosphoric acid and 0.8 grams of hydrazine hydrate were employed.

(~1957) (4958) ~ ~ ~ 9 25 ~ (4959) F,xample 9 25% Rare earth mixtureO 25Ago.lMl2PlAS0.50x + 75~ Al _ This catalyst was prepared in the same manner described in Example 8, except that 0.269 grams of silver acetate were employed.

Comparative Examples B, C, and Examples lO to 20 The results of the experiments using catalysts within formula I in the oxidation of methacrolein to produce methacrylic acid are shown in TABLE I. The following definitions are used in measuring the carbon atoms in the feed and the products.

Moles of Methacrylic Acid Recovered lO0 % Single Pass Yield Moles of Methacrolein in the Feed x Moles of Methacrolein Reacted Total ~onversion Moles of Methacrolein in the ~eed x lO0 Sin~le Pass Yield SelectiVitY = To-tal COnversion x lO0 o o o o o o~ ~
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Example 21

5%Uo.25Mol2plAso.sox + 75% Alundum A solution was prepared consisting o~ 105.9 grams of ammonium heptamolybdate, (NH4)6Mo7024.4H20, (o.6 mole Mo), 700 mls. of distilled water at 60C and 4.0 grams of ammonium arsenate, NH4H2AsO4, (O.025 mole As) as solution in 25 mls. of water. A white precipitate formed which was heated at 100C about one-half hour. To this mixture was added 5.3 grams of uranyl acetate (0.0125 mole U)~ followed by the addition of 5.8 grams of 85% solution phosphoric ac~d (0.05 mole P). One-half hour later 2O5 grams of hydrazine hydrate were added. The slurry was evaporated to a thick paste, dried overnight in an oven at 110 to 120C, and ground and screened to less than 80 mesh size. The catalyst was then coated to 25% active level on 1/8t' SA 5223 Alundum balls. Calcination was the same as in Comparative Example A.

Example 22 5~ Tio.2Mo12PlAso.sox ~ 75% Alundum This catalyst was prepared in the same manner described in Example 21, except 7.72 grams of 20% titanium trichloride solution were employed and hydrazine hydrate was deleted in the catalyst preparation.

(4957) (4958) (4959) Example 23 25~ (Rare earth miX~ure)O 2T1o.lM12PlAs0.50x + 75%
-This catalyst was prepared in the same manner described in Examplq 2l~except 3.54 grams of rare earth chlorlde mixture, 0.5 grams o~ hydrazine hydrate were employed and 3.85 grams of 20% titanium trichloride solution were added.

, , Examples, ?4 to 39 Preparation of the Catalysts 25% XaYbMol2PlAsO.50x 75~

Various catalysts of the invention were prepared.
The catalysts were prepared according to ~he procedure OI' Example 21, using 105.9 grams of ammonium molybdate~ 700 mls.
of 60C distilled water and 4.0 grams of ammonium arsenate in solution of' 25 mls. of water. The catalytic components delineated by X and/or Y were added immediately preced1ng the addition of 5.8 grams of 85% solution phosphoric acid.
2.5 grams o~ hydrazine hydrate were added in all prepara~ions, e~cept no hydrazine was added in Examples 2-~, 30, 32 and 3~;
1.0 gram of hydrazine was added in Example 14. To prepare the catalysts, the following compounds and amounts were used:
Example Element Com~ound Amount a ~.

24 NbO.25 niobium chloride 3.37 PbO.25 lead acetate 4.75 26 ZnO.25 zinc acetate 2.75 27 ReQ.25 rhenium sesquioxide 3.03 2 8 AgO.l~iO.2 20% titanium trichloride 7.72 silver acetate o.8 29 Ago lZnO 2 zinc acetate 2.19 ' silver acetate o.8 (4957) (4958) ~ (4959) Example Element Compound ~ E~
, Nb Tl 2 niobium chloride O.67 0.05 . 20% titanium trichloride solution 7.72 31 ReO 1CuO 25 rhenium sesquioxide 1.21 copper acetate 2.48 32 Ti znO 20% titanium chloride 5.78 0.15 .l zinc acetate l.l 33 ZnO 1 zinc acetate 1~09 (rare earth rare earth chloride mixture 3.54 mixture)~ 2 (Moly Corp. Product No.4700) 34 Tio o5CU0.05 20% titanium chloride 1.92 (rare earth copper acetate 3.54 mixture)O 2 rare earth chloride mixture Zno.05CU0.05 zinc acetate 0.55 (rare earth copper acetate 0.50 mixture)O 2 rare earth chloride mixture 3.54 : 36 GaO.25 gallium oxide l.l 7 ~0 2A~o 05CuO 05 zinc acetate 2.19 aluminum chloride o.6 : copper acetate 0.50 38 Tio 2Rare earthO 05 20% titanium chloride 7.7 Cu Moly Corp. rare earth 5 mixture (4700) 0.90 copper acetate 0.50 39 Rare earth Pb lead acetate 3.8 0-1 0-2 rare earth mixture 1.77 Exam~le 4 5% l2PlAso.5Nbo.25Ago 05x + 75~o Alundum This catalyst was prepared in the same manner described in Example 21~except that 34.25 grams of ammonium molybdate, 150 mls. water, 1.28 grams o~ ammonium arsenate, : 0.537 grams niobium chloride, 0.134 grams of silver acetate, 1~86 grams of 85% phosphoric acid~ and 0.8 grams of ~ydrazine hydrate were employed.

(4957) ~ Q ~ (4958) Example 41 5% 12PlASo sNbo 2sCuO l~x + 75% Alundum This catalyst was prepared in the same manner as described in Example 24, except 0.322 ~rams of copper acetate were added in addition to the niobium chloride.

Example 42 5% nO.2AlO.08CU0.05~l2P1 32Aso 5x ~ 75% Alundum This catalyst was prepared in the same manner described in Example 37, except that o.96 grams of aluminum chloride hydrate and 7.6 grams of 85~ phosphoric acid were employed.

Example 43 25~ ReO.lA10.091~U0~05Ml?Pl.32ASO 5~x ~ 75% Alundum This catalyst was prepared in the same manner described in Example 42, except that 1.1 grams of aluminum chloride hydrate and 1.21 grams of Re207 were employed.

Comparative Examples B to D and Examples 44 to 67 The results of the experiments using catalysts within formula II in the oxidation of methacrolein to produce methacrylic acid are shown in TABLE II below. The same definitions described above are used in measuring the carbon atoms in the feed and the products.
In the same manner described above, catalysts of the invention may be efrectively utilized in the prep-aration of acrylic acid from acrolein.

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e ~ ~ 0 (4g57) ~ (495g) Examples 68 to 73 Various catalysts within formula III were prepared as follows:
Example 68 5% Ago.25Mo12PlAso~sox ~ 75% Alundum A solution was prepared consisting of 105.9 grams of ammonium heptamolybdate, (NH4)6Mo7O24.4H2O, (o.6 mole Mo), 700 mls. of distilled water at 60C and 4.0 grams o~
ammonium arsenate, NH4H2AsO4, (0.025 mole As), as solution in 25 mls. of water. A white precipitate formed which was heated at 100C about one-half hour. To this mixture was added 2.08 grams of silver acetate (0.0125 mole Ag), followed by the addition of 5.8 grams of 85% solution phosphoric acid (0.05 mole P). One-half hour later 2.5 grams of hydrazine hydrate were added. The slurry was evaporated to a thick paste, dried overnight in an oven at 110 to 120C, and ground and screened to less than 80 mesh size. The catalyst was then coated to 25% actlve level on 1/8" SA 5223 Alundum balls. Calcination was the same as in Comparative Example A.

Example 69 0.05cdo.2Mol2Pl.o~so~5ox + 75~ Alundum Thls catalyst was prepared in the same manner described in Example 68, except that 150 mls. of water, 34.25 grams of ammonium molybdate, 1.28 grams of ammonium arsenate, 0.862 grams of cadmium acetate, 0.318 grams of gold chloride, 1.86 grams of 85~ phosphoric acid and o.8 grams of hydrazine hydrate were employed.

Example 70 5% RUo.2Mol2PlA~so.5~x ~ 75~ Alundum This catalyst was prepared in the same manner described in Example 68~ except that 500 mls. of water, 5 ~ (4958) (4959) 70.6 grams of ammon~um molyhdate~ 2~64 grams of ammonium arsenate, 1.74 grams of ruthenium chloride, RuC13 3H2O, (0.006 mole Ru~, 3.84 grams of phosphoric acid, and 1.6 grams of hydrazine hydrate were employed.

Exam~es 71 to 73 Preparation of the Catalysts 25% XaYbMol2PlAsO.5Ox 75%
. . _ ,, . _ . _ . . , _ _ .
Various catalysts of the invention were prepared.
The catalysts were prepared according to the procedure of Example 68, using 105.9 grams of ammonium molybdate, 700 mls. of 60C distilled water and 4.0 grams of ammonium arsenate in solution of 25 mls. of water. The catalytic components delineated by X and/or Y were added immediately preceding the addition o~ 5.& ~rams o~ 85~ solution phos-phoric acid, and 2.5 grams of hydrazine hydrate. To prepare the catalysts, the following compounds and amounts were used:
Exam~Ie Element Compound Amount~ ~.
. .
71 Ago.l silver acetate o.8 72 RhO.25 rhodium acetate 2.15 73 Auo 25 gold chloride 4.92 Comparati_e Examples B to_D and Examples 74 to 80 The results of the experiments using catalysts within formula III in the oxidation of methacrolein to produce methacrylic acid are shown in TABLE III. The same definitions described above are used in measuring the carbon atoms in the f'eed and the products.
In the same manner described above, catalysts of the invention may be effectively utilized in the preparation of acrylic acid from acroleln.

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Claims (54)

WE CLAIM:

1. The catalyst composition selected from the group consisting of formula I
XaYbMo12PcAsdOx wherein X is a rare earth element or a mixture thereof;
Y is at least one element selected from the group consisting of Ag, Tl, Rh, Pd, Ru, Pt, Cd, Al, Au, Cu, alkaline earth metal, Cl, and NH4;
wherein a is 0.001 to 10;
b is 0 to 10;
c is 0.1 to 5;
d is 0.01 to 5;
x is the number of oxygens required to sat-isfy the valence states of the other elements present;
formula II
XaYbMo12PcAsdOx wherein X is at least one element selected from the group consisting of U, Ti, Nb, Re, Zn, and Ga;
Y is at least one element selected from the group consisting of Cu, a rare earth element, Ag, Ta, In, Th, Cd, Tl, NH4, Cl, Ni, Se and Ge;
wherein a is 0.001 to 10;
b is 0 to 10;
c is 0.1 to 5;
d is 0.01 to 5;
x is the number of oxygens required to sat-isfy the valence states of the other elements present;
formula III
XaYbMo12PcAsdOx wherein X is at least one element selected from the group consisting of Ag, Rh, Au and Ru;
Y is at least one element selected from the group consisting of Cd, Tl, Pd, Al, Ge, Cu, Pt, Ni, alkaline earth metal, NH4 and Cl;

and wherein a is 0.001 to 10;
b is 0 to 10;
c is 0.1 to 5;
d is 0.01 to 5;
x is the number of oxygens required to sat-isfy the valence states of the other elements present.

2. The catalyst composition of claim 1 wherein the catalyst is described by the formula XaYbMo12PcAsdOx wherein X is a rare earth elemnt or a mixture thereof;
Y is at least one of Ag, Tl, Rh, Pd, Ru, Pt, Cd, Al, Au, Cu, alkaline earth metal, Cl and NH4;
wherein a is 0.001 to 10;
b is 0 to 10;
c is 0.01 to 5;
d is 0.01 to 5;
x is the number of oxygens required to sat-isfy the valence states of the other elements present.

3. The catalyst of claim 2 wherein X is cerium, erbium, or a mixture of rare earth elements consisting essentially of Ce, La, Nd and Pr.

4. The catalyst of claim 2 wherein X is a mixture of rare earth elements consisting essentially of Ce, La, Nd and Pr.

5. The catalyst of claim 2 wherein X is cerium.

6. The catalyst of claim 2 wherein X is erbium.

7. The catalyst of claim 2 wherein Y is at least one of silver, thallium and copper.

8. The catalyst of claim 2 wherein Y is silver.

9. The catalyst of claim 2 wherein Y is thallium.

10. The catalyst of claim 2 wherein Y is copper.

11. The catalyst of claim 2 wherein b is zero.

12. The catalyst of claim 2 wherein a is 0.001 to 3.

13. The catalyst of claim 2 wherein b is 0.001 to 3.

14. The catalyst of claim 2 which is coated on an inert support.

15. The catalyst of claim 14 consisting essen-tially of an inert support material having a diameter of at least 20 microns and an outer surface and a continuous coating or said active catalyst strongly adhering to the outer surface of said support.

16. The catalyst of claim 15 wherein the active catalyst is about 10 to about 100 percent by weight of the inert support.

17. The catalyst of claim 15 wherein the support is selected from the group consisting of silica, alumina, Alundum?, alumina-silica, silicon carbide, titania and zirconia.

18. The catalyst of claim 15 wherein the particle size of the inert support is 0.2 cm. to 2 cm.

19. In the process for the production of acrylic acid and methacrylic acid by the oxidation of acrolein and methacrolein respectively, with molecular oxygen in the vapor phase at a reaction temperature of about 200°C to about 500°C in the presence of a catalyst, and optionally in the presence of steam, the improvement comprising using as a catalyst a catalyst of claim 1.

20. The catalyst composition of claim 1 wherein the catalyst is described by the formula XaYbMo12PcAsdOx wherein X is at least one element selected from the group consisting of U, Ti, Nb, Re, Pb, Zn and Ga;
Y is at least one element selected from the group Consisting of Cu, a rare earth element, Ag, Ta, In, Th, Cd, Tl, alkaline earth metal, NH4, Cl, Ni, Al and Ge;
and wherein a is 0.001 to 10;
b is 0 to 10;
c is 0.1 to 5;
d is 0.01 to 5;
x is the number of oxygens required to sat-isfy the valence states of the other elements present.

21. The catalyst of claim 20 wherein a is 0.001 to 3.

22. The catalyst of claim 20 wherein b is 0.001 to 3.

23. The catalyst of claim 20 wherein b is zero.

24. The catalyst of claim 20 wherein X is uranium.

25. The catalyst of claim 20 wherein X is titan-ium.

26. The catalyst of claim 20 wherein X is nio-bium.

27. The catalyst of claim 20 wherein X is rhenium.

28, The catalyst of claim 20 wherein X is zinc.

29. The catalyst of claim 20 wherein X is gallium.

30. The catalyst of claim 20 wherein X is titan-ium and niobium.

31. The catalyst of claim 20 wherein X is titanium and zinc.

32. The catalyst of claim 20 wherein Y is at least one element selected from the group consisting of Cu, a rare earth element, Al and Ag.

33. The catalyst of claim 20 wherein X is rhenium and Y is copper.

34. The catalyst of claim 20 which is coated on an inert support.

35. The catalyst of claim 34 consisting essen-tially of an inert support material having a diameter of at least 20 microns and an outer surface and a continuous coating of said active catalyst strongly adhering to the outer surface of said support.

36. The catalyst of claim 35 wherein the active catalyst is about 10 to about 100 percent by weight of the inert support.

37. The catalyst of claim 35 wherein the support is selected from the group consisting of silica, alumina, Alundum?, alumina-silica, silicon carbide, titania and zirconia.

38. The catalyst of claim 35 wherein the particle size of the inert support is 0.2 cm. to 2 cm.

39. In the process for the production of acrylic acid and methacrylic acid by the oxidation of acrolein and methacrolein respectively, with molecular oxygen in the vapor phase at a reaction temperature of about 200°C to about 500°C in the presence of a catalyst, and optionally in the presence of steam, the improvement comprising using as a catalyst a catalyst of claim 20.

40. The catalyst composition of claim 1 wherein the catalyst is described by the formula XaYbMo1PcAsdOX

wherein X is at least one element selected from the group consisting of Ag, Rh, Au and Ru;
Y is at least one of Cd, Tl, Pd, Al, Ge, Cu, Pt, Ni, alkaline earth metal, NH4 and Cl;
and wherein a is 0.001 to 10;
b is 0 to 10;
c is 0.01 to 5;
d is 0.01 to 5;
x is the number of oxygens required to sat-isfy the valence states of the other elements present.

41. The catalyst of claim 40 wherein a is 0.001 to 3.

42. The catalyst of claim 40 wherein b is 0.001 to 3.

43. The catalyst of claim 40 wherein b is zero.

44. The catalyst of claim 40 wherein X is silver.

45. The catalyst of claim 40 wherein X is rhodium.

46. The catalyst of claim 40 wherein X is ruthenium.

47. The catalyst of claim 40 wherein X is gold.

48. The catalyst of claim 40 wherein Y is cad-mium.

49. The catalyst of claim 40 which is coated on an inert support.

50. The catalyst of claim 49 consisting essen-tially of an inert support material having a diameter of at least 20 microns and an outer surface and a continuous coating of said active catalyst strongly adhering to the outer surface of said support.

51. The catalyst of claim 50 wherein the active catalyst is about 10 to about 100 percent by weight of the inert support.

52. The catalyst of claim 50 wherein the support is selected from the group consisting of silica, alumina Alundum?, alumina-silica, silicon carbide, titania and zirconia.

53. The catalyst of claim 50 wherein the particle size of the inert support is 0.2 cm. to 2 cm.

54. In the process for the production of acrylic acid and methacrylic acid by the oxidation in the presence of a catalyst of acrolein and methacrolein respectively, with molecular oxygen in the vapor phase at a reaction temperature of about 200°C
to about 500°C in the presence of steam, the improvement comprising using as the catalyst a catalyst of claim 40.