MIXED METAL PHOSPHORUS OXIDE CATALYSTS FOR THE OXIDATIVE DEHYDROGENATION OF CARBOXYLIC ACIDS UTILIZING THEM AND PREPARATION THEREOF

Abstract: A catalyst composition represented by the formula A a Fe b P c D d O x wherein A is selected Cd, Cr, Ge, Te, Th, Ti, U, V, Zr, rare earths and mixtures thereof; wherein D is selected from Ag, Cu, Mn and mixtures thereof; and wherein a = 0-1.0 b = 0.75-1.5 c = 1.0-2.0 d = 0-2.0 a + d is greater than zero and x is the number of oxygens needed to satisfy the valence requirements of the remaining elements. This catalyst is particularly suitable for the oxydehy­ drogenation of saturated carboxylic acids, such as isobutyric acid, to form alpha, beta unsaturated carboxylic acids, such as methacrylic acid.

Description: Mixed Metal Phosphorus Oxide Catalysts for the Oxidative Dehydrogenation of Carboxylic Acids Utilizing them ard preparation thereof This invention relates to the catalytic, oxidative dehydrogenation of saturated carboxylic acids to their corresponding unsaturated acids and to catalysts useful for this purpose. More particularly, it is directed to the production of unsaturated carboxylic acids such as methacrylic acid from saturated carboxylic acids such as isobutyric acid utilizing promoted iron phosphorus oxide catalysts. The production of unsaturated carboxylic acids from their corresponding saturated acids using iron phosphorus oxide catalysts, with or without various promoters, is disclosed in the art. U.S. Patent No. 3,948,959 discloses the preparation of unsaturated acids by oxidation of the corresponding saturated acid using iron phosphorus oxde catalysts promoted with Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba. U.S. Patent Nos. 3,634,494; 3,652,654; 3,855,279; 3,917,673 and 4,029,695 disclose the preparation of unsaturated acids and esters from saturated acids and esters using iron phosphorus oxide catalysts, containing bismuth and/or lead promoters, optionally with other promoter elements, including Mn, U, Pr, Ca, Sr and Cr. Prior art catalysts characteristically have exhibited short life and thermal instability. We have found that unsaturated acids, particulari methacrylic acid, can be produced from their corresponding saturated acids, such as isobutyric acid, using iron phosphorus oxide catalysts promoted with particular elemer.tJ, in increased yields corresponding to an increase of catalyst activity and/or selectivity over prior art catalysts. The catalysts of the present invention exhibit increased life and thermal stability with respect to the prior art catalysts. Although promoters such as Mn, U, Cr, were disclosed as being suitable promoters in an iron lead mixed phosphate system if present in low amounts, and promoters such as Co, Ni, Cu, Zn, Cd and Ce were disclosed for that system as less than suitable promoters, we have found that these elements exhibit excellent promotional activity in the iron phosphorus oxide system for the oxydehydrogenation of saturated carboxylic acids wherein the iron phosphorus oxide is free of lead phosphate or oxide. The present invention provides a process for the preparation of unsaturated acids by contacting their corresponding saturated acids with molecular oxygen or an oxygen-containing gas in the vapour phase, at a reaction temperature of 2500C to 6000C in the presence of a catalyst having the empirical formula A Fe P D 0 a bcdx wherein A is selected from Al, B, Be, Cd, Co, Cr, Ga, Ge, In, Ni, Te, Th, Ti, TI, U, V, Zn, Zr, rare earths and mixtures thereof, wherein D is selected from Ag, Cu, Mn and mixtures thereof, and wherein a = 0-1.0 b = 0.75 - 1.5 c = 1.0 - 2.0 d = 0 - 2.0 a + d is greater than zero and x is the number of oxygens needed to satisfy the valence requirements of the remaining elements. Preferably a equals 0.15 - 0.5 and d equals 0.2 - 1.5. The present invention further provides the above defined catalysts as new oxydehydrogenation catalysts. Preferably a equals 0.15 - 0.5 and d equals 0.2 - 1.5. Preferred rare earth metal promoters are La, Ce, Nd, Sm, Eu, Dy, Ho, Tm, Yb and Lu. Amongst the other elemnts for A, thorium is preferred. In the process of the invention, saturated carboxylic acids are oxidatively dehydrogenated in the vapour phase, in the presence of promoted iron phosphorus oxide catalysts to form the corresponding unsaturated acid. The saturated acids preferably correspond to the formula EMI3.1 wherein R1, R2, and R3 are each independently selected from the group consisting of hydrogen and alkyl groups containing 1 to 4 carbon atoms. The acids may contain other functional groups such as aryl or nitrile, provided the functional groups do not interfere with the dehydrogenation reaction, under the reaction conditions required. The dehydrogenation occurs essentially in the alpha, beta position. The process of the present invention is highly suitable for the oxidative dehydrogenation of isobutyric acid to methacrylic acid. The promoted iron phosphorus oxide catalysts of the present invention may be prepared according to methods known in the art. One method of preparing the catalysts of the present invention includes introducing a compound of iron, and a compound containing the promoter element into water and contacting with a phosphorus compound, or the iron and promoter containing compound are introduced into an aqueous solution of phosphoric acid. Preferably, the compounds used containing iron and the promoter elements are soluble in water, and may include salts such as nitrates, halides, sulfates, acetates, carbonates, formates and the like. The resulting solution or slurry is evaporated to dryness, and the resulting solid is calcined at from 300 to 7000C. Alternatively, the catalyst may be prepared in an organic liquid medium. Alternatively, the aqueous solution or slurry can be adjusted to a pH of 5 - 6 before drying. The catalyst may be formed into tablets, pellets or like shapes, and may be prepared for use in either fixed or fluid beds. The catalyst may be combined with inert diluents such as silica. Alternately, the catalyst may be coated upon inert supports, such as silica, alumina, alumina-silica, silicon carbide, titania, zirconia, zeolites and clays such as kieselguhr. Techniques of costing are described in U.S. Patent No. 4,077,912. The inert supports preferably are of at least 20 microns in diameter. The promoted iron phosphorus oxide catalysts of the present invention exhibit enhanced activity and selectivity for the oxydehydrogenation of saturated carboxylic acids, particularly isobutyric acid. The catalysts also exhibit long life and thermal stability. The saturated acids are contacted with the catalyst in the vapour phase, together with molecular oxygen. The molecular oxygen is most conveniently added as air, but synthetic streams containing oxygen are also suitable. In addition to the carboxylic acid feed and molecular oxygen, other gases may be added to the reactant feed. For example, steam is preferably added to the reactant feed to aid in the reaction, although the mechanism by which it does so is not certain. Inert diluents such as nitrogen, carbon monoxide, carbon dioxide and argon may also be added. The molar ratio of the reactants may vary widely and are not critical. The ratios of carboxylic acid: air: steam are in the range of 1:2.5 - 50:0 - 50 and are preferably 1:3 - 10:10 - 30. Diluents may be present in the range of O - 40 moles per mole of carboxylic acid. The reaction temperature may vary widely and is dependent upon the particular carboxylic acid and catalyst employed. Normally, temperatures of 2500 to 6000C are employed with temperatures of 3250 - 4500C being preferred. The contact time may vary from a fraction of a second to 50 seconds. In fixed bed reactions the contact time is preferably 0.5 seconds to 10 seconds, for fluid bed, preferably from 2 seconds to 20 seconds. The reaction may be conducted at atmospheric, superatmospheric or subatmospheric pressure, preferably from 1 psia (0.07 kg/cm2) to 100 psia (7 kg/cm2), most preferably between 10 (0.7 kg/cn12) to 30 psia (2.10 kg/cm2). In the production of methacrylic acid from isobutyric acid, the major by-product is acetone (generally about 5 - 15% yield) which may be removed from the product by conventional methods. The following Examples illustrate the invention. Catalysts tested in the below examples were prepared according to the following procedure. Fe(N03)3.9H20, the appropriate promoter metal nitrate and H3P04 (85%) were added to water in the amounts necessary to provide the molar ratios set forth in the tables below, for each of the particular catalysts reported. The solution of the components was evaporated to a dry paste with heating and stirring. The paste was dried for 16 hours at 1100C, and the resulting solid was calcined for 2 hours at 5400C. The solid was crushed and screened to 14 - 30 mesh (0.595 - 1.41 mm). The catalyst particles were processed according to the examples below, and were tested for the oxydehydrogenation of isobutyric acid to methacrylic acid in a 20 cc fixed bed reactor. The reactor consisted of a length of stainless steel tubing having an outer diameter of 1.3 cm, and containing a full length 0.31 cm diameter axial thermowell. The reactor was heated with a split stainless steel block furnace. The isobutyric acid was fed to the reactor by passing air through a saturator filled with isobutyric acid and maintained at a temperature of 1080C. Water was fed by means of a tubing pump and vapourized in a compartment maintained at 1540C before entering the reactor. Liquid products were analyzed on a Hewlett Packard 5710 A F.I.D. gas chromotograph. Gaseous products were analyzed on a conventional split column system. The test reactions were run at atmospheric pressure, unless otherwise noted. Reaction conditions such as temperature, feed ratios, contact time and catalyst working rate (WWH = weight of isobutyric acid/ weight of catalyst/hour) are listed in the tables below. Results of the tests report red in the tables below are reported in terms as follows: Single Pass Yield = Moles of Methacrylic Acid Formed x 100 Moles of Isobutyric Acid Fed Total Conversion = Moles of Isobutyric Acid Reacted x 100 Moles of Isobutyric Acid Fed Selectivity = Single Pass Yield x 100 Total Conversion 100% Active Catalysts EXAMPLES 1 - 13 Iron phosphorus oxide catalysts promoted with manganese (added as manganese nitrate) in varying molar ratios were prepared according to the procedure set forth above. The crushed and screened catalysts were charged to the reactor. The results of the tests, together with the amount of manganese in the catalysts are reported in Table I. EXAMPLES 14 - 39 Iron phosphorus oxide catalysts promoted with silver (added as silver nitrate) in varying amounts were prepared according to the procedure set forth above. The crushed and screened catalysts were charged to the reactor. The results of the tests, together with the amount of silver in the catalysts are reported in Table II. EXAMPLES 40 - 50 Iron phosphorus oxide catalysts promoted with copper (added as copper nitrate) in varying amounts were prepared according to the procedure set forth above. The crushed and screened catalysts were charged to the reactor. The results of the tests, together with the amount of copper in the catalysts are reported in Table III. EXAMPLES 51 - 62 Catalysts of the formula Tho 2FelP1 1.840 were x prepared from iron and thorium nitrates according to the procedure set forth above. The crushed and screened catalysts were charged to the reactor. The results of the tests are reported in Table IV. EXAMPLES 63 - 118 Catalysts having the formula AaFe1P1.84Ox were prepared with the designated promoter metal nitrates as set forth in the procedure above. The crushed and screened catalysts were charged to the reactor. The results of the tests and the amount and identity of the promoter metal are reported in Table V. EXAMPLES 119 - 124 Catalysts having the formula AaFe1P1.84D2Ox containing two promoter elements were prepared as set forth in the procedure above. The crushed and screened catalysts were charged to the reactor The results of the tests and the amounts and identities of the promoters are reported in Table VI. Diluent-containing catalysts EXAMPLES 125 - 132 Catalysts having the formula Ag 0.8 Fe1? 1.840 x were prepared according to the procedure set forth above, with the addition of various amounts of silica to the catalyst during preparation by slurrying in water. The crushed and screened catalysts were charged to the reactor. The results of the tests and the weight percents of active material and silica are reported in Table VII. Coated Catalysts EXAMPLES 133 - 140 Catalysts of the formula A Fe P 0 were a 1.0 1.84 x prepared according to the procedure set forth above. The crushed and screened catalysts were ground to a fine powder, and coated upon Alundum SA 5209 spheres (trade designation of Norton Company) according to the method set forth in U.S. Patent No. 4,077,912, with water as the wetting agent. The results of the tests, the catalyst used and the weight percent of catalyst loading (based upon total weight) are reported in Table VIII. EXAMPLES 141 - 150 Catalysts of the formula A0,6F 6fez 1.80x were prepared according to the procedure set forth above, except that the pH of the aqueous solution was adjusted to about 6 by addition of concentrated NH4OH solution. The dried catalysts were ground to a fine powder and coated on Alundum which had been ground to 10 - 20 mesh, using the method set forth in U.S. Patent No. 4,077,912 with absolute ethanol as a wetting agent. The coated particles were dried at 1750C for 30 minutes and calcined for 2 hours at 5400C. The catalyst loading was 17 weight percent. The catalysts were tested in a 5 cc reactor consisting of a 6 1/2" (16.5 cm) stainless steel tube of 5/16" (0.8 cm) inner diameter immersed in a molten salt bath. Feed ratios were 1 IBA/5 AIR/25 H2 0 at a contact time of about 2 seconds. Reaction temperature was 4150C. Run time was one hour. Results of the tests and the identity of the promoter elements contained in the catalysts are listed in Table IX. We have found that the iron phosphorus oxide catalysts, promoted according to the present invention, are not particularly suited to the oxydehydrogenation of saturated carboxylic acid esters, due to the hydrolysis of the ester by water formed as a by-product of the reaction even if steam is not co-fed. The oxydehydrogenation of the ester with these catalysts generally results either primarily in the formation of the unsaturated acid, or in low conversions to both acid and ester. A catalyst of the formula Th0,2Fe 1.0 P l.840x was prepared according to the procedure of Examples 51 62. Methyl isobutyrate was oxydehydrogenated over this catalyst in the 20 cc reactor described above at 4440C with a feed ratio of MIBA/AIR/H20/N2 equals 1/4.5/18/7.8 and a contact time of 1.6 seconds. Total conversion was 95.6%, but yield of methyl methacrylate was only 11.6% with a yield of methacrylic acid of 38.6%. With no steam being co-fed, (replaced by nitrogen), yield of methyl methacrylate increased to 23%, but total conversion decreased to 47.8%. As is demonstrated by the test results reported in Tables I to IX, promoted iron phosphorus oxide catalysts according to the present invention exhibit high activity and selectivity in the oxydehydrogenation of saturated carboxylic acids, particularly isobutyric acid, to the corresponding unsaturated acid. The catalysts of the invention additionally exhibit long life and thermal stability, as is demonstrated by the test results reported in the tables. TABLE I OXYDEHYDROGENATION OF ISOBUTYRIC ACID TO METHACRYLIC ACID OVER MnaFe1.0p1.84Ox CATALYSTS Hours Example Molar Feed Ratio Temperature Contact Methacrylic Acid % on No. Ratio-Mn(a) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 1 0.33 1/4.8/24/7 429 0.9 0.3 58.7 64.1 91.6 22 2 0.33 1/4.8/24.7 447 0.9 0.3 54.9 57.0 96.4 41 3 0.33 1/4.1.24.7 410 1.0 0.34 76.1 76.9 98.9 22.5 4 0.33 1/4.1.24.7 410 1.0 0.34 74.6 75.4 98.8 47 5 0.5 1/4.4/24.7 393 1.0 0.34 76.2 77.6 98.3 36 6 0.5 1/3.4/24.7 390 1.0 0.34 76.7 81.8 93.8 58.5 7 0.5 1/3.7/24.7 419 1.0 0.34 79.3 81.5 97.3 114.5 8 0.7 1/4.1/24.7 368 1.0 0.51 77.8 79.7 97.5 24.5 9 0.7 1/3.3/24.7 397 1.0 0.51 77.8 81.5 95.4 50.5 10 0.7 1/3.7/24.7 409 1.0 0.51 74.9 79.1 94.7 73.5 11 1.0 1/4.7/32.3 399 0.7 0.40 67.9 70.8 95.9 22 12 1.0 1/4.7/37.3 389 0.7 0.40 68.2 69.7 93.5 45 13 1.0 1/4.7/25.3 413 0.9 0.40 63.8 69.1 92.4 54 TABLE II OXYDEHYDROGENATION OF ISOBUTYRIC ACID TO METHACRYLIC ACID OVER AgaFe1.0p1.84Ox CATALYSTS Hours Example Molar Feed Ratio Temperature Contact Methacrylic Acid % on No. Ratio-Ag(a) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 14 0.33 1/4.7/24/7 385 1.0 0.23 67.7 75.3 89.9 24.4 15 0.33 1/4.8/24.7 382 1.0 0.23 69.0 70.2 98.3 52.5 16 0.33 1/4.8/24.7 378 1.0 0.23 66.8 69.2 96.6 73.6 17 0.66 1/4.9/25.3 406 0.9 0.27 71.9 71.9 100 24.6 18 0.66 1/4.4/25.3 382 1.0 0.27 74.3 76.1 97.5 50.9 19 0.70 1/4.5/25.3 387 1.0 0.18 73.8 76.1 96.9 45.9 20 0.75 1/4.8/24.7 368 1.0 0.20 74.9 80.8 92.7 24 21 0.75 1/5 /24.7 388 1.0 0.20 80.0 81.1 98.7 36 22 0.75 1/5.5/25.6 391 0.9 0.20 80.2 82.1 97.6 108 23 0.75 1/5 /17.3 407 1.2 0.20 70.6 72.9 96.8 198 24 0.75 1/5 /30.5 390 0.8 0.20 75.1 76.8 97.8 243 25 0.8 1/4.5/24.7 388 1.0 0.19 78.4 97.6 98.5 46.5 26 0.8 1/3.6/24.7 395 1.0 0.19 80.4 82.2 97.8 83 27 0.8 1/4.7/24.7 406 1.0 0.19 73.1 73.1 100 156 28 0.8 1/4.8/24.7 383 1.0 0.19 73.1 75.1 97.3 244 TABLE II (CONT'D) AgaFe1.0P1.84Ox Hours Example Molar Feed Ratio Temperature Contact Methacrylic Acid % on No. Ratio-Ag(a) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 29 0.8 1/4.8/17.5 390 1.3 0.19 70.9 74.4 95.3 250 30 0.85 1/5.5/24.7 368 1.0 0.18 73.6 76.7 95.9 54.5 31 0.85 1/4.8/24.7 368 1.0 0.18 81.4 84.5 96.3 84 32 0.85 1/4.5/24.7 370 1.1 0.18 77.6 80.7 96.2 127 33* 0.8 1/5 /26.2 376 0.9 0.26 74.7 75.3 99.2 24 34* 0.8 1/4.1/26.2 373 0.9 0.26 76.3 78.4 97.3 48.5 35* 0.8 1/3.6/32.9 376 0.8 0.26 79.9 81.9 97.6 59.5 36 1.0 1/4.7/24.7 386 1.0 0.22 73.7 76.1 96.9 26.5 37 1.0 1/4.7/24.7 389 1.0 0.22 71.0 78.2 90.8 52 38 1.0 1/4.8/24.7 360 1.1 0.14 70.4 72.7 97.0 24 39 1.5 1/5 /24.7 366 1.0 0.13 69.4 71.2 97.4 25.8 * Molar ratio Fe = 1.2 TABLE III OXYDEHYDROGENATION OF ISOBUTYRIC ACID TO METHACRYLIC ACID OVER CuaFe1.0p1.84Ox CATALYSTS Hours Example Molar Feed Ratio Temperature Contact Methacrylic Acid % on No. Ratio-Cu(a) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 40 0.2 1/4.8/24/7 405 1.0 0.27 68.1 72.1 94.4 24 41 0.2 1/4.8/24.7 387 1.0 0.27 70.0 72.1 97.1 46 42 0.33 1/4.8/24.7 396 1.0 0.28 66.2 66.3 99.9 27 43 0.33 1/4.9/24.7 386 1.0 0.28 67.1 71.2 94.3 72 44* 0.33 1/4.3722.0 374 1.7 0.32 65.7 69.9 94.0 107 45 0.66 1/4.8/24.7 368 1.0 0.26 70.9 72.9 97.3 25 46 0.66 1/4.8/24.7 368 1.0 0.26 71.4 74.0 96.6 49 47* 0.66 1/4.8/13.0 410 0.9 0.77 61.9 67.0 92.4 60 48* 0.66 1/4.2/22.6 386 0.9 0.52 68.1 72.6 93.8 67 49* 0.66 1/4.7/12.9 430 0.9 0.77 63.1 68.1 92.8 76 50 1.0 1/4.9/24.7 429 0.9 0.27 49.5 55.9 88.5 24 * Run at reactor outlet pressure 12 PSIG TABLE IV OXYDEHYDROGENATION OF ISOBUTYRIC ACID TO METHACRYLIC ACID OVER Th0.2Fe1.0p1.84Ox CATALYSTS Example Feed Ratio Temperature Contact Methacrylic Acid % No. 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Hours on Stream 51 1/5 /11 400 1.7 0.34 71.8 71.2 99.8 39 52 1/5 /11 398 1.7 0.34 67.5 70.6 95.6 68 53 1/5 /11 402 1.7 0.34 60.5 65.4 92.5 136 54 1/5 /15 402 1.4 0.34 66.9 69.0 96.9 203 55 1/4 /20 413 1.1 0.34 66.7 72.9 91.5 330 56 174 /26 423 0.9 0.34 65.7 71.2 92.2 401 57 1/5.5/26 412 0.9 0.34 63.3 67.1 94.3 499 58 1/5 /24 397 1.0 0.34 61.0 70.9 86.0 616 59 1/5 /24 406 1.0 0.34 65.3 68.9 94.7 809 60 1/5 /25 426 1.4 0.22 57.9 66.4 87.2 979 61 1/5 /25 407 0.9 0.34 70.2 71.6 98.1 1,045 62 1/5 /25 402 1.0 0.34 68.8 69.4 99.1 1,074 TABLE V OXYDEHYDROGENATION OF ISOBUTYRIC ACID TO METHACRYLIC ACID OVER AaFe1.0p1.84Ox CATALYSTS Promoter & Hours Example Mole Ratio Feed Ratio Temperature Contact Methacrylic Acid % on No. (Aa) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 63 Ce0.2 1/5 /31 391 1.8 0.18 53.8 57.0 94.3 8 64 Ce0.2 1/8 /50 390 1.8 0.11 58.7 59.7 98.3 16 65 Ce0.33 1/4.8/24.7 428 0.9 0.28 61.0 65.1 93.8 19 66 Ce0.33 1/4.8/24.7 446 0.9 0.28 61.9 64.0 96.6 95 67 Ce0.33 1/3.9/26.1 432 0.9 0.29 70.9 74.0 95.9 24 68 Ce0.33 1/3.9/26.1 442 0.9 0.29 69.2 73.5 94.2 50 69 Cr0.22 1/4.8/24.7 425 0.9 0.36 55.6 60.5 92.0 50 70 Cr0.22 1/4.8/24.7 425 0.9 0.36 49.1 63.7 91.5 70 71 Cr0.22 1/4.6/26.1 432 0.9 0.36 65.3 68.3 95.5 23 72 Cr0.22 1/5 /26.1 423 0.9 0.36 67.0 67.8 98.8 36 73 Dy0.22 1/5 /25 411 1.0 0.23 65.8 66.7 98.7 47 74 Dy0.22 1/5 /25 417 0.9 0.23 65.6 68.5 95.7 74 TABLE V (CONT'D.) AaFe1.0P1.84Ox Hours Example Feed Ratio Temperature Contact Methacrylic Acid % on No. Promoter(Aa) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 75 Eu0.22(Aa) 1/5 /25 407 0.9 0.28 63.5 65.8 96.5 24 76 Eu0.22 1/5 /25 407 0.9 0.28 62.3 65.7 94.9 41 77 Eu0.22 1/4.6/26.1 396 0.9 0.29 68.1 72.5 93.9 31 78 Ce0.2 1/4 /26 412 1.7 0.22 48.5 52.6 92.3 79 Ce0.2 1/4 /25 418 1.7 0.22 54.8 57.3 95.7 80 Ho0.22 1/4.8/24.7 412 0.9 0.26 58.4 61.7 94.6 40 81 Ho0.22 1/4.8/24.7 414 0.9 0.26 54.1 63.6 85.1 57 82 Ho0.22 1/5 /26.1 434 0.9 0.27 63.4 64.2 98.7 24 83 Ho0.22 1/4.9/26.1 424 0.9 0.27 67.3 69.0 97.6 54 84 La0.22 1/5.4/24.7 424 0.9 0.3 63.5 66.0 96.2 26 85 La0.22 1/5.4/24.7 425 0.9 0.3 64.2 66.4 96.7 30 86 Lu0.22 1/4.8/24.7 424 0.9 0.30 59.2 62.5 94.8 27 87 Lu0.22 174.8/24.7 434 0.9 0.30 53.7 63.0 85.3 50 TABLE V (CONT'D.) AaFe1.0P1.84Ox Hours Example Feed Ratio Temperature Contact Methacrylic Acid % on No. Promoter(Aa) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 88 Nd0.22 1/4 /23 396 1.7 0.17 60.3 62.9 95.8 7 89 Nd0.22 1/4 /24 402 1.7 0.17 65.4 70.3 93.1 30 90 Ni0.33 1/4.8/24.7 432 0.9 0.33 57.2 60.7 94.2 25 91 Ni0.33 1/4.8/26.1 428 0.9 0.32 64.7 64.8 99.8 25 92 Ni0.33 1/4,8/26.1 418 0.9 0.32 69.1 69.7 99.2 50 93 Ni0.33 1/3.7/26.1 413 0.9 0.32 73.2 75.1 97.5 71 94 Sm0.22 1/4.4/25.3 425 0.9 0.27 66.7 67.6 98.7 25 95 Sm0.22 1/4.8/25.3 432 0.9 0.27 66.2 69.0 96.0 49 96 Ti0.2 1/4 /22 409 1.6 0.26 63.1 66.7 94.6 6 97 Ti0.2 1/4 /28 413 1.3 0.26 58.2 62.2 93.6 12 98b Th0.2 1/4.1/25.3 410 1.0 0.28 75.1 75.8 99.0 23 99b Th0.2 1/3.7/25.3 410 1.0 0.28 76.3 77.4 98.6 48 TABLE V (CONT'D.) AaFe1.0P1.84Ox Hours Example Feed Ratio Temperature Contact Methacrylic Acid % on No. Promoter(Aa) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 100c Th0.2 1/4.8/25.3 417 0.9 0.34 71.6 72.6 98.6 23 101c Th0.2 1/3.8/25.3 419 1.0 0.34 72.6 74.8 98.4 35 102d Th0.2 1/4.8/25.3 392 1.0 0.25 68.8 68.9 99.9 24 103d Th0.2 1/3.5/25.3 382 1.0 0.24 76.2 77.2 98.6 44 104 Tm0.22 1/4.8/24.7 412 0.9 0.27 60.1 65.3 92.0 25 105 Tm0.22 1/4.8/24.7 423 0.9 0.27 56.4 62.7 89.9 46 106 U0.3 1/3.3/24.7 404 1.0 0.21 78.0 80.9 96.4 24 107 U0.2 1/5.4/24.7 418 0.9 0.21 78.2 71.2 99.9 25 108 U0.2 1/5.4/24.7 394 0.9 0.23 74.2 75.0 98.9 48 109 U0.2 1/5.3/24.7 395 0.9 0.23 72.5 73.0 99.2 67 110 U0.2 1/4.7/24.7 382 1.0 0.23 75.0 76.5 98.0 73 111 U0.2 1/4.0/24.7 388 1.0 0.23 76.1 77.7 98.0 99 a Molar ratio Fe = 0.8 d Molar ratio P = 1.5 TABLE V (CONT'D.) AaFe1.0P1.84Ox Hours Example Feed Ratio Temperature Contact Methacrylic Acid % on No. Promoter(Aa) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 112 V0.22 1/4.8/25 391 1.0 0.41 50.1 51.1 98.1 25 113 V0.22 1/4.7/25 382 1.0 0.41 49.8 52.2 95.4 45 114 Yb0.22 1/4 /23 392 1.7 0.18 64.5 68.4 94.3 6 115 Yb0.22 1/4 /23 396 1.7 0.18 61.1 66.3 92.2 15 116 Zn0.33 1/4 /25 442 1.6 0.2 58.4 60.3 96.9 10 117 Zr0.2 1/4 /23 398 1.7 0.16 65.1 66.7 97.6 5 118 Zr0.2 1/4 /22 398 1.7 0.16 65.6 70.0 93.7 7 TABLE VI OXYDEHYDROGENATION OF ISOBUTYRIC ACID TO METHACRYLIC ACID OVER AaFe1.0p1.84DdOx CATALYSTS Promoter & Hours Example Mole Ratio Feed Ratio Temperature Contact Methacrylic Acid % on No. (AaDd) 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 119 Ag0.4Mn0.4 1/4.3/26.1 400 0.9 0.29 75.1 75.4 99.6 19 120 Ag0.4Mn0.4 1/4.3/26.1 385 0.9 0.29 74.1 76.4 97.8 24 121 Ag0.4Mn0.4 1/4.3/36.8 385 0.7 0.29 74.1 77.8 95.3 44 122 Ag0.5U0.3 1/4.5/25.3 387 1.0 0.18 74.6 75.9 98.3 20 123 Ag0.5U0.3 1/4.5/25.3 277 1.0 0.18 75.1 76.9 98.6 25 124 Ag0.5U0.3 1/4.5/25.3 382 1.0 0.18 74.2 75.8 97.9 43 TABLE VII OXYDEHYDROGENATION OF ISOBUTYRIC ACID TO METHACRYLIC ACID OVER AgFe1.0p1.84Ox WITH SILICAQ DILUENTS Weight Hours Example Percent Feed Ratio Temperature Contact Methacrylic Acid % on No. Diluent 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream 125 20 1/4.8/26.1 415 0.9 0.16 75.0 76.1 98.6 26 126 20 1/4.2/26.1 419 0.9 0.16 74.5 76.3 97.6 39 127 20 1/4.0/25.3 388 1.0 0.23 77.0 97.1 97.3 49 128 30 1/4.4/25.3 380 1.0 0.23 72.6 73.4 98.8 25 129 30 1/3.8/25.3 375 1.0 0.23 73.5 75.8 96.9 53 130 40 1/4.5/25.3 382 1.0 0.25 73.5 76.0 96.7 25 131 40 1/3.9/25.3 394 1.0 0.25 75.1 76.6 98.1 49 132 50 1/4.6/25.3 397 0.9 0.26 70.4 71.8 98.5 24 TABLE VIII OXYDEHYDROGENATION OF ISOBUTYRIC ACID TO METHACRYLIC ACID OVER COATED CATALYSTS Hours Example Weight % Feed Ratio Temperature Contact Methacrylic Acid % on No. Active 1BA/Air/H2O C Time (Sec.) WWH % Yield % Selctivity Conversion Stream Ag0.8Fe1.0P1.84Ox on 10-30 mesh alundum 133 16.4 1/4.1/24.7 445 0.9 0.18 76.0 77.2 98.4 23 134 16.4 1/3.8/36.8 434 0.7 0.18 69.2 75.3 91.9 31 135 30 1/3.9/26.1 427 0.9 0.15 78.2 82.6 94.7 24 136 30 1/4 /26.1 432 0.9 0.15 79.0 81.7 96.7 36 Mg0.5Fe1.0F1.84Ox on 1/8 inch alundum 137 35 1/5 /25.9 409 0.9 0.21 69.5 72.2 96.2 23 138 35 1/4.7/25.3 421 0.9 0.21 66.8 67.7 98.7 48 139 45 1/4.8/26.1 414 0.9 0.22 64.9 66.2 98.0 26 140 45 1/4.2/36 430 0.7 0.22 66.6 67.4 98.9 34 TABLE IX OXYDEHYDROGENATION OF ISOBUTYRIC ACID TO METHACRYLIC ACID OVER 17 WEIGHT PRECENT COATED AaFe1.0P1.8Ox ON ALUNDUM PROMOTER AND METHACRYLIC ACID EXAMPLE NO. MOLE RATIO % YIELD % SELECTIVITY % CONVERSION 141 Ag0.6 55.1 55.1 100 142 Cd0.3 50.4 50.5 99.8 143 Co0.2 51.3 51.3 100 144 Dye 2 54.7 55.0 99.5 145 La0.2 55.6 55.6 100' 146 Mn0.3 46.1 55.5 83 147 Ni0.3 44.9 44.9 100 148 0.15 63.7 64.1 99.3 149 U0.15 40.6 40.8 99.6 150 Zr0.15 48.5 48.5 100

Claims: CLAIMS: 1. A catalyst composition represented by the formula AaFebPcDdOx wherein A is selected Cd, Cr, Ge, Te, Th, Ti, U, V, Zr, rare earths and mixtures thereof; wherein D is selected from Ag, Cu, Mn and mixtures thereof; and wherein a = 0-1.0 b = 0.75-1.5 c = 1.0-2.0 d = 0-2.0 a + d is greater than zero and x is the number of oxygens needed to satisfy the valence requirements of the remaining elements, 2. A catalyst as claimed in Claim 1 characterised in that the rare earths are selected from La, Ce, Nd, Sm, Eu, Dy, Ho, Tm, Yb, and Lu. 3. A catalyst as claimed in Claim 1 or Claim 2 characterised in that a is 0.15 to 0.5. 4. A catalyst as claimed in any of Claims 1 to 3 characterised in that d is 0.2 to 1.5. 5. A catalyst as claimed in any of Claims 1 to 4 in which D represents at least silver. 6. A catalyst as claimed in any af Claims 1 to 4 characterised In that D represents at least manganese. 7. A catalyst as claimed in any of Claims 1 to 4 characterised in that D represents at least copper, 8. A catalyst claimed in Claim 1 characterised in that A represents at least thorium. 9. A catalyst claimed in Claim 1 characterised in that A represents at least uranium. 10. A catalyst as claimed in Claim I characterised in that A represents at least one rare earth element. 11. A catalyst as claimed in any of Claims 1 to 10 characterised in that it additionally contains inert diluents, 12. A catalyst as claimed in any of Claims 1 to 11 characterised in that it is coated upon a support. 13. A process for the oxydehydrogenation of saturated carboxylic acids to form alpha, beta unsaturated carboxylic acids comprising contacting said saturated acids with molecular oxygen or an oxygen containing gas in the vapour phase at, a reaction temperature of from 2500C to 6000C in the presence of a catalyst as claimed in any of Claims 1 to 12. 14. A process as in Claim 13, characterised in that the saturated acid is represented by the formula EMI25.1 wherein R1, R2, and R3 are each independently selected from hydrogen 'and alkyl groups containing from 1 to 4 carbon atoms. 15. A process as claimed in Claim 14 characterised in that the acid comprises isobutyric acid. 16. A process as claimed in any of Claims 13 to 15 characterised in that the saturated acid is additionally contacted with an inert diluent gas. 17. A process as claimed in any of Claims 13 to 15 characterised in that said saturated acid is additionally contacted with steam. 1R. A process as claimed in any of Claims 14 to 17 characterized in that the reaction temperature is within the range of 3250C to 4500 C. 19. A process as claimed in any of Claims 14 to 18 characterised i n that the reaction is conducted at a pressure greater than atmospheric pressure. 20. A process for the preparation of catalysts as claimed in Clal; 1 wherein the constituents of the catalyst are prepared by introducing a compound of iron and a conpound containing the promoter element into a liquid medium, such as water and contacting with the phosphorus compound, or introducing them into a solution of phosphoric acid in a liquid medium, such as water and z ecovering the catalyst by drying and calcining.

Inventors: CALLAHAN, JAMES LOUIS, HARDMAN, HARLEY FOCH, PEDERSEN, SVEND ERIK
Applicants: THE STANDARD OIL COMPANY
Application year: 1981
Main classification: B01J27
IPC codes: B01J27, C07C67, C07C51, C07C255, C07C253, C07C57, B01J23, C07B61