CS195708B2 - Oxidative catalyst for oxidation,ammoxidation and oxidehydrogenation - Google Patents

Abstract

The oxidation catalyst has the general formula XaAbDcEdFefBigMo12Ox, wherein: X is yttrium, zirconium, silver, sulphur, cerium, thorium, praseodymium, ruthenium, gallium, niobium, germanium, chromium, tin, manganese, indium, copper, tungsten, tantalum, tellurium, lanthanum, or a mixture thereof, A is an alkali metal, thallium or a mixture thereof, D is nickel, cobalt, magnesium, strontium, calcium, zinc, cadmium or a mixture thereof, E is phosphorus, arsenic, boron, tungsten, antimony or a mixture thereof, it also being possible for E to be sulphur if X is tungsten, a is a number greater than 0 and smaller than 5, b and d are numbers from 0 to 4, c is a number from 0.1 to 20, f and g are numbers from 0.1 to 10 and x is the number of oxygen atoms required for saturating the valency of the other elements present. The catalyst can be used for a very wide range of oxidation reactions, such as the oxidative dehydrogenation of olefins and oxidation and ammoxidation of methyl-substituted aromatic compounds.

Description

Catalysts comprising iron, bismuth, molybdenum and nickel, cobalt, magnesium, zinc, cadmium, strontium or calcium together with promoters, yttrium, zirconium, silver, sulfur, cerium, thorium, praseodyne, ruthenium, gallium, niobium, germanium, chromium, tin, manganese, indium, copper, tellurium, lanthanum, tantalum, tungsten or mixtures thereof.

Catalysts known, for example, from U.S. Patents 3,642,930 and 3,144,631 have some drawbacks, in particular they do not provide sufficiently satisfactory selectivity and yield in a single pass. Therefore, efforts have been made to improve these catalysts by the presence of promoters, which has been achieved according to the invention.

The catalysts of the invention have significant advantages over other catalysts of this kind when used for the oxidation, amoxidation and oxydehydrogenation reactions.

The oxidation catalyst of the invention is based on a catalyst of formula

A _b D _c E _d Fe _f BlgMo ₁₂ O _x where

And denotes alkali metal, thallium or a mixture thereof,

D denotes nickel, cobalt, magnesium, calcium, strontium, cium, zinc, cadmium or a mixture thereof,

E represents phosphorus, arsenic, boron, tungsten, antimony, or a mixture thereof and abad is 0 to 4, c is 0.1 to 20, fag is 0.1 to 10, and x is the number of oxygen required to saturate the valence of the other elements present, and characterized in that the oxidation catalyst comprises at least one additional component and has an empirical formula

X _and AbDcE _d Fe _f Bi _g Mo ₂ Ox where

X represents yttrlum, zirconium, silver, sulfur, cerium, thorium, praseodymium, ruthenium, gallium, tantalum, lanthanum, niobium, germanium, chromium, tin, manganese, indium, copper, tellurium, tungsten or a mixture ^thereof: a is greater than 0 and less than 5 a

A, D, E, b, c, d, f and g are as defined above with the proviso that when

X means niobium, germanium, chromium, tin, manganese, indium, copper, tellurium. or a mixture thereof,

A has a meaning other than thallium and further b is greater than 0 and less than 4 and with the further condition that if

X means tungsten,

E has a different meaning from tungsten, but is optionally sulfur

D is at least one metal selected from the group consisting of nickel, magnesium, calcium, strontium, zinc and cadmium.

The catalysts of the invention are prepared as described in Example a. are useful for a wide range of known oxidation reactions. In these reactions, the novel catalyst of the invention replaces the catalysts previously used. . Reactions. se. performed under substantially the same conditions. Of particular interest is the use of these catalysts for the oxidation and oxidative dehydrogenation of olefins, but may also be suitable for other reactions such as oxidation and amoxidation of methyl-substituted aromatic compounds.

Examples 1 to 9

Oxidative dehydrogenation of 1-butene

A reactor made of a 8 mm stainless steel tube having an inlet for the reactants and an outlet for the products is used. The reactor is equipped with a band filled with 2.5 ml of catalyst.

Various catalysts of the invention are prepared as described below. All contain 80% active ingredients and 20% silica.

P ^ 1 ^ key

Cro 5 К on _e 1N12,5 С O4 with F ^ © ^ Ο 3B mu ϋχ

Dissolve 63,56 g of ammonium heptamolybdate (ΝΗ4) βΜθ7θ2.4H2O in 100 ml of water, and with stirring a. heating add 51.66 g of 40% - Nalco silica sol. To the suspension was added 1.50 g.

Separately, 36.36 g of ferric nitrate Fe (NO3) 3 is heated and dissolved in 10 ml of water. . 9H2O. 14.55 g of Bi (NO3) 3.5H2O, 39.29 g of Co [NO3] 2.6H2O, 21.81 g of Ni (NO3) 2.6H2O and 3.03 g of a 10% KNO3 solution are then dissolved in the solution. The nitrate solution is slowly added to the molybdenum-containing suspension. The mixture is heated and stirred until it begins to thicken. Dry the solid in an oven at 120 ° C with occasional stirring. The final catalyst was calcined in air at 550 ° C for 16 hours.

Example 2

Te0,5K ₀ .Ni2 ₅ Co ₄ 5Fe3BiMo _{1 x} H2O

The catalyst is produced in the same manner as in Example 1, except that the CrC3 is replaced by 4.04 g of TeCl4.

Example 3

Geo, 5Ko, iNi2,5CO4i ^] ^ (e3BiMOi2O _x

The catalyst is produced in the same manner. in the manner shown in Example 1, except; that chromium oxide CrOs is replaced by. . 1.57 grams of GeO2.

He attaches

W () i5Ko, iNi2,5C045Fe3BiMOi20x

The catalyst was prepared in the same manner as in Example 1 except that the chromium trioxide CrOs was replaced with 4.04 grams (NH4J & W7O24.6H2O).

Example 5

Mn015Ko, ll ^: 12.5iCo4j5FeзBiM012O _x

The catalyst was prepared in the same manner as in Example 1, except that the chromium oxide (SiO2) was replaced with 5.37 grams of a 50% magnesium nitrate solution.

Example

Th ₀ ,, 5Ko iNÍ2,5Co4 ₍₅ ie3l ^ ^ ii ^ _(x ^ _ J20

The catalyst was prepared in the same manner as in Example 1 except that the chromium trioxide CrOs was replaced with 8.28 g of Th (NO3) 4O. - 4H2O.

Example 1 - d 7.

Nb0.5Ko, IN2.5CC4.5Fe3BiMo10Ox

Dissolve in 50 ml of hot water. 31, -8 - g ammonium heptamolybdate. To this solution was added 2.0. - gram - NbCls. suspended in water, - 26.5. grams of 40 percent of Nalco silica sol and a mixture of 10.9 g of nickel nitrate and 19.7 g of cobalt nitrate.

A solution of 18.2 g of ferric nitrate is prepared separately. 7.2 g of bismuth nitrate and 0.19 g of KOH, as a 45% solution, are slowly added to the molybdenum suspension. The rest of the preparation. is the same as in - example 1.

Example 8

Pro / ₎ Breastfeeding _2,5 (Co4,5Fe3BiMoi2O _x

The catalyst was prepared in the same manner as in Example 1, except that 2.60 g of chromium trioxide was replaced

PrO2.

Example 1 a d 9 θθοοΚο, ιΝΙί ^ Οο, ^ ΕβίΒίΜΟυΟχ

The catalyst was prepared as described in Example 1, p. except that chromium trioxide is replaced by 8.22 'g (NH4) 2C & (NO $) 6.

₍ Catalyst samples are ground and sieved to give a fraction of 20 to 35 mesh / 25 millimeters, which is charged in a volume of 2.5 ml db of the reaction zone · reactor. 1-hutene, air and steam applied in a molar ratio of 1: 11: 4 is fed through the catalyst at a temperature of 350 ° C at an actual contact time of 1 s.

The results of the experiments are presented as follows:

% conversion = ° / o selectivity = ^ ·% yield at one = passage of reacted olefin X 100 dosed olefin obtained product X 100 reacted olefin obtained product X 100 dosed olefin

The results of these experiments are shown in Table 1.

Isomerized 1-butene does not count as reacted olefin. ,

Table 1 (Oxidative dehydrogenation of 1-butene to butadiene p

Xo / iKuNh4O4 BiMouOx

Example Catalyst X = Conversion Results,% Butadiene selectivity Yield of butadiene in one pass 1 · Cr 100 ALIGN! 98 97.7 2 » Te 98.8 98 97.3 3 Ge 98.8 98 96.8 4 W 98.6 96 . 95.7 2 * Mn 98.4 97 95.2 2 * Th 98.4 97 95.2 7 Nb ₄ 97.6 95 92.6. 8 * Ex 92.1 97.5 94 2 * Ce 92.1 . 100 ALIGN! 92

* 'no steam is added

Example 10 to. 17

Oxidative dehydrogenation of 1-butene. with catalysts containing germanium. Various catalysts containing germanium are prepared as follows:

Example

The catalyst was prepared in the same way as the catalyst of Example 1, except that potassium was not added and the chromium trioxide SiO2 was replaced by 1.57 g of GeO2. , example 11

The catalyst was prepared as in Example 10 except that normal potassium was added and 61.04 g of nickel nitrate was used instead of nickel and cobalt. · '

Example 1 a d 1 2

The catalyst was prepared as in Example 11, except that the nickel nitrate was replaced by 61.12 g of cobalt nitrate.

Example 13 /

The catalyst is produced. as in Example 11, except that 72.83 g of ammonium heptamolybdate and 3.03 g of a 45% KOH solution are used. '

Example 1 1.4

The catalyst is prepared as described in Example 11, except that 53.85 grams of Mg (NO3) 2.6H2O is added instead of nickel and cobalt and GeO2 is used instead of GeO2.

3.22 g GeCla.

Example 15

The catalyst was prepared as described in Example 11, except that the nickel nitrate was replaced with magnesium nitrate and GeCl2 was used as in Example 14.

Example 1 6

The catalyst was prepared as in Example 11, except that cobalt was replaced by magnesium nitrate as a 50% solution.

Example 17

The catalyst was prepared as in Example 11, except that 2.72 g of GeCU for germanium was used, 21.48 g of a 50% magnesium nitrate solution replaced nickel, and 3.03 g of a 45% KOH solution was used.

The catalysts were tested as in Examples 1-9. The results are summarized in Table 2.

Table 2

Catalysts containing germanium for the conversion of 1-butene to butadiene

Results,% Yield

Example Catalyst Conversion Selectivity in one pass 10 Ge0,5NÍ2.5CO4,5Fe3BÍMOi2Ox 98.8 91 90.4 11 G60.5lK), IIN7Fe3BiMO] 20x 99.9 94 ' 94.3 86.8 12 Geo, 5Ko, iCo ₇ Fe3BiMOi2Ox 87.4 99 13 Geo.sKojjNib. 5CO43FO3BIMO13 ₍ 75θχ 100.0 99 99.2 14 Geo.sKo.iMgyF ^ BiMo ^ Ox 98.7 «98 96.8 15 Dec Geo ₎ 5Ko, 1Mg2.5C04, FFeзBiMOi2Oχ 99.4 99 98.1 16 Ge ₀ .5K0. iNi ₂ .5МП4. 5Fg ₃ BiMoi2O _x 96.9 97 93.7 17 Ge0.4Ko, 8Mn2C0 ₅ Fe3BiM012Ox 55.2 99 54.6

Example 18

Two promoters in a thallium-containing catalyst

Catalyst 80%

Geo, 5Cri, 5Tlo, iNi2CO3Feo, 5BiMoi20 _x and 20% SiO2 were prepared in the same manner as described in the above examples and used in 1-butene oxydehydrogenation using 1:11 1-butene and air at a temperature of 350 ° C and actual contact time of 1 s.

The 1-butene conversion was 89.6%, the selectivity was 98% and the yield at 1 vent was 88.1%.

Example 19

Cesium-containing catalyst

80% catalyst

Many of the 5C50, Ni2, sCo.45Fe3B1Mo2Ox and 20% SiO2 were prepared as outlined in Example 5, except that the potassium compound was replaced with 0.59 g of CsNo3 cesium nitrate. Using the batch and conditions of Example 18, the conversion of 1-butene to product was 100%, the selectivity to butadiene was 99%, and the yield in one pass. 98.6 ° / o.

Examples 20 to 28

Oxydehydrogenation of 2-butene

Catalysts produced in the examples. of the above are used for the oxydehydrogenation of 2-butene. to butadiene. The reactor and catalyst volume of the examples above are used at actual. contact time 1 second. A mixture of 57.5% trans · and 42.5% cis-2-butene is reacted. The ratio of 2-butene to air is 1:11. The results of these experiments are shown in Table 3. The parentheses around the elements in the catalyst formula indicate that the elements are the same as those shown in Table 3. previous attempts.

Table 3 Oxydehydrogenation of 2-butene to butadiene. Example Catalyst Reaction Results,% Conversion temperature, select

° C vita in one pass

20 May Ceo.s (Kq. ^^^ BIMo ^ OJ 350 95.4 93 88.3 21 Nb0,5 (KoлNi2.50O4 ₅ ee BLMo _{3 1 x} 2 O) 350 93.0 95 88.1 22nd Pro, s (Ko, iNi2,5Co _{4 (} 5Fe3BiMo12Ox) 375 97.7 89 87.3 23 M По.5 (Kod ^^^ BiMo ^ Ox) 385 95.1. : · 93 88.9 24 Cro5 (Ko _i IN2,5CO45Fe3BÍMoi2O _x ) 385 95.6 95 90.9 25 Ge ^ o5 (K (0.1Ni2.5Co ₄ .5eeзBiMO12O _x ) 385 84.4 95 80.5 26 Wo.s (Ko.1Ni2.5C04.5F e3BiMoi2O _x} 385 85.0 . , 95 80.3 27 Mar: Th _0, 5 (K ₁ NÍ2,5Co45Fe3BiMoi2O _x) 400 90.5 92. 82.7 28 * Ge ^ o, 5Ko, ₈ Ni2,5Co ₄ , ₅ ee3BiM ^ o ₁ 375Ox 375 95.7 90 86.5

* contact time 4 s

Examples 29 to 37

High air to olefin ratio

The catalyst of the invention, prepared as described above, is used for the oxydehydrogenation of a 2-butene mixture in the same manner as in Examples 20 to 28, except that the ratio of 2-butene to air is 1:31. 350 ° C, and actual contact time of 1 s.

The results of these experiments are shown in Table 4.

The lanthanum-containing catalyst of Example 37 was prepared by substituting CrOs for 6.22 g of La (NO3) 3 ', 5H2O in the catalyst of Example' 1.

Table 4

Oxydehydrogenation of 2-butene with catalyst X0l5K0l1N · 12l5C0 ^| 4l5eeзBiMO12Oχ Example Catalyst, Result, ° / o X = Conversions Selectivity Yield in one pass

29 Mn 100.0 97 96.8 30 Cr 96,6 ^х 96 92.5 311 ' Nb 100.0 93 92.8 32 Ce 100.0 89 88.9 33 ¹ ' Ce 100,0, 91 90.9 34 Ge. 81,5 ' 98 80.0 352) W 92.9 91 84.2 36 ² ' Th 96.7 90 ' 86.7 37 La 100.0 95 95.4

(i) Reaction temperature 340 ° C.

2j Reaction temperature 385 ° C.

Example 38

Example 39

High air ratio process with different potassium-containing catalyst.

Catalyst of the formula 80% Wo 5Ko, 5Ni2,5Co4,5Fee3iMoi.20 _X and 20% of S1O2 was prepared as described In Example 9, except that. potassium is added five times. The catalyst was tested for butadiene production using the 2-butene mixture mentioned above at an air to 2-butene ratio of 3: 1, actual contact time, 1 s and 385 ° C. The 2-butene conversion was 96.4%, the selectivity was 91% and the yield in one pass was 88.1%.

Oxydehydrogenation of isoamylene

With the catalyst of Example 13 in a 5 ml reactor, a mixture of equal volumes of 2-methyl-1-butene and 2-methyl-2-butene is oxyhydrogenated to isoprene. At 400 ° C and an actual contact time of 2 seconds, the isoamylene conversion is 85.9%, the selectivity to isoprene is 82% and the yield, on one pass to isoprene, is 70.2%.

Example 40

Production of isoprene with chromium-containing catalyst

The same procedure as in Example 39 and the catalyst of Example 1 were used to produce isoprene. The conversion was 86.2%, the selectivity was 70% and the 'single pass yield' was 60.5%.

Comparative Examples A and B and Examples 41 to 74

Comparison of a promoter-containing catalyst according to the invention with a base catalyst

A 5 ml fixed bed reactor was made from a stainless steel tube with an internal diameter of 8 mm. Catalysts prepared as described below are charged to the reactor. and heated to 420 ° C 'at air flow. At the reaction temperature for Comparative Example B and Examples 41 to 74, a reaction mixture consisting of propylene, ammonia, oxygen, nitrogen and steam in a ratio of 1.8: 2.2: 3.6: 2 is fed through the catalyst at a contact time of 3 s, 4: 6. The ratio of olefin feed weight to catalyst WWH weight per reaction is 0.10.

For Comparative Example A, a reaction mixture of propylene, ammonia, oxygen, nitrogen and steam was used in a ratio of 1: 1.1: 2.1: 7.9. : 4 at a temperature of 420 ° C and a contact time of 6 seconds. WWH is 0.03. This example is shown to show that the base catalyst is produced under normal production conditions at a lower WWH.

Catalysts are produced as follows:

Comparative Examples A and B% Ko, iNi2,5CO4,5Fe3BiPo, 5Moi20 _x 4 ~ 20% SIO2

A solution of 127.1 g of ammonium heptamolybdate (NH4) eMo7O2i is prepared. 4 HzO and water. To this solution was added 6.9 g of a 42.5% H3PO4 solution and 102.7 g of a 40% Nalco silica sol to form a suspension.

Separately, an aqueous solution containing 72.7 g of ferric nitrate, Fe (NO3) 3, was prepared. . 9 H2O, 29.1 g bismuth nitrate, Bi (NO3) 3.5 H2O, 78.6 g cobalt nitrate Co (NO3) 2.6 H2O, 43.6 g nickel nitrate Ni (NO3j2.6 H2O and 6.1 g 10 The metal nitrate solution is slowly added to the suspension, the resulting mixture is evaporated to dryness and the solid obtained is heated at 290 ° C for 3 hours, at 425 ° C for 3 hours and at 550 ° C. hours.

Example 41% Geo, 6Ko, iNi2,5Co4,5Fe3BiPo, 5Moi20 _x 4 ~ 20 percent SIO2

63.56 g of ammonium heptamolybdate are dissolved in 60 ml of hot water. This solution was added to 53.25 g of 40% Nalco silica sol. The mixture is heated at low temperature with stirring for about 5 minutes. To the resulting suspension was added 3.46 g of H 3 PO 4 as a 42.5% solution and the mixture was heated for 2 minutes.

Separately, 36.36 g of cesium nitrate is mixed with 10 ml of water and melted on a hot plate with constant stirring. Then 14.55 g of bismuth nitrate, 39.29 g of cobalt nitrate, 21.80 g of nickel nitrate are added until the previous metal nitrate has melted. 3.03 g KNO3 are added as a 10% solution and 1.88 g GeO2 and melted. .

Solution containing metal nitrates. is slowly added to the suspension and heating is continued until the mixture begins to solidify. The mixture is dried in an oven at 120 ° C with occasional stirring. The dried catalyst was calcined at 550 ° C for 16 hours.

Examples 42 to 66

The other catalysts of the examples were prepared in the same manner as the catalyst of Example 41. Germanium, tin, chromium and titanium were added to the catalysts as oxides. Copper and silver are added to the catalysts in the form of nitrates. Ruthenium and beryllium - are added to the catalysts as chlorides. Tungsten is introduced into the catalyst as ammonium tungstate, which is added together with ammonium heptamolybdate. Although different anions are used, the individual anions of the catalyst component do not appear to be significant.

These catalysts do not contain phosphorus; the promoter elements of the invention are added to the catalyst in a molybdenum-containing slurry.

Example 67% Gai, oKo, iNi2,5Co4,5Fe3BiPo, 5'Moi4O _x 20 percent S1O2

The same way, . as described in the above examples, a catalyst is prepared using both. a suspension containing '24.7 g of ammonium heptamolybdate', 19.4 g of 40% NalCo silica sol and 1.15 g of a H3PO4 42.5% suspension, and a suspension containing 12.1 g of ferric nitrate, 4.8 g bismuth nitrate, 13.1 grams of cobalt nitrate, 7.3 grams of nickel nitrate, 1.0 grams of a 10% 'potassium nitrate solution' and 2.5 grams of gallium nitrate Ga (NOs) 3.3 H2O. The suspensions were combined, evaporated and hot worked as described above.

Example 1 'a' d 68

80,% Ini, oKM-Ni2.5Co4.5F & 5BiPo3oši3 (0 _x 4-20 percent SiOa)

A suspension containing 71.6 grams of ammonium heptamolybdate, 58.0 grams of 40% Nalco silica sol and 3.4 grams of a 42.5% phosphoric acid suspension, and a suspension containing 36.4 grams of ferric nitrate, 14.6 grams of nitrate bismuth, 39.3 g cobalt nitrate, 21.8 g nickel nitrate, 3.0 g 10% potassium nitrate solution and 4.5 g indium chloride. The slurry was combined and the solid catalyst was treated hot as described above.

Example 69% B2.4Wo, 6Ko, IN2.5Co4.5Fe3BiPo, 5Moio, eO _x + 20% S1O2 ammonium, 4.8 g ammonium heptawolframate (NH4) 6W7O24.6 H2O, 4.5 g boric acid, 3.5 g.42.5% phosphoric acid solution and 52.3 g of 40% Nalco silica sol. A solution of 36.4 g of ferric nitrate, 14.6 g of bismuth nitrate, 39.3 g of cobalt nitrate, 21.8 g of nickel nitrate, 3.0 g of a 10% potassium nitrate solution is added to the suspension. The resulting suspension was evaporated and the solid treated hot as described above.

The results of the propylene anoxidation experiments leading to the formation of acrylonitrile are given in Table 4. The brackets used in Table 4 have no other meaning than to emphasize the differences in the catalysts.

A suspension of 57.2 g of heptamolybdose is prepared in Table 5

Production of acrylonitrile

Comparison of the catalysts of the invention with the base catalyst

Example Catalyst active components Yield per pass,% Comparative (Ko, iNi2.5Co4.5Fe3BiPo, 5Moi20 _x ) 80, Г Comparative В (Ko, iNi2.5Co4.5Fe3BiPo, 5Moi20 _x } 73.1. 41 Geo, 6 (Ko, iN12.5Co4.5Fe3BiPo, 5Moi20 _x ) 80.7. 42 Gei, 0 (Ko, lN2.5C04.5Fe3BIPo, 5M0120 _x ) 76.4 43 Sno, 5 (K0, lN2.5CO4.5Fe3BIP0.5MO12O _x ) 75.7 44 Sni, o (Ko, iNi2.5Co4.5Fe3BiPo, 5Moi20 _x i 75.0 45 CUO, 1 [KO, lN2,5C04,5Fe3BIPo, 5Moi20 _x ) 77.9 46 Ag0, l (Ko, lNi2,5C04,5Fe3BÍ Ρθ, δΜθ12θ _χ ) 74.2 47 Cro, 5 (Ko, iNi2.5Co4.5Fe3BiPo, 5Moi20 _x ) 78.3 48 Ruo, i (Ko, iNi2.5Co4.5Fe3BiPo, 5Moi20 _x ) 76.4 49 Ti0.5 (Ko, iNi2.5Co4.5Fe3BiPo, 5Moi20 _x ) 74.3 50 Cuo, iGeo, 6 (Ko, iNi2.5Co4.5Fe3BiPo, 5Moi20 _x ) . . . 76,2 ..... 51 Ago, iGeo, 6 (Ko, iNi2 ₎ 5Co4.5Fe3BlPo, 5Moi20 _x ) 75.4 52 Ruo, iGeo, 6 (Ko, iNi2.5Co4.5Fe3BiPo, 5Moi20 _x ) 79.3 53 CUO, 1B1, O (K0, lN2.5CO4.5Fe3BlP0.5MO12O _x ) 76.7 54 AgO, lBl, O (Ko, 1N2,5C04,5F езВ1Р0,5МО12О _х ) 75.8 55 RUO, 1B1,0 (Ko, lN2,5C04,5Fe3BIPo, 5M0120 _x j 76.5 56 Cro, 6Wo, 6 (Ko, iNi2.5Co4.5Fe3BiPo, 5Moio, eO _x ) 73.7 57 Gei.o (Ko, iNi2.5Co4.5Fe2BlPo, 5Moi20 _x ) 79.1 58 Cro, 5Gei, O (Ko, lN2.5C04.5Fe2BIPo, 5M0120 _x ) 79.2 59 Sni, o (Ko, iNi2.5Co4.5Fe2BiPo, 5Moi20 _x ) 76.6 60 Wo.sGei.o (Ko, iNi2.5C04.5Fe ₂ BiMoi20 _x ) 78.4 61 СГ0,5 (Ko, lN2,5C04,5Fe3BÍMoi20 _x ) 79.5 62 Wo, 5 (K0, lN2,5CO4,5Fe3BÍMoi2O _x ) 81.6 63 Ti0.5 (Ko, lNi2.5C04.5Fe3BiMoi20 _x ) 78.6 64 Cuo, iBo, 5 (K0, lN2.5CO4.5Fe3BIMO12O _x ) 80.2 65 Sno, 5 (Ko ₎ iNi2.5C04.5Fe3BiMoi20 _x ) 80.6 66 Geo, 5 (Ko, iNi2.5Co4.5Fe3BiMoi20 _x i 79.1 67 Gai, oKo, iNi2.5Co4.5Fe3BiPo, 5Moi40 _x 76.1 68 Ini, oKo, iNi2,5Co4 ₎ 5Fe3BiPo, 5Mo3,50 _x 76.1 69 B2.4Wo, 6Ko, iNi2.5Co4.5Fe3BiPo, 5Moio, 80 _x 75.7 »WWH = 0.03

It is evident from the examples above that high throughput conversions at a high weight ratio of olefin feed to catalyst per hour (WWH) are achieved using the catalysts of the invention.

Examples 70 to 76

Propylene amoxidation

The various catalysts of the invention are prepared as follows:

Example 1 70% Qty, 5KO, lN12,5C04,5Fe3BiMoi20 _x 4- 20% S1O2

The same procedure as in Comparative Examples A and V is followed except that 10.74 g of 50 wt. % Of Mn (NO3) 2 solution instead of phosphorus.

Example 71% Tho, 5Ko, iNi2,5Co4,5Fe3BiMoi20 _x 4 ~ 20% SiO2

Using the same procedure as above, step 16 except that 16.56 grams of Th [NO 3) 4.4 H2O was used instead of phosphorus.

Example 72% Zro, 5Ko, iNi2.5Co4.5Fe3BiMoi20x + 20%

The same procedure as above was followed except that 9.68 grams of ZrOCl2 was used instead of phosphorus. 8 H2O.

Example 73% Yo, 5Ko, iNi2,5Co4,5Fe5BiMoi20 _x + 20% SiO2

The same procedure as above is followed except that 10,96 grams of Y (NO3) 3.5 НгО is used instead of phosphorus.

The catalysts are ground and sieved to give a 20-35 mesh fraction which is charged into a 5 mL reaction zone of a stainless steel tubular reactor. The amoxidation is carried out using a feed of propylene, ammonia, oxygen, nitrogen and steam in a ratio of 1.8: 2.2: 3.6: 2.4: 6. The bath temperature surrounding the reactor is maintained at 420 ° C and the actual contact time is 3 .

The results of these experiments are shown in Table 6.

Table 6

Propylene amoxidation in use

A0.5K0.1N12.5CO4.5Fe3BiMoi2Ox

Example Catalyst, A = Konyerze Results, ° / o Selectivity Yield in one pass 70 Mn 99.6 82 81.8 71 Th 94.2 83 78.2 72 Zr 98.8 77 76.3 73 Y 99.6 74 73.9 Examples 74 to 77 nitrll. The reaction is in progress at 400 ° C in use

Amoxidation of isobutylene

In the same manner as described above, various catalysts are produced and tested in the amoxidation of isobutylene to 1: 1.5: 11: 4 methacrylonadium isobutylene, ammonia, air and steam with an actual contact time of 3 seconds. Each catalyst contains 20% / o silicon dioxide.

к

7.

The results are given in the table

Table 7 of methacrylonitrile,

Example

Amoxidation

Catalyst, A = isobutylene to methacrylonitrile

A _and Ni2.5Co4.5Fe3BiMoi2Ox

Results,% Selectivity

Conversion

Yield in one pass

74 Well, 5CSO, l 99.8 75 74.9 75 Cro, 5C50, i 100.0 79 79.0 76 Geo, 5Cso, ^x 97.0 77 74.7 77 Wo, 5CSO, 1x ^x 96.0 74 71.4

^x additional heat treatment of the catalyst at 650 ° C for 2 hours ** as well as ad * at 410 ° C

IV

Example 1 a d 78

Propylene amoxidation

A catalyst of the formula is produced

CrWo, 5Ko, iNi2,5Co4,5Fe2BiMoi20 _x * and heat treated at 550 ° C for I8 hours at 600 ° C for 2 hours. Propylene amoxidation is carried out in a 5 ml reactor at 440 ° C, contact time 3 s and weight ratio. olefin feed to catalyst weight per hour (WWH) 0.10 using a propylene, ammonia, oxygen, nitrogen and steam feed in a ratio of 1.8: 2.2: 3.6: 2.4: 6. The propylene conversion is 96, 8%, the selectivity to acrylonitrile is 86 why, and the yield in one pass to acrylonitrile is 83.2%.

Example 79

Propylene amoxidation

In the same manner as in Example 78, a catalyst of 80% MnCro, 5Ko, 1Ni2.5Co4.5Fe2BlMoi20 _x and 20% is prepared.

SiO 2 and heat treated at 550 ° C for 16 hours and at 600 ° C for 2 hours. When the catalyst is used for the production of acrylonitrile, the propylene conversion is 99.0%, the selectivity to acrylonitrile is 85.6% and the yield in one pass is 84.7%.

Example 80

Propylene amoxidation

In the same manner as in Example 78 The catalyst was prepared in 80% GewO, 5Ko, iNi2,5Co4,5Fe2BlMoi20 _x S1O2, 20% and heat treated at 550 ° C for 16 hours. The propylene conversion was 97.8%, the selectivity was 85.1% and the yield in one pass was 83.1%.

Example 81

Propylene amoxidation

In the same manner-as in Example 79 catalyst was prepared in 80% PrWo, 5Ko, iNi2,5Co4,5Fe2BiMoi20 _x and 20% SiO2 is used к ammoxidation of propylene. The propylene conversion was 99.2%, the selectivity was 83 percent and the yield in one pass was 82.7 percent.

Example 1 a d 82

Propylene amoxidation

In the same manner as in Example 80, the catalyst was made from 80% MnSbo, 5Ko, iNi2.5Co4.5Fe2BiMo20 _x and 20%.

S1O2 and tested, using a reaction temperature of 420 ⁹ C. The propene conversion was 100% and the yield per pass and selectivity of 80.4 ° / o.

Examples 83 to 90

Fluid bed amoxidation

In a fluid bed reactor having an internal diameter of 3.8 cm with a sieve component, amoxidation is carried out. % of propylene using different catalysts according to the invention which contain 20% of silicon dioxide. The catalysts were heat treated at 550 ° C for 16 hours and then for 2 hours at the temperature indicated in Table 8. The reactor was charged with 395 ml of catalyst. The feedstock used is propylene, ammonia and air in a ratio of 1: 1.2: 10.5, the ratio of the olefin feeded to the catalyst weight per hour [WWH] is 0.12, the pressure is 84 kP, and the contact time is 5.5 s. the results are shown in Table 8.

Table 8

Propylene amoxidation in a fluidized bed reactor using catalysts of formula A _and Ko, iNi2,5Co4,5Fe2BiMoi20 _x

Example Catalyst, A _and = Heat treatment ° C Reaction temperature ° C Conversion Results,% Selectivity Yield in one pass. 83 Wo.sFe 625 420 96.3 79 76.1 84 Wo.sFe 625 435 99.7 78 77.8 85 Cro, 5Fe 625 435 '97, 7 79 77.2 86 Cro.sFe 625 445 98.7. 79 78.0 87 MnCro, 5 600 435 95.9 83 79.6 88 MnCro.5 600 445 97.7 83 81.1 89 CrWo, 5 600 435 96.2 84 80.5 90 CrWo, 5 600 445 97.9 83 81.3 Examples 91 to 101 5 ml of stainless steel tube with an internal diameter of 0.8 cm. Oxidation of isobutylene at atmospheric pressure catalysts made from above. Catalysts

were tested at a reaction temperature of 371 ° C using an isobutylene, air and steam feed

The various catalysts described above are prepared as described above. For fixed bed reactor manufactured by Ta b Oxidation of isobutylene to methacrolein and pressure acids using ka A _and N12,5CO4 ratio of 1: 10: 4 and actual contact time of 4 sec. The results of these experiments are shown in Table 9. u 1 к and 9 ieline methacrylic catalysts of formula i, 5Fe3BiMoi2O _x Results, ° / o лот pass at atmospheric Example Catalyst Yield on eating MA Conversion Selectivity MAA Total 91 Pro, 5Ko, i 61.6 2.2 63.8 91.3 69.9 92 Mno.sKo.i 68.5 2.9 71.4 100.0 71.4 93 Geo, 5Ko, i 67.0 4,5 71.5 100.0 71.5 94 Nbo, 5Ko, i 52.2 2.5 54.7 82.9. 66.1 95 Tho, 5Ko, i 74.3 2.6 76.9 100.0 76.9 96 Sbo, 5Ko, iCuo, i 66.1 1.4 67.5 100.0 67.5 97 Cro 5Cso 5 * 58.9 2.9 61.8 81.7 75.6 98 MnO, 5C50, 5Ko, 5 68.3 3.4 71.7 100.0 71.7 99 Geo, 5Cso, 5Ko, 5th 77.1 1.0 78.1 94.3 82.9 100 ALIGN! NbO, 5CSO, 5Ko, 5 75.3 1,2 76.5 94.7 80.8 101 SbO, 5CSO, 5So, 25 74.1 1.0 75.1 91.4 82.1

MA - methacrolein * 0.84 atp

MAA - methacrylic acid

Examples 102 to 106

Oxidation of isobutylene at higher pressure

In the same manner as described in Examples 91 to 101, the various catalysts prepared above were used in higher pressure reactions. Unless otherwise stated, an excess pressure of 0.84 kg / cm ^{2 is used} . Reaction temperatures and results are shown in Table 10; the same mixture as described above is used and the actual contact time is 3.5 to 4 seconds. The ratio of the weight of olefin feed to catalyst weight per hour (WWH) is 0.098 to 0.159.

F

T 'a b u 1k a 10'

Oxidation of isobutylene to methacrolein and methacrylic acid at higher pressure in the presence of a catalyst of formula

AaNÍ2,5CO4,5Fe3BÍMO12O _x

Example Catalyst, A _and - Temperature Results, ° / o. . ° C Yield in one pass

MA MAA Total Conversion Selectivity 102 Geo, 5Cso, 5th 371 68.4 . F, 6 74.0 96, F 76.7 103 MnO, 5C 50, 1 343 64, F 4.8 69.3 99.6 69, F 104 Tho, 5C 50, 5 343 61, F 3, F 6F, 0 89.0 73.0 10F Ceo, 5C 50, 2 . 363. 70.3 6.4 76.7 98.9 77.6 106 * SbO, 5CSO, 5So, 25 371 '77, 2 1.6 78.8 92.8 8F, 0

MA = methacrolein

MAA - methacrylic acid ^x 0.68 atp.

Example 107

Propylene amoxidation

In the same manner as given in Preparation 41, the catalyst of formula is prepared Tao 5Ko, iN12,5Co4,5Fe5BiMoi20 _x and tested. to the amoxidation of propylene. The yield in one pass was 78.8%, the selectivity was 81% and the propylene conversion was 97.4%.

Claims (1)

Oxidation catalyst · for oxidation, amoxidation and oxydehydrogenation reactions, based on catalyst of formula ABDC _(IEE BigMoi _{R 2} O wherein _x And it means alkali metal, thallium, Xor their mixture, D denotes nickel, cobalt, magnesium, calcium, strontium, zinc, cadmium, or a mixture thereof, E represents phosphorus, arsenic, boron, tungsten, antimony, or a mixture thereof, and abad. Means 0 to 4, c is 0.1 to 20, fag is 0.1 to 10, and x is the number of oxygen required to saturate the valence of the other elements present characterized in that the oxidation catalyst comprises at least one additional component X, so that it has an empirical formula of the invention X represents yttrium, zirconium, silver, sulfur, cerium, thorium,. praseodymium, ruthenium, gallium, tantalum, lanthanum, niobium, germanium, chromium, tin, manganese ,. indium, · copper, tellurium, tungsten or a mixture thereof, 'a is greater than 0 and less than F · a A, D, E, b, c, d,. f and g have. as defined above, provided that when X is niobium, germanium, chromium, tin, manganese, indium, copper, tellurium, or a mixture thereof, And he has another. b is greater than 0 and less than 4, and with the further condition that when X is tungsten, E has a meaning other than tungsten, but is optionally sulfur and D is at least one metal selected from the group consisting of nickel, magnesium, calcium, strontium, zinc and cadmium.