SU843706A3 - Catalyst for acrolein oxidation to acrylic acid - Google Patents

Description

iron, nickel, phosphorus, indium, ismuth, lanthanum, rhenium, titanium and rare-earth elements, and an element selected from the group containing manganese, obalt, phosphorus, nickel and copper, in 5 the composition of the catalyst corresponds to the empirical formula

Md (, V | Q Xj Ye 0. De C - antimony or germanium, or

tungsten; 10

1X is an element selected from the group containing silver, magnesium, thallium, cadmium, iron, nickel, phosphorus, indium, bismuth, lanthanum, rhenium, titanium and rare-earth elements; Y is an element selected from the group consisting of manganese, cobalt, phosphorus, nickel and copper; 20

, 2; , l-0.5;

., 2; 25

f is the number of oxygen atoms required to saturate the valence of all elements. The proposed catalyst has increased activity and selectivity of acrolein conversion reaches 100% with selectivity for acrylic acid up to 96.

 The catalysts are made by displacing the ingredients in the desired proportions, the resulting aqueous suspension is dried and the product is calcined. The ingredients used to produce the catalysts can be 40 oxides, halides, nitrates, acetates or other salts of a particular compound. If a carrier is used, the material comprising the carrier is typically introduced into the catalyst 45 along with other ingredients. After the catalyst elements form a slurry, it is dried dry and the resulting solid is heated in the presence of air at 50 200-600 C. Calcination can be carried out outside the catalytic reactor, or activation can be carried out directly at the place of use.

The proposed catalysts are tested in an oxidation reaction of unsaturated aldehydes to obtain the corresponding acid.

The method involves contacting unsaturated aldehyde and molecular oxygen in the presence of steam at a temperature of 200-500 ° C. The ratio of reactants can vary greatly, but the molar ratio of molecular oxygen and aldehyde is usually between 0.5 and 5. The best is to add molecular oxygen in the form of air. The amount of steam can vary greatly from a small amount formed in the reactor to 20 moles or more of steam per mole of aldehyde. In practice, 1-10 moles of steam are added to the reaction feed per mole of aldehyde used.

The proposed catalyst is obtained as follows.

PRI me R A. Catalzato

6.54 g of ammonium metavanadate is added to 250 cm of hot distilled water. After about 15 minutes of heating and stirring, the reagent is dissolved and 39.50 g of ammonium heptamolybdate is added to it and dissolved in it. Then 2.71 g of antimony oxide () are added. The solution is evaporated almost to dryness with constant heating and stirring, and then the contents are placed in a dryer at a temperature of IIO-120 ° C for 16 hours. The dried material is ground and passed through a 50 mesh sieve. 20% of the obtained powder is applied to the alundum beads.

The obtained balls are dried at 110-120 C for 3 h, and then activated by heat treatment at 2 h.

Example. Mo catalyst, tSb V, Oug, oh.

The reaction of comparative example A is repeated with the use of 6.37 ammonium metavanadate, g of ammonium heptamolybdate and 1.51 g of silver acetate, and then 2.64 antimony oxide (ShjOj) is added.

PRI mme R 2. The catalyst Mo, iSb V, MgejO, r.

The reaction of Comparative Example A is repeated using 6.48 g of ammonium metaadadate, 39.13 g of ammonium heptamolybdate and 1.98 g of magnesium acetate, and then 2.64 g of antimony oxide are added.

PRI me R 3. Catalyst Moi Sb V, Tlp, tOw ;,. 5 Comparative A reaction is repeated using 4.80 ammonium metavanadate, 29, Pg ammonium hepta libdate and 1.04 g acetate tate, followed by addition of 2.02 g of antimony oxide. I Example4. Catalysis MO, iSb, V, Cd ,, 04у, g. The comparative reaction of A is repeated using 4.85 ammonium metavanadate, 29.27 g of ammonium molybdate hept and 0.736 g of cadmium acetate, after which 2.01 antimony oxide is added. Example 5. The catalyst MO ,, Sb, V, Mg ,, 0 ,,,. The reaction of comparative example A is repeated using 1, ammonium metavanadate, 32.23 g of ammonium molybdate hept and 0.65 g of magnesium acetate, after which 2.21 g of antimony oxide are added. Example 6 Mo, iV, Sb,. The reaction of comparative example A is repeated using 4.75 g of ammonium metavanadate, 28.65 g of ammonium molybdate hepta, 1.13 g of silver acetate and 0.66 g of manganese acetate, after which 1.96 g of antimony oxide is added. Example 7. Catalyst Mo / iVj Sb, Cdo, iCoo,,. The reaction of comparative example A is repeated using 4.79 g of ammonium metavanadate, 28.95 g of ammonium heptamolybdate, 0.73 g of cadmium acetate and 0.34 g of cobalt acetate, after which 1.99 g of antimony oxide is added. PRI me R 8. The catalyst Mo, iVj sb cd ,, PO, Oh. The reaction of comparative example A is repeated using 4.79 g of ammonium metavanadate, 28.95 g of ammonium hepgamolybdate, 0.73 g of cadmium acetate 6.16 g of 85% phosphoric acid, after which 1.99 g of antimony oxide is added. , Example 9. Catalyst To, 2Nio, 046, Sb. The reaction of comparative example A is repeated using 4.75 g of ammonium metavanadate, 28.66 g of ammonium heptamolybdate, 1.03 g of thallium acetate and 0, 39 g of yurate nickel hexahydrate, after which lj, 97 g of antimony oxide are added. 6 The catalysts of the following examples 10-17 (comparative example B) are prepared and compared with already known catalytic compositions (example A) for the reaction of the oxidation of acrolein to acrylic acid. ExampleB Catalyst Mo, x Vj Gei Oitf, f. 6.67 g of ammonium metavanadate are added to 250 cm of hot distilled water. After the reagent is dissolved by heating and stirring, 40.27 g of ammonium heptamolybdate is added first, and then 1.99 g of Ge. The resulting mixture is evaporated almost to dryness with constant heating and stirring. The contents are placed in a dryer at a temperature of 120 ° C for 16 hours. The dried material was crushed and passed through a 50 mesh sieve. 20% of the obtained powder was applied to alundum beads. The resulting beads are dried at 120 ° C for 3 hours and then thermally treated at 2 hours. Example 10. Catalyst Mo “Vj Ge Per, 0“ i; . The reaction of comparative example B is repeated using 4.90 g of ammonium metavanadate, 29.54 g of ammonium heptamyl libdate, 1.46 g of germanium oxide (GeO), after which 0.564 g of iron nitrite is added. PRI me R 11. Catalyst Mots Vj Ge Nifl, 5-0 “g, h. The reaction of Example B is repeated using 6.55 g of ammonium metavanadate, 39.52 g of ammonium heptamolybdate, 1.95 g of germanium oxide and 2.71 g of nickel nitrite hexahydrate. The catcher is prepared as described above. Example 12 Catalyst O, g V, Ge, T, Qt, s, i The reaction of Example B is repeated using 4.89 g of ammonium metavanadate, 29.56 g of ammonium heptamolybdate, 1.46 g of germanium oxide and 1.06 g tata tally. The catalyst is manufactured in the manner indicated above. Example 13. Catalyst o, t VjGe P, Otf, t Example 1 is repeated using 4.98 g of ammonium metavanadate, 0.10 g of ammonium heptamolybdate, 48 g of germanium oxide and 0.163 g of 5% HjPO. The catalyst is made as indicated above. 14. Catalyst Example Example Vj Ge In 0.1 (fs; Repeat Example B using 4.94 g of ammonium metavanadate, 29.81 g of ammonium heptamolybdate, 1.4. Germanium oxide and 0.921 acetate indium. The catalyst is made as indicated above Example 15. Catalyst Mo / g Vj Ge B1b, hO Ca. Example B is repeated using 4.89 g of ammonium metavanadate, 29.50 g of ammonium heptamolybdate, 1.46 g of germanium oxide and 0.63 g of bismuth oxide. The catalyst is made by the above method. Example 16. Catalyst Moft ultrasonic Ge RE tsu Q, b, d. Example B is repeated using 4.70 g ammonium metavanadate , 28.36 g of ammonium heptamolybdate, 1.40 g of germanium oxide and 2.58 g of rare earth metal mill hexahydrate. The catalyst is made by the above method. If the rare-earth metal chloride was in the form of oxide, this would be 46.2% for rare-earth oxide, where, 2: GeOj 48.0; 33, Oj NdjOs 13.0; RHBO) K 4.5; other oxides of rare-earth metals 1.5. l Example 17. Vi Gei T1 eji Cu ' v / fO v, j catalyst. Example B is repeated using 4.87 g of ammonium metavanadate, 29.45 g of ammonium heptamolybdate, 1.45 g of oxGy germanium, 1.06 g acetale thallium and 0.277 g of copper acetate The catalyst is made as indicated above. Example B. Catalyst Co "Vi, g ,. To 250 cm hot distilled. 6.16 g of ammonium metavanadate are added to the water. After this reagent was dissolved by heating and stirring, 5.84 g of ammonia metamath ramate and 37.21 g of heptamolib ammonium were added and quickly dissolved. The solution is evaporated almost to dryness by continuous heating and stirring, and then the contents are placed in a dryer for 16 hours at a temperature of 120 ° C. The choi material is then ground and passed through a 50 mesh screen. 20% by. Applied powder is applied to apundum beads. 8 The obtained balls are dried at, and then activated by heat treatment at 2 h. Example 18, Catalyst Mo / g Vj .W /, TIff, f Oad, /. Example B is repeated using the same reagents, in the same quantity, after which 5.22 g of a 20% titanium chloride solution is added. The catalyst is made by the above method. Example 19. Catalyst Mo “V, V /, Renj, Oi ,, e. Example B is repeated using the same reagents, in the same quantity, after which 0.942 g of ammonium perrhenate is added. The catalyst is made as indicated above. Example 20. Catalyst Mo, 1 V 3 W, 2 La 0.5- O i, f, a. Example B is repeated using the same reagents, in the same quantity, after which 1.43 g of lanthanum oxide () is added. The catalyst is made as indicated above. EXAMPLE 21 Catalyst ModVj); CO (} 4 0 8 8, o. Repeat Example B using 4.44 g of ammonium metavanadate, 4.21. G of ammonium meta-tungstate and 26.84 g of ammonium heptamolybdate and then 1.03 g of lanthanum oxide and 0.315 g of cobalt acetate are added. The catalyst is obtained by the above method. Example 22. Mots catalyst V, S, D 1 ao, g Cu ", d Oitu, o. Repeat example B using 4 , 43 g of ammonium metavanadate, 4.20 g of ammonium meta-tungstate, 26.75 g of ammonium heptamolybdate, after which 1.03 g of lanthanum oxide and 0.50 g of fine acetate are added. The catalyst is obtained as indicated above Example 23. Mo / i catalyst UZ, f Mn, 0. Example B is repeated using 4.45 g of ammonium metavanadate, 4.22 g of ammonium metatungstate, 26.85 g of ammonium heptamolybdate, and then 1 03 g of lanthanum oxide and 0.31 g of manganese acetate. The catalyst is obtained by the above method. The catalysts obtained above are placed in a reactor, the design of which includes a system of stainless steel pipes with an inner diameter, the reaction zone is 20 cm. .

9843706. ten

The reaction raw material is co-temperature, the acrolein / air / Ni / par mixture used in the course of the reaction, and obtained by a conversion print in a molar ratio of 1/8, 5 /, 5/6. are given in table. 1-3, where the con reactions shown are carried out at atmospheric pressure, are given as follows, contact time 2c. s tick marks:

Acrolein Noli, XOO reacted

Conversion,%

Single yield,% Selectivity,% Mojm of the exacted acrolein

Moths of the reduced product xYO Moths of the original source of Mo1Sh reduced acrylic acid xOO of Mo hydro-reacted acrolein

20% of the active ingredient, on the auxillary balls.

Table 1

X

20% of the active ingredient deposited on the alundum beads.

, Mo, V, W ,,,

MowVj W, iT5p, s-Ove, 293

Mo "UZ WvReo, zO; j302

MoijV, li ,, i Iaa f0ifr, s319

Mo / i V, W ,,, - tO efl342

Mo It Vj W, Lao, r Cuo ,, o320

° "Vj WjjLa jMni ,, Ove, o348

table 2

Claims (1)

TABLE 3 13 Claims of the invention A catalizer for the oxidation of acrolein to acrylic acid, including molybdenum, van; oxides and oxygen, about the fact that, in order to increase the catalyst’s reactivity and selectivity, it additionally contains antimony or germanium or tungsten an element selected from a Q group containing silver, magnesium, thallium, cadmium, zkelezo, nickel, phosphorus, indium, bismuth, lanthanum, renne, titanium, and rare earth elements, and an element selected from the group containing manganese, cobalt, phosphorus, nickel and copper, as a result of in the catalyst corresponds to the empirical formula of Noah Vg Ce Xv (Ye Of, where C is antimony or germanium, or tungsten; X is an element selected from the group consisting of silver, magnesium, thallium, cadmium, iron, or Ni-843436 05. 14 01. with CL 1TOTI Kel, phosphorus, indium, bismuth lanthanum, rhenium, titanium and red, goat elements, Y is an element selected from the group containing manganese, cobalt, phosphorus, nickel and copper; a-12; , 2; deO, l-0.5;; 2; f is the number of oxygen atoms required to saturate the valence of all elements. Priority on the grounds: 5.76 at C - antimony 5.76 at C - germanium 6.76 at C - tungsten. Sources of information, taken into account in the examination. US patent No. 35667773, 260-530, published. 1971. US Patent 3,644,509, 260-530 N, published. 1972 (ProP).