DE2243012C3 - Catalyst containing antimony, iron, cobalt and its use for the synthesis of unsaturated nitriles - Google Patents

Description

worm

T is the reaction temperature,

C is the molar conversion of propylene

S is the molar selectivity to acrylonitrile, based on the moles of converted propylene, and

R is the molar yield of acrylonitrile, based on the propylene introduced,

means.

Example 2

A solution of 404 g of Fe (NO ₃ ) ₃ · 9 H ₂ O in 100 ecm of water was prepared. To this solution was added a solution containing 5.8 g of Co (NO ₃ ) _? 6 H ₂ O and 11.5 g of H ₈ TeO ₆ in 100 ecm of water. The resulting solution was ^{heated to 70 °} C., and then 291.5 g of Sb ₂ O _{3 were added} in small portions. The reaction mixture was dried and the powder was dried again in an oven at 200 ^° C. for 8 hours.

The product was granulated and then ^{calcined at 800 °} C. for 5 hours. The tests carried out after suitable stabilization at each selected temperature under the test conditions described in Example 1 gave the following results:

T C s R

76
89
96

72
84
81

55
75
78

Example 3

to wash. A solution containing 5.7 g of H ₈ TeO ₆ and 2.4 g of CoCl ₂ was added to the precipitate. The mixture was heated to boiling until the water was completely removed. The product thus obtained was dried for 8 hours at 250 ⁰ C, granulated and then calcined at 850 ° C for 4 hours. The catalyst, which was tested under the same conditions as in Example 1, gave the following results:

A catalyst with the same composition as that of Example 2 was prepared in the following manner: A solution of 228 g SbCl ₃ in 400 ecm water and 50 ecm HCl was _{added to a solution of 135 g FeCl 3} · 6 H _{2 O in 250 ecm water} with a concentration of 36%.

_{28% NH 4} OH was added to the resulting solution until it was neutralized. The precipitate was filtered off and washed twice with 100 ecm of water

CC)

465
475

88
93

81
78

71
73

Example 4

A catalyst having the same composition as that of Example 2, but _{containing the SiO 2} (30 percent by weight) carrier, was prepared as follows:

2.9 g Co (NO ₃ ) g · 6 H ₂ O and 5.7 g H ₆ TeO ₈ were added to a solution containing 202 g Fe (NO ₃ ) ₃ · 9 H ₂ O in 100 ecm of water. 145 g of Sb ₂ O _{3 was} added in small portions to the solution. _{280 g of SiO 2} sol (30 percent by weight SiO ₂ ) were added to the slurry obtained in this way, and the reaction mixture was dried with continuous stirring. The product thus obtained was calcined at 25O ⁰ C dried for 8 hours and at 800 ° C for 5 hours.

The catalyst, which was investigated under the same conditions as described in Example 1, gave the following results:

( ⁰ C)

Γ / ο)

470
480

85
93

82
79

70 73

The following table shows the amounts calculated from the amounts used in the preceding examples Catalyst composition.

example Deployed connection Deployed crowd Calculated from this No. the conn as equivalents of the metal atom ratio of dung in g Sb: Co: Fe: Te 1 Sb ₂ O ₃ 291.5 2 gram atoms Sb 1: 0.01: 0.5 Co (NO ₃ ), · 6H ₂ O 5.8 0.02 gram atoms Co Fe (NO ₃ ) _;) · 9 H ₂ O 404 1 gram atom of Fe 2 Sb ₂ O ₃ 291.5 2 gram atoms Sb 1: 0.01: 0.5: 0.025 Co (NO ₁ ) Ji • 6H ₂ O 5.8 0.02 gram atoms Co Fe (NO _a ) ₃ · 9H ₂ O 404 1 gram atom of Fe H ₆ Te O ₆ 11.5 0.05 gram atoms of Tc 3 SbCl ₃ 228 1. Gram atom Sb 1: 0.01: 0.5: 0.025 CoCl ₂ (hexahydrate) 2.4 0.01 gram atoms Co FcCl ₃ -OII ₂ O 135 0.5 gram atoms Fe H ₆ TcO ₆ 5.7 0.025 gram atoms Te 4th Sb ₂ O, 145 1. Gram atom Sb 1: 0.01: 0.5: 0.025 Co (NO ₃ ) ₂ · 6H ₂ O 2.9 0.01 gram atoms Co Fe (NO ₃ ), · 9H ₂ O 202 0.5 gram atoms Fc H ₆ Te O ₈ 5.7 0.025 gram atoms Te

Claims (2)

corresponding amounts, optionally adding patent claims: silicon dioxide as a carrier, subsequent evaporation, drying, granulating and calcining in air. 1. Antimony, iron, cobalt, optionally tellurium The improved catalyst can be beneficial for the and, if appropriate, silicon dioxide can be used as a carrier for the synthesis of unsaturated nitriles Catalyst of the empirical formula where the starting materials are olefins, ammonia, Oxygen or gases containing oxygen Sb ₁ Fe _0-5 Co _0- OiTe _n Og. wenuet. The catalyst according to the invention can where η is zero or 0.025 and q continues to saturate for the synthesis of unsaturated aldehydes and the necessary oxygen to dienes can be used to generate the metal valencies, whereby the starting point is amount is obtained by the formation of insoluble materials olefins and oxygen or air and Precipitations of the starting metals from aqueous water may be used. The Invention Solutions of their salts with aqueous alkaline, proper catalyst is particularly advantageous for syn- Solutions, or through the implementation of soluble theses of acrylonitrile from propylene, ammonia, acid Salting of the starting metals with an antimony 15 slioff or air at temperatures in the range of 350 oxide, in which the empirical formula corresponds - up to 500 ° C. the amounts, if necessary addition of silicon- The catalyst according to the invention can according to dioxide as a carrier, subsequent evaporation, known processes for the preparation of these species Drying, granulating and calcining in air. obtained from compounds. For example 2. Use of the catalyst according to claim 1 20 can be carried out by the catalyst according to the invention for the synthesis of unsaturated nitriles from olefins, coprecipitation, using soluble ammonia and oxygen or gases that convert the acidic bonds of metals as starting materials contain. turns and adds an aqueous alkaline solution. _ ^^ __ He can by implementing a soluble salt like 25 iron nitrate can be obtained with an antimony oxide and evaporation to dryness. The cobalt compounds The invention relates to new catalysts, the manure and possibly the other activators Antimony, iron, cobalt, optionally tellurium and can be used together or separately at each stage of the optionally contain silicon dioxide as a carrier, manufacturing process are added, preferably which are particularly suitable for the synthesis of unsaturated 30, they are, however, before the calcination of the catalysis Nitriles from olefins, ammonia and oxygen tor added at high temperature. The catalysis suitable. gates produced according to the various processes Catalysts for oxidation and ammonia are always dried, last at Oxidation of olefins, the iron and antimony, temperatures in the range from 750 to 95O ⁰ C in air hold are known. For example, such cata- 35 are calcined for a period of 2 to 16 hours. catalysts in Japanese Patent 4 20 264 The catalysts of the invention can thus- (Nitto) and in Belgian patent 6 22 025 probably in reactors with a stationary catalyst bed described. It is also known that this Kata as well as in reactors with a fluid catalyst bed lysers can be used activated by adding activators. can be (see, for example, the Italian 40 The following examples explain the invention.
U.S. Patent 3,59,097 and U.S. Patent. . . .
33 38 952). In particular, Example 1
33 38 952 taught that as activators practically 404 g Fe (NO _{3) 3} · 9 H ₂ O were heated to 8O ⁰ C. use all elements of the periodic _{table. 5.8 g Co (NO 3} ) ₂ · 6 H ₂ O were separated in 50 ecm can. In the same patent specification this wide 45 is solved and this solution was poured into the iron nitrate definition of the elements useful as activators solution. The resulting solution was limited to 25 elements for sind. Stirred from US Pat. No. 80 ^Q C, and then 291.5 g of Sb ₂ O ₃ proschrift 34 09 697 are added to the oxidative dehydrogenation of the ionic manner. The reaction mixture was known currency-butenes to butadiene using a catalyst rend dried 4 hours at 230 ⁰ C,
based on antimony, iron and cobalt in 50 The mass was granulated and used at 800 ⁰ C while the ratio of 1: 0.116: 0.116. Calcined for 2 hours. 6 ecm of the catalyst obtained in this way A catalyst has now been found; the antisators were placed in a tubular steel reactor containing mon, iron, cobalt and optionally tellurium with an inner diameter of 10 mm and is particularly advantageous for the synthesis unheated and heated with an electric furnace. the saturated nitrile is suitable. 55 Mixture entering the reactor at a speed The invention therefore relates to an antimony, iron, speed of 4.3 1 per hour was filled, the hut Cobalt, optionally tellurium and optionally the following composition (molar ratios: propy- Catalyst containing silica as a carrier In / air / ammonia = 1/12 / 1.3. the empirical formula The experiments that can be made after suitable stabilization 60 at any selected temperature and pressure, Sb ₁ ^ e ₀₆ Lo ₀₁ O ₁ Ie _n Oi which was slightly higher than atmospheric pressure, through which η is zero or 0.025 and q which led to saturation, gave the following results:
the amount of oxygen necessary for the metalworking
is obtained by the formation of insoluble precipitates of the starting metals from aqueous solutions of their 65
Salts with aqueous alkaline solutions, or reaction of soluble salts of the starting metals with
an antimony oxide, in which the empirical formula T C. S. R. ( ⁰ C) (%) (%) (%) 450 76 72.5 55 465 82 72 59 480 87 68 r 59.2