Catalyst for oxidative ammonolysis ethylenediamine compounds based on metal oxides, method thereof and method of oxidative ammonolysis of ethylenediamine connections

 

(57) Abstract:

Describes a catalyst for the oxidative ammonolysis of Ethylenediamine compounds of General formula I

[ AaBbOx]p[CcDdFeeMefEiFjOy]q< / BR>
where A is bismuth, tellurium, antimony, tin and/or copper, B is molybdenum and/or tungsten and C is an alkali metal, thallium and/or samarium, a is 0.01 to 8, b is 0.1 - 30, c - 4, and x and y indicate the number determined by the valency and frequency of the non-oxygen elements in the formula (I), wherein D in the formula (I) means an alkaline earth metal, Nickel, copper, cobalt, manganese, zinc, tin, cerium, chromium, cadmium, molybdenum, bismuth, and/or mercury, Me - cobalt, E is phosphorus, arsenic, boron and/or antimony, F - metal rare earths, vanadium and/or uranium, d - not more than 20 e - not more than 20, f - not more than 20, i - 5 j - no more than 15, and p and q denote the number that provides the ratio of p : q = 0.001 - 0,099 obtained by the following methods: (a) education key phases of the composition of AaBbOx(b) the education side of the phase composition of CcDdFeeMefEiFjOyor water-soluble salts of the elements side phase or a mixture of at least one vodorastvorimie as water-soluble salts, (C) mixing the key phases with side phase, (g) if necessary, drying, obtained according to (b) mixture, followed by calcification and, if necessary, the molding formed in such a way catalyst mass known techniques, and the average particle size of at least one part of the catalyst that differ in chemical composition from the other components is from 10 nm to less than 1 μm. Describes how catalyst and method of oxidative ammonolysis of Ethylenediamine compounds. The technical result is an increase in the activity of the catalyst. 3 S. and 1 C.p. f-crystals, 1 table.

The invention relates to oxidation catalysts, in particular catalysts for oxidative ammonolysis Ethylenediamine compounds based on metal oxides, the method thereof and method of oxidative ammonolysis of ammonolysis Ethylenediamine connections.

Known catalyst for the oxidative ammonolysis of Ethylenediamine compounds based on metal oxides with the General formula

[MmNnOx]q[AaCbDcEdFeNfOy]p,

where M is bismuth, tellurium, antimony, tin and/or the beryllium, calcium, strontium, barium, zinc, cadmium and/or mercury, D - iron, chromium, cerium and/or vanadium, E is phosphorus, arsenic, boron, antimony, F - metal, rare earths, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, GA, indium, silicon, germanium, lead, thorium and/or uranium, a - 0 to 4, b is 0 to 20, c is from 0.01 to 20, d is 0-4, e - 0-8, f - 8-16, m is 0.01 - 10 , n - 0,1 - 30, x and y indicate the number determined by the valency and frequency of the non-oxygen elements, and q and p denote the number that provides the ratio q : p is equal to 0.1-10 (see application EP N 0000835, MKI B 01 J 23/88, 1976).

A compound of the formula [MmNnOx] is denoted as "a key phase, and a compound of the formula [AaCbDcEdFeNfOy] referred to as "second phase". For obtaining the known catalyst in the specified European application it is recommended to form a compound of the formula [MmNnOx] in the absence of other groups and then mix it with oxides or water-soluble salts of the elements side phase, followed by drying the resulting mixture and calcification.

A disadvantage of the known solutions is that the activity and selectivity of the catalyst are not polnocny has a higher activity and better selectivity when used for the oxidative ammonolysis of Ethylenediamine connections.

The problem is solved by the proposed catalyst based on metal oxides with the General formula (1).

[AaBbOx]p[CcDdFeeMefEiFjOy]q(1)

where A is bismuth, tellurium, antimony, tin and/or copper, B is molybdenum and/or tungsten and C is an alkali metal, thallium and/or samarium, a is 0.01 to 8, b is 0.1-30, c - 4, and x and y indicate the number determined by the valency and frequency of the non-oxygen elements in the formula (1), due to the fact that the D in the formula (1) means an alkaline earth metal, Nickel, copper, cobalt, manganese, zinc, tin, cerium, chromium, cadmium, molybdenum, bismuth and/or mercury, Me - cobalt, E is phosphorus, arsenic, boron and/or antimony, F - metal rare earths, vanadium and/or uranium, d - not more than 20 e - not more than 20, f - not more than 6, i - not more than 6, j - no more than 15, and p and q denote the number that provides the ratio of p:q = 0.001 - 0,099 obtained by the following methods:

(a) education is a key phase of the composition of AaBbOx,

(b) the education side of the phase composition of CcDdFeeMefEiFjOyor water-soluble salts of the elements side phase or a mixture of at least one water-soluble salts of these elements and at least od what asianam key phases with side phase. (g) if necessary, drying the obtained according to p. (b) mixture, followed by calcification and, if necessary, the molding formed in such a way catalyst mass by known methods, with an average value of at least one part of the catalyst is different in chemical composition from the other components is from 10 nm to less than 1 micron.

The proposed catalyst may be deposited on an oxide carrier.

The proposed catalyst can be used for carrying out the method of oxidative ammonolysis of ethyleneimine compounds, which is an additional object of the present invention.

A further object of the present invention is a method of preparation of the catalyst through the formation of key phases of the composition of AaBbOxwhere A denotes the bismuth, tellurium, antimony, tin and/or copper, B is molybdenum and/or tungsten, and - 0.01 to 8 and b is 0.1 to 30, and side phase composition CcDdFeeMefEiFjOywhere C is an alkali metal, thallium and/or samarium, C - 4, while x and y indicate the number determined by the valency and frequency of the excellent in oxygen elements key and side phases, is Chou phase of the composition, in which D denotes alkaline earth metal, Nickel, copper, cobalt, manganese, zinc, tin, cerium, chromium, cadmium, molybdenum, bismuth and/or mercury, Me - cobalt, E is phosphorus, arsenic, boron and/or antimony, and F is the metal of the rare earths, vanadium and/or uranium, d - not more than 20 e - not more than 20, f - not more than 20, i - not more than 6 and j - no more than 15, at the same stage of calcification assign the catalyst composition [AaBbOx]pCc[DdFeeMefEiFjOy]qwhere A,B,C,D, Me, E, F, a,b,x,c,d,e,f,i,j and y know how the above values, a p and q indicate the number that provides the ratio of p:q = 0.001-0,099.

According to a preferred form of the method of obtaining the proposed catalyst is at least one part of catalyst (key phase, a preliminary step key phase by phase or soda oxide phase one of the side phase compounds) are ground well-known techniques, for example, using a ball or jet mill, and wet grinding is preferred. Attainable chopping average particle size of preferably chosen in the range from 10 nm to less than 1 μm, preferably 10-800 nm, particularly preferably 10-600 nm.

ZAT is part of the catalyst, which, if necessary, also pre-ground, preferably in solution or suspension.

The resulting mixture is usually subjected to drying, preferably spray drying. The resulting pre-catalyst, as a rule, subjected to calcination at temperatures of 400-900oC, preferably 500-800oC, preferably in the air stream. The time of calcination, usually chosen in the range of 0.1 - 20 hours.

Preferably the catalytically active mass is applied to the media, such as, for example, silica gel, aluminum oxide, titanium dioxide or zirconium dioxide. According to a preferred form of execution of the invention before spray drying of the oxide carrier, such as silica gel, aluminum oxide, titanium dioxide or zirconium dioxide, is added to the mixture of both components of the catalyst, and thus obtained catalyst can be used directly in organic synthesis reactor with a fluidized bed.

In addition, the calcined catalyst can be crushed and molded by known techniques, for example, due to the fact that it is being compressed by known techniques in hollow cylinders or bundles.

aBbOx] crush, to grind it preferably subjected to calcination at temperatures of 400 - 900oC, which is usually carried out in the air stream. As a rule, the time of calcination is chosen in the range of 0.1-20 hours.

On the basis of well-known suitable sources other components of the proposed desired catalyst composition is transferred to the possible homogeneous, preferably superfine, dry mix (for example, by mixing a water-soluble salts, such as halides, nitrates, acetates, carbonates or hydroxides in aqueous solution, followed by spray drying an aqueous solution or by suspension of water-insoluble salts, such as, for example, oxides, water environment and then spray drying the resulting slurry, which in the framework of this proposal, referred to as a preliminary step side phase. Important is only that the components of the pre-stage side of the phases are already oxides or compounds which can be converted to oxides by heating, if necessary in the presence of oxygen.

Then soda preliminary stage the key is th mixture is preferably compacted by pressing, and then (usually in the air stream) is subjected to calcinations, expediently at temperatures of 400 - 900oC, for several hours.

In the case of the preparation of the catalyst without carrier extrusion mass is carried out, as a rule, directly to the desired geometry of the catalyst, and as such catalysts prefer hollow cylinders with an outer diameter of 2 to 210 cm in length, 2 to 10 mm and wall thickness 1 to 3 mm, However, after the calcination, the proposed catalyst can also be crushed and applied on an inert carrier. The application can also be made up of calcification. Needless to say that the proposed catalyst can also be used in powder form.

The invention is illustrated by the following examples.

Example 1

(a) Receiving a key phase

0.5 kg of a solution of nitrate of bismuth (iii) in aqueous nitric acid (11 wt.% bismuth, 6.4 wt.% nitric acid, calculated on the solution) is mixed with 67 g of tungstic acid and stirred at a temperature of 50oC for one hour. The resulting suspension is subjected to spray drying at a temperature of 290oC and calcined at a temperature of 750oC for 2 hours. Thus obtained calcinelli to the average size of the particles of 400 nm (measured by laser electronography company Sympatec) equipped with a mixer mill. You get a suspension of 1 (preliminary stage key stage).

(b) Receiving side phase

to 5.57 kg solution heptamolybdate ammonium in 16 l of water mixed with solution 3,83 kg of nitrate of cobalt (II) and 2.66 kg nitrate iron (III) in 8 l of 10% by weight of nitric acid, 19,1 kg BW of an aqueous mixture containing 49 wt.% colloidal silica, and 15.4 g of an aqueous solution containing 48 wt.% potassium hydroxide. You get a suspension 2.

Then, the suspension 1 is mixed with a suspension of 2. The resulting mixture is evaporated to dryness spray drying with subsequent calcification, first at a temperature of 290oC for three hours, then at a temperature of 425oC for a further three hours and finally at a temperature of 610oC for a further three hours. Thus obtained catalyst on colloidal silica gel can be used directly in the fluidized bed reactor.

The catalyst has the following composition: [Bi2W2O9]0,05[Mo12Co5Fethe 2.5K0,05Ox]. The molar ratio of active mass and the carrier is 1:60.

Example 2

Oxidative ammonolysis

(a) In a reactor with a fixed catalyst bed assests/SUP>C. the Volume ratio of propene, ammonia, water vapor and air is 1: 1,3 : 10: 4,7. Contact time (volume (gas)/volume of catalyst per unit time is 4.5 seconds. As the catalyst used, the catalyst of example 1.

(b) Repeat example 2 (a) using a known catalyst of example 1 prototype.

The results of oxidative ammonolysis summarized in table.

1. Catalyst for oxidative ammonolysis Ethylenediamine compounds of General formula I

[AaBbOx]p[CcDdFeeMefEiFjOy]q,

where A is bismuth, tellurium, antimony, tin and/or copper;

B is molybdenum and/or tungsten;

C - alkali metal, thallium and/or samarium;

a - 0.01 to 8;

b - 0,1 - 30;

c - no more than 4,

and x and y indicate the number determined by the valency and frequency of the non-oxygen elements in the formula I,

wherein D in formula I is alkaline earth metal, Nickel, copper, cobalt, manganese, zinc, tin, cerium, chromium, cadmium, molybdenum, bismuth and/or mercury, Me - cobalt, E is phosphorus, arsenic, boron and/or antimony, F - metal rare earths, vanadium and/or uranium, d - not more than 20 e - not more than 20, f - not more than 20, i - not the mi techniques: (a) education key phases of the composition of AaBbOx(b) the education side of the phase composition of CcDdFeeMefEiFjOyor water-soluble salts of the elements side phase or a mixture of at least one water-soluble salts of these elements and at least one soda phase of one of these elements, which are not available as a water soluble salt, (C) mixing the key phases with side phase, (g) if necessary, drying, obtained according to (b) mixture, followed by calcification and, if necessary, the molding formed in such a way catalyst mass known techniques, and the average particle size of at least one part of the catalyst, differing in chemical composition from the other components is from 10 nm to less than 1 micron.

2. The catalyst p. 1, characterized in that it is deposited on the oxide carrier.

3. The method of producing catalyst according to PP.1 and 2 through the formation of key phases of the composition of AaBbOxwhere A denotes the bismuth, tellurium, antimony, tin and/or copper, B is molybdenum and/or tungsten, a - 0,01 - 8 and b - 0.1 to 30, and side phase composition CcDdFeeMefEiFjOywhere C OSN is updated and the frequency of the non-oxygen elements key and side phases, mixing both phases and subsequent calcination of the mixture of these phases, characterized in that use side phase of the composition, in which D denotes alkaline earth metal, Nickel, copper, cobalt, manganese, zinc, tin, cerium, chromium, cadmium, molybdenum, bismuth and/or mercury, Me - cobalt, E is phosphorus, arsenic, boron and/or antimony, and F is the metal of the rare earths, vanadium and/or uranium, d - not more than 20 e - not more than 20, f - not more than 20, i - not more than 6 and j - no more than 15, with the stage of calcification assign the catalyst composition [AaBbOx]p[CcDdFeeMefEiFjOy]qwhere A, B, C, D, Me, E, F, a, b, x, c, d, e, f, i, j and y are the specified values, and p and q denote the number that provides the ratio of p : q = 0.001 - 0,099.

4. Method of oxidative ammonolysis of Ethylenediamine compounds known techniques, characterized in that it is carried out in the presence of a catalyst at PP.1 and 2.

 

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