Method of preparing catalyst for synthesis of n-methylaniline

FIELD: organic synthesis catalysts.

SUBSTANCE: invention provides improved method for preparing catalyst for synthesis of N-methylaniline from aniline and methanol. Method comprises impregnation of alumina carrier with copper nitrate solution, to which were added nitrates of modifying metals selected from group consisting of manganese, chromium, iron, cobalt, and zinc, after which impregnated carrier is dried at temperature ensuring effective conversion of deposited nitrates into oxides of corresponding metals. When calcined, catalyst is subjected to additional impregnation with copper ammine solution, wherein Cu content (on conversion to oxide) lies within 0.6 to 7.0% based on the weight of catalyst, then dried at 100-120°C, and re-calcined at 230-250°C. After first calcination Cu content is 10.1-13% and after the second it rises by 0.6-5.0%. Lifetime of catalyst increases by a factor of 1.3 to 2.

EFFECT: increased lifetime of catalyst.

1 tbl, 12 ex

 

The invention relates to a method for producing catalysts for the synthesis of N-alkyl aromatic amines, mainly N-methylaniline (MMA).

N-methylaniline is one of the most effective ashless antiknock additive to gasoline. The main industrial method for obtaining a vapor-phase catalytic alkylation of aniline with methanol. As catalysts are the most common copper oxide with additives of oxides of various metals modifiers (i.e. additives that improve the properties of the catalyst activity, selectivity, durability); such catalysts can be obtained by co-deposition or by impregnation of the carrier with metal salts followed by calcination, the practical value of the obtained catalysts obtained by the last method (applied catalysts). For example, a known applied catalyst "Virgin" on the basis of the oxides of copper and manganese (TU 6-09-55-35-88), the catalyst containing the oxides of copper, manganese, chromium and zinc (RF patent 1327342, publ. 15.12.94), a catalyst based on oxides of copper, manganese, chromium, iron and cobalt (RF patent 2205067, publ. 27.05.03). The method of producing catalysts described in the patent includes the following stages:

- dissolution in water when heated to 80-90°With the calculated amount of copper nitrate and nitrate modifier metals;

- PR is Pitka media (mainly γ -aluminum oxide) solution of nitrates,

- calcination at a temperature of 360-400°to convert nitrates to oxides.

Thus prepared catalyst is loaded into the contact device and restore methanol at a certain temperature, followed by the synthesis of N-methylaniline, feeding into the reactor a gaseous mixture of aniline and methanol in a molar ratio of 1:2 at a temperature of 220-250°C. the Problem of increasing activity and selectivity of catalysts, increasing the duration of their work, the researchers decided mainly by the selection of reactive metals, their optimal ratio.

So, activity and duration of work of the industrial catalyst KA-99, received the patent of the Russian Federation 2205067 (chosen as a prototype) and contains a 10.1-16.4% of copper oxide and the oxides of active metals, largely exceed the similar characteristics of other known catalysts. The duration of operation of the catalyst CA-99 is more than 900 hours, including 4 of the regeneration cycle, when the contact load on the mixture aniline-methanol 800-1000 l/h by reducing the activity of the catalyst to about 80%conversion of aniline with all regeneration cycles the catalyst overload. The process of replacing the spent catalyst in the fresh time consuming.

It is known that the same what caused the catalysts for various processes can be obtained using ammonium complexes (Aminatou) metals. Known, in particular, the catalyst for hydrogenation and the reaction of the Fischer-Tropsch derived by impregnation of the carrier - titanium dioxide - water solution of ammonium complex of cobalt (PCT 28687, publ. 08.04.04); catalysts and absorbents on the basis of aluminum oxide impregnated with a solution of ammonium complex copper and subjected to calcination, and depending on the temperature after calcination on the surface of the carrier are present mainly elemental copper, oxide or carbonate (U.S. patent 6703342, publ. 09.03.04). There is a method of liquid-phase synthesis of N-substituted cyclic amines using a catalyst containing 20-30% of copper, calculated on oxide and the resulting impregnated inert carrier ammonium complex copper, followed by drying and calcining (U.S. patent 5847131, publ. 08.12.98). In the identified applicant sources there are no data on the effect of the used precursors (nitrates or Aminatou metals) and calcination conditions on the stability of the catalysts.

The aim of the present invention is to increase the duration and stability of the catalyst.

This goal is achieved by the proposed method, which involves the following stages:

- preparation of an aqueous solution of copper nitrate with the addition of nitrate modifier metals, which use metals from the group including manganese, chromium, iron, cobalt, zinc;

- impregnation of the carrier - aluminum oxide - solution of nitrates;

- calcination at a temperature of 360-400°at which the decomposition of the nitrates to oxides of the respective metals (first heating);

- additional impregnation of the calcined catalyst solution emmakate copper with the calculated concentration;

- drying at 100-120°and calcining dopropexchange catalyst at a temperature of 230 to 250°at which the decomposition of the complex ammonium salts (second heating).

The amount and concentration of solutions of nitrate of copper and emmakate copper expect so that its content in the catalyst, counting on the oxide, after the first calcination was 10.5-13% by weight of catalyst, and after the second calcination increased by 0.6 to 5.0%. The solution emmakate copper is prepared, in turn, from copper nitrate and an aqueous solution of ammonia.

Comparative tests on the synthesis of MMA using catalysts, treated and untreated ammirata copper, showed that this treatment has a significant impact on the duration of its operation.

The stability of the catalyst is increased by 1.5-2.0 times that riodic to a significant reduction of the overload contact apparatus and to improve the economic and social components of the process N-alkylation of aniline with methanol. It should be noted that a corresponding increase in the copper content (in terms of oxide) in the catalyst, obtained in a known manner, does not lead to similar effect.

The following are specific embodiments of methods of making the catalyst and process data N-alkylation of aniline with methanol using a catalyst obtained well-known and offered by way of illustrating the technical result achieved.

Example 1 (prototype).

130 cm3distilled water, heated to 80-90°C, dissolved under stirring consistently 89,0 g of copper nitrate trihydrate, 24.4 g of manganese nitrate setevogo, 18.0 g of chromium nitrate deviations, with 16.8 g of iron nitrate deviations and 5.8 g of cobalt nitrate setevogo. In the prepared solution of the nitrate load of 200 g γ-aluminum oxide with a grain size of 5-7 mm, heated to about 380°C. the resulting mass is dried under stirring and calcined for three hours at a temperature of 350-400°to complete decomposition of the nitrates and remove oxides of nitrogen.

The catalyst has the following composition, % wt.:

the copper oxideto 12.0
manganese oxide3,0
the chromium oxide1,4
iron oxide1,
the cobalt oxide0,8
aluminium oxide81,4

(composition of the obtained catalyst, the content of copper oxide in which approximately corresponds to the average value of the interval specified in the formula of the patent-prototype, hereinafter referred to as composition 1).

Changing the number of downloaded nitrates of metals, in the same conditions obtain a catalyst containing, % wt. (part 1A):

the copper oxidethe 10.1
manganese oxide3,0
the chromium oxide1,4
iron oxide1,4
the cobalt oxide0,8
aluminium oxide83,3

and the catalyst containing, % wt. (part 1B):

the copper oxidethe 15.6
manganese oxide3,0
the chromium oxide1,4
iron oxide1,4
the cobalt oxide0,8
aluminium oxide77,8

i.e. catalysts, in which the content of copper oxide is taken respectively on the lower and upper limit specified in the formula of the patent-prototype.

100 g To the of telesfora loaded into the reactor flow type and restore at 250° With pairs of methanol for two hours.

On the reduced catalyst at 220°served With a mixture of aniline and methanol at a molar ratio of 1:2 and the contact load of 900 g 1 DM3catch synthesis Products after their condensation in the refrigerator collected in the receiver. After the distillation of water and methanol, the organic layer is subjected to analysis

For part 1: the content of N-methylaniline makes 97.9%, aniline - 2,1%, N,N-dimethylaniline - traces. The output of the N-methyl-aniline production 98,8%. The stability of the catalyst 230 hours.

For part 1A: the content of N-methylaniline is 97.5%, aniline - 2,4%, N,N-dimethylaniline - 0,1%. The output of the N-methyl-aniline production of 98.5%. The stability of the catalyst 220 hours; and for part 1B: the content of N-methylaniline makes 97.9%, aniline - 2,1%, N,N-dimethylaniline - traces. The output of the N-methyl-aniline production 98,8%. The stability of the catalyst 230 hours.

Example 2.

The original catalyst for impregnation ammirata copper prepared by the method described in example 1 (composition 1). After calcination of the catalyst at 350-400°With the temperature reduced to 230 to 250°and impregnating it with an aqueous solution of emmakate copper, total copper content in which in terms of oxide is 0.6% wt. in relation to the weight of the original catalyst. After impregnation the catalyst is dried at a temperature of 100-120°C and annealed at 230 to 250°

The catalyst has the following composition, % the speakers.:

the copper oxide12,6
manganese oxide2,9
the chromium oxide1,4
iron oxide1,3
the cobalt oxide0,8
aluminium oxide81,0

After calcination 100 cm3the catalyst loaded into the reactor flow type and restore in pairs of methanol for two hours.

After recovery of the catalyst in the reactor at a temperature of 220°served With a mixture of aniline and methanol in a molar ratio of 1:2 and the contact load of 900 g 1 DM3catch Produce after reactor condense and collect in the receiver and after the distillation of water and methanol is subjected to analysis.

The content of N-methylaniline is 97.3%, aniline - 2,1%, N,N-dimethylaniline to 0.6. The output of the N-methyl-aniline production of 98.3%. The stability of the catalyst to 300 hours, which exceeds the stability of the original catalyst 1.3 times.

Example 3.

The original catalyst prepared according to example 1 (composition 1), impregnation ammirata copper is carried out, as described in example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 0.9% wt. to the mass of the original catalyst.

The catalyst, after drying and calcining has a composition, % wt.:

the copper oxide12,8
manganese oxide2,8
the chromium oxide1,4
iron oxide1,3
the cobalt oxide0,7
aluminium oxide81,0

After calcination 100 cm3catalyst placed in the reactor flow type and restore in pairs of methanol for two hours at 250°C.

After recovery of the catalyst in the reactor at 220°served With a mixture of aniline and methanol in a molar ratio of 1:2 and the contact load of 900 g 1 DM3catch Produce after reactor condense and collect in the receiver and after the distillation of water and methanol is subjected to analysis.

The content of N-methylaniline is 98.3%, aniline - 1,3%, N,N-dimethylaniline is 0.4. The output of the N-methyl-aniline production 98.4% of the Stability of the catalyst 390 hours, which surpasses the stability of the original catalyst 1.7 times.

Example 4.

The original catalyst prepared according to example 1 (composition 1), impregnation of the catalyst with ammirata copper spend the same manner as described in example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 1.5% wt. in relation to the weight of the original catalyst.

The catalyst, after drying and calcining has a composition, % wt.:

the copper oxide13,7
manganese oxide2,7
the chromium oxide1,3
iron oxide1,3
the cobalt oxide0,7
aluminium oxide80,3

Testing of the catalyst were carried out as described in the previous examples.

The content of N-methylaniline in catalyzate is 98,1%, aniline - 1,1%, N,N-dimethylaniline was 0.8%. The output of the N-methyl-aniline production of 98.3%. The stability of the catalyst 470 hours, which is two times higher than the stability of the original catalyst.

Example 5.

The original catalyst prepared according to example 1 (composition 1), impregnation of the catalyst with ammirata copper spend the same manner as described in example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 2.5% wt. in relation to the weight of the original catalyst.

After drying and calcining the catalyst has a composition, % wt.:

the copper oxide14,6
manganese oxide2,6
the chromium oxide1,2
iron oxide1,2
the cobalt oxide0,7
aluminium oxide79,7

Testing of the catalyst PR the lead according to example 1.

The content of N-methylaniline in catalyzate was 98.0%, aniline and 1.5%, N,N-dimethylaniline and 0.5%. The output of the N-methyl-aniline production 98,0%. The stability of the catalyst 380 hours, which exceeds the stability of the original catalyst 1.7 times.

Example 6.

The original catalyst prepared according to example 1 (composition 1), impregnation of the catalyst with ammirata copper spend the same manner as described in example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 3.0% wt. in relation to the weight of the original catalyst.

After drying and calcining the catalyst has a composition, % wt.:

the copper oxide15,0
manganese oxide2,5
the chromium oxide1,2
iron oxide1,2
the cobalt oxide0,7
aluminium oxide79,4

Testing of the catalyst is carried out according to example 1.

The content of N-methylaniline in catalyzate is to 97.1%, aniline - 2,0%, N,N-dimethylaniline was 0.9%. The output of the N-methyl-aniline production 98,1%. The stability of the catalyst 330 hours, which exceeds the stability of the original catalyst in 1,4 times.

Example 7.

The original catalyst prepared according to example 1 (composition 1), impregnation of the catalyst with ammirata copper spend way is, described in example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 5.0% wt. in relation to the weight of the original catalyst.

After drying and calcining the catalyst has a composition, % wt.:

the copper oxide17,1
manganese oxide2,4
the chromium oxide1,1
iron oxide1,1
the cobalt oxide0,6
aluminium oxide77,4

Testing of the catalyst is carried out according to example 1.

The content of N-methylaniline in catalyzate is 95,8%, aniline - 2,8%, N,N-dimethylaniline is 1.4%. The output of the N-methyl-aniline production to 97.1%. The stability of the catalyst 280 hours, which exceeds the stability of the original catalyst 1.2 times.

Example 8.

The original catalyst prepared according to example 1 (composition 1), impregnation of the catalyst with ammirata copper spend the same manner as described in example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 7.0% wt. in relation to the weight of the original catalyst.

After drying and calcining the catalyst has a composition, % wt.:

the copper oxide18,8
oxide Marga is CA 2,3
the chromium oxide1,0
iron oxide1,0
the cobalt oxide0,5
aluminium oxide76,4

Testing of the catalyst is carried out according to example 1.

The content of N-methylaniline in catalyzate is to 92.1%, aniline - 4,6%, N,N-dimethylaniline was 3.3%. The output of the N-methyl-aniline production is 95.2%. The stability of the catalyst is 240 hours, slightly differing from the stability of the original catalyst (230 hours).

Example 9.

The catalyst prepared according to the patent of the Russian Federation 1327342, impregnated with a solution of emmakate copper according to example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 1.5% wt. in relation to the weight of the original catalyst.

After drying and calcining the catalyst has a composition, % wt.:

the copper oxide14,0
manganese oxide2,9
the chromium oxide1,1
zinc oxide0,6
aluminium oxide81,4

The content of N-methylaniline in catalyzate is 97,2%, aniline - 2,0%, N,N-dimethylaniline was 0.8%. The output of the N-methyl-aniline production of 97.8%. The stability of the catalyst 250 hours, which exceeds stabil the activity of the original catalyst 2.5 times.

Example 10.

The catalyst prepared according to the patent of the Russian Federation 1327342, impregnated with a solution of emmakate copper according to example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 2.5% wt. in relation to the weight of the original catalyst.

After drying and calcining the catalyst has a composition, % wt.:

the copper oxide15,0
manganese oxide2,7
the chromium oxide1,0
zinc oxide0,6
aluminium oxide80,7

The content of N-methylaniline in catalyzate is 97,0%, aniline - 1.8%, and N,N-dimethylaniline is 1.2%. The output of the N-methyl-aniline production of 97.5%. The stability of the catalyst 200 hours, which exceeds the stability of the original catalyst 2 times.

Example 11.

The original catalyst prepared according to example 1 (part 1A), impregnation of the catalyst with ammirata copper spend the same manner as described in example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 2.0% wt. in relation to the weight of the original catalyst.

After drying and calcining the catalyst has a composition, % wt.:

2,9
the copper oxide12,1
manganese oxide
the chromium oxide1,4
iron oxide1,4
the cobalt oxide0,8
aluminium oxide81,4

Testing of the catalyst is carried out according to example 1.

The content of N-methylaniline in catalyzate or 97.7%, aniline - 2,3%, N,N-dimethylaniline - traces. The output of the N-methyl-aniline production 98,9%. The stability of the catalyst is 280 hours.

Example 12.

The original catalyst prepared according to example 1 (part 1B), impregnation of the catalyst with ammirata copper spend the same manner as described in example 2, using the solution emmakate copper, the copper content in which in terms of oxide is 2.0% wt. in relation to the weight of the original catalyst.

After drying and calcining the catalyst has a composition, % wt.:

the copper oxidethe 17.3
manganese oxide2,9
the chromium oxide1,4
iron oxide1,4
the cobalt oxide0,8
aluminium oxide76,2

Testing of the catalyst is carried out according to example 1.

The content of N-methylaniline in catalyzate makes 97.9%, aniline - 1.8%, and N,N-dimethylaniline to 0.3%. The output of the N-methyl-aniline production 98,8%. The camera is lnost catalyst 310 hours.

Characteristics of the known catalysts and catalysts prepared according to examples 2-12 shown in the table. For catalysts in examples 2-12 shows the total copper content in terms of oxide and separately state the amount of copper in terms of oxide, which is caused by the impregnation ammirata copper. The content of copper deposited by impregnation ammirata, in these examples varies in concentration ranging from 0.6 to 7% wt. From the data on the results of the N-alkylation of aniline with methanol using these catalysts, it follows that the additional impregnation ammirata allows to increase service life of the catalyst is 1.3-2 times; taking into account all the process indicators optimum amount of copper deposited by impregnation ammirata, 0.9-5% wt.

A method of producing a catalyst for the synthesis of N-methylaniline-based copper oxide, comprising preparing a solution of nitrate of copper with the addition of nitrates, the modifying group metals, including manganese, chromium, iron, cobalt, zinc, carrier impregnated alumina with a solution of nitrate, drying and calcining the impregnated carrier at a temperature of providing effective transformation applied nitrates to oxides of the respective metals, characterized in that after calcination the catalysis of the torus is subjected to additional impregnation with a solution of emmakate copper, the copper content in which in terms of oxide is 0.6-7.0 wt.% in relation to the weight of the catalyst, dried at 100-120°C and annealed at 230 to 250°and after the first calcination, the content of copper oxide is 10.1-13% by weight of catalyst, and after the second calcination it increases by 0.6 to 5.0%.



 

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11 cl, 1 tbl, 8 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention provides catalyst for hydrofining of petroleum fractions, which catalyst shows elevated strength and stability upon regeneration. This is achieved supplementing alumina-based carrier with texturing additives selected from alumina and gibbsite thermochemical activation product in amount 5 to 30 wt %. Alumina additive is used with particle size not larger than 15 μm and gibbsite thermochemical activation product with that not larger than 45 μm. As binding agent in catalyst, nitric acid is used at molar ratio to alumina (0.01-0.03):1 and/or aluminum nitrate/ aluminum metal reaction product in amounts 1 to 5% based on alumina. Prior to be impregnated, catalyst is steamed at elevated temperature and impregnation is carried out from aqueous solution of nickel-cobalt-molybdenum-containing complex at pH 1-3.

EFFECT: improved performance characteristics of catalyst.

2 cl, 3 tbl, 10 ex

FIELD: catalyst preparation methods.

SUBSTANCE: immobilized ionic liquid is prepared by anion-assisted immobilization of ionic liquid, for which purpose a carrier is treated with anion source, for instance with inorganic halide to produce ionic liquid or applying it onto carrier. Alternatively, ionic liquid may be immobilized because of cation covalently linked to carrier, e.g. through silyl groups, or incorporated into carrier via synthesis of carrier in presence of acceptable base. Immobilized ionic liquid are meant for use as catalysts, e.g. in Friedel-Krafts reaction.

EFFECT: optimized preparation procedures.

18 cl, 10 ex

FIELD: precious metal technology.

SUBSTANCE: invention relates to a method for preparation of novel platinum-containing materials, which find always increasing demand in national economy, in particular in heterogeneous catalysis. According to invention, platinum is sublimated on high-temperature glass cloth with preliminarily deposited calcium oxide layer. Thus prepared material is a composite constituted by high-temperature glass cloth with deposited calcium oxide layer bearing (Ca,Si)O2 rods on its surface, said rods having oxidized platinum on their ends and metal particles 3-20 nm in size in underlayer.

EFFECT: enabled preparation of novel platinum-containing material with platinum in finely dispersed state.

7 cl, 1 dwg, 1 tbl, 6 ex

FIELD: production of catalytic neutralizers.

SUBSTANCE: high-efficiency catalytic neutralizer has internal and external layers on inert carrier which contain noble metals of platinum group deposited on materials of base and oxygen-accumulating components. Inner layer of proposed catalytic neutralizer contains platinum deposited on first base and first oxygen-accumulating component and its external layer contains platinum and rhodium deposited on second base only; this second layer contains additionally second oxygen-accumulating component. Production of catalytic neutralizer includes application of coat on carrier made from composition containing powder-like materials including first material of base and first oxygen-accumulating component followed by drying, calcining, immersing the carrier with coat in solution of platinum precursor; coat is calcined and external layer is applied over previous layer. Specification describes two more versions of production of catalytic neutralizer.

EFFECT: enhanced ability of catalytic neutralizer for reduction of catalytic activity after aging due to discontinuation of delivery of fuel.

24 cl, 1 dwg, 11 tbl, 5 ex, 3 ex

FIELD: inorganic synthesis.

SUBSTANCE: iron-chromium-nickel spinels are prepared by homogenization of original oxides of nickel(II), iron(III), and chromium(III) in presence of 0.5-1.5% of potassium halides as mineralizing agent followed by briquetting and heat treatment of oxides at 800-1000°C.

EFFECT: enabled preparation of spinels at lowered temperatures and in shorter time.

2 tbl, 2 ex

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