The method of obtaining aliphatic alpha, omega-aminonitriles in the gas phase

 

(57) Abstract:

The invention relates to organic chemistry. Describes how to obtain aliphatic alpha, omega-aminonitriles partial hydrogenation of aliphatic alpha, omega-dinitriles at a temperature of from 100 to 250oC, a pressure of from 0.01 to 3 MPa, and a molar ratio of hydrogen to dinitrile from 2 : 1 to 300 : 1 in the presence of Nickel catalyst on a carrier, in the gas phase, which is that the hydrogenation is carried out in a reactor with a fixed bed with molded catalyst during the loading of the catalyst is from 0.03 to 10 kg of dinitrile per 1 kg of catalyst at 1 o'clock This method allows to increase the load of the catalyst without sacrificing selectivity. 2 C.p. f-crystals, 1 table.

The present invention relates to the production technology of aminonitriles, in particular to a process for the preparation of aliphatic alpha, omega-aminonitriles partial catalytic hydrogenation of aliphatic alpha, omega-dinitriles.

In the journal J. Mol. Cat. 61 (1990), pages 197-205 describes the gas-phase hydrogenation of adiponitrile on a modified alkaline metal of iron and Nickel catalysts in the absence of ammonia. Further, in the journal J. Chern. Soc. Faradey Trans. 89 (1993), page 3981-3986 description is.%, which modified potassium. When the reaction temperature 170oC and normal pressure is reached the output to 85% at a conversion of 65%. The disadvantage of these methods is that the catalysts are powdered and are therefore not suited for krupnopanelnogo use in a fixed bed, in particular due to insignificant life. A further drawback is that a large excess of hydrogen and a small maximum load of catalyst equal to 0.02 kg of dinitrile per 1 liter of catalyst per hour.

The objective of the invention is to develop a method of producing aliphatic alpha, omega-aminonitriles partial hydrogenation of adipodinitrile, which allows to increase the load of the catalyst without sacrificing selectivity.

The problem is solved in a method of producing aliphatic alpha, omega-aminonitriles partial hydrogenation of aliphatic alpha, omega-dinitriles at a temperature of from 100 to 250oC, a pressure of from 0.01 to 3 MPa, and a molar ratio of hydrogen to dinitrile from 2 : 1 to 300 : 1 in the presence of Nickel catalyst on a carrier, in the gas phase, due to the fact that the hydrogenation is carried out in a reactor with a fixed bed with molded Catalogne compounds according to the invention use of aliphatic alpha,omega-dinitrile General formula I

NC-(CH2)n-CN (I)

in which n denotes an integer from 1 to 10, in particular 2, 3, 4, 5 and 6.

Especially preferred compounds of formula I are dinitrile succinic acid, dinitrile glutaric acid, dinitrile adipic acid (adiponitrile), dinitrile pipelinewall acid and dinitrile cork acid (superolateral), the most preferable is adiponitrile.

According to the proposed method above dinitrile formula I is subjected to partial hydrogenation in the presence of the specified catalyst in the alpha,omega-aminonitriles General formula II

NC-(CH2)n-CH2-NH2(II)

and n has the above meaning.

Especially preferred aminonitriles formula II are those in which n has a value of 2,3,4,5 or 6, in particular 4, i.e., the nitrile 4-aminobutanoic acid, nitrile 5-aminopentanoic acid, nitrile 6 aminohexanoic acid (6-aminocaproyl), nitrile 7 aminopentanoic acid and nitrile 8 aminooctanoic acid, the most preferred is 6-aminocaproate.

The reaction is preferably carried out at temperatures of from 150 to 220, in particular from 160 to 200oC. the Pressure is preferably in predilatation of dinitrile. Usually choose a molar ratio of hydrogen to dinitrile from 2 : 1 to 300 : 1, preferably from 10 : 1 to 200 : 1.

The reaction can be carried out in the presence of ammonia or amine. In particular, the use of ammonia can lead to an increase in service life of the catalyst. Typically, the amount of ammonia or amine is from 5 to 50, preferably from 10 to 30 wt.%, counting on the entered dinitrile.

As carriers can be, for example, alumina, silica, aluminosilicates, titanium dioxide, zirconium dioxide, magnesium oxide, preferred is aluminum oxide, silicon dioxide, aluminium silicates, the most preferred is aluminum oxide.

According to a preferred form of execution of the invention using the catalyst, the modified metal selected from the group consisting of lithium, sodium, potassium, cesium.

The proposed method is carried out at a preferred loading of the catalyst is 0.05 to 3 kg of dinitrile per kg of catalyst per hour.

The metal content in the catalyst on the carrier are usually selected so that it ranged from 0.1 to 80, preferably from 0.2 to 70, particularly preferably from 0.5 to 50 wt.%, counting on the media.

The process is preferably carried out continuously in a fixed bed is rigidly located a catalyst, for example, by dipping or irrigation. By changing the residence time in the reaction zone can be targeted to regulate the degree of conversion and the selectivity.

The catalyst is prepared by known methods. Usually getting is as follows: precipitated water-soluble salts such as nitrates, sulfates, chlorides, formate or acetate of the metal on the carrier. If desired, the resulting catalyst precursor is processed into rods, tablets or pellets which are dried and then calcined. The catalyst on the carrier can also be obtained by impregnation of the carrier water-salt of the corresponding metal (metals), optionally in the presence of the above-mentioned modifier, in particular compounds of cesium, or the corresponding metal salt solutions nabryzgivajut to the media.

The deposition is done usually by the addition of precipitants, the changing importance of the pH or temperature change.

The resulting mass of the catalyst is dried usually at a temperature of from 80 to 150, preferably from 80 to 120oC.

The calcination is conducted Oba is According to the proposed method used the catalyst on the carrier retains high activity over a long period of time. Get the alpha, omega-aminonitriles with high yield and high selectivity. Alpha, omega-aminonitriles are valuable starting compounds for obtaining cyclic lactams, in particular 6-aminocaproate is the starting compound for caprolactam.

The following examples illustrate the obtaining of the catalyst on the carrier

Example 1

Mix 225g rods of aluminum oxide (diameter 4 mm, a BET surface 1 m2/g) with 67 ml of an aqueous solution of nitrate of Nickel (Nickel content: 16,72 g, calculated as metallic sodium), and incubated for 2 hours at room temperature with frequent, good stirring. Then dry the resulting catalyst precursor 16 hours at 120oC and calcined 4 hours at 350oC. Then the whole process repeated.

After cooling, put the rods in apparatus for the recovery and 2 hours and rinsed with nitrogen to 20 l per hour. Then heated for 2oC / min and 20 l of hydrogen per hour up to 300oC and kept at this temperature for 20 hours. After cooling in a stream of nitrogen, the catalyst Passepartout a mixture of air with nitrogen, and the temperature rise is a maximum of 20oC. the obtained rods catalyst contain 1st difference before impregnation with Nickel nitrate are impregnated with lithium nitrate (32 ml of 3.4 wt.%-aqueous solution). The resulting bars catalyst containing 13 wt.% Nickel (calculated as metal, is attributed to aluminum oxide) and 0.1 wt.% lithium (calculated as metal, is attributed to aluminum oxide).

Example 3. Repeat example 1 with the difference that before impregnation with Nickel nitrate are impregnated with sodium nitrate (32 ml of 1.4 wt.%-aqueous solution). The resulting bars catalyst containing 13 wt.% Nickel (calculated as metal, is attributed to aluminum oxide) and 0.1 wt.% sodium (calculated as metal, is attributed to aluminum oxide).

Example 4. Repeat example 1 with the difference that before impregnation with Nickel nitrate are impregnated with potassium nitrate (32 ml of 1.0 wt.%-aqueous solution). The resulting bars catalyst containing 13 wt.% Nickel (calculated as metal, is attributed to aluminum oxide) and 0.1 wt.% potassium (calculated as metal, is attributed to aluminum oxide).

Example 5. Repeat example 1 with the difference that before impregnation with Nickel nitrate are impregnated with cesium nitrate (32 ml of 0.5 wt.%-aqueous solution). The resulting bars catalyst containing 13 wt.% Nickel (calculated as metal, is attributed to aluminum oxide) and 0.1 wt.% zeine, which has a BET surface 5.5 m2/g (SCS 9 company Pesina). The resulting bars catalyst containing 13 wt.% Nickel (calculated as metal, is attributed to aluminum oxide) and 0.1 wt.% cesium (calculated as metal, is attributed to aluminum oxide).

Example 7. Repeat example 5 with alumina which has a surface on BET 7.7 m2/g (SPH 512 firm Rhone Poulenc). The resulting bars catalyst containing 13 wt.% Nickel (calculated as metal, is attributed to aluminum oxide) and 0.1 wt.% cesium (calculated as metal, is attributed to aluminum oxide).

The following example illustrates the proposed method.

Example 8. Miss from 3 to 20 g dinitrile adipic acid per hour in the evaporator (300oC) and from him passed through 100 ml of the catalyst by the method of irrigation with 100-200 l/h of hydrogen. The gaseous reaction product is condensed in the scrubber and subjected to gas chromatographic analysis. Additional parameters of the reaction and the results are summarized in the table below.

1. The method of obtaining aliphatic alpha, omega-aminonitriles partial hydrogenation of aliphatic alpha, omega-dinitriles at a temperature of from 100 to 250oC, a pressure of from 0.01 to 3 MPa and the molar zootoxin is audica fact, the hydrogenation is carried out in a reactor with a fixed bed with molded catalyst during the loading of the catalyst is from 0.03 to 10 kg of dinitrile per 1 kg of catalyst per hour.

2. The method according to p. 1, wherein the used catalyst is modified with a metal selected from the group consisting of sodium, lithium, potassium, cesium.

3. The method according to p. 1 or 2, characterized in that aliphatic alpha, omega-dinitrile use adipodinitrile obtaining 6-aminocaproate.

 

Same patents:

The invention relates to the field of organic chemistry, namely to a process for the preparation of aliphatic alpha, omega-aminonitriles partial hydrogenation of aliphatic alpha, omega-dinitriles at elevated temperature and elevated pressure in the presence of solvent and catalyst, consisting in the fact that the use of catalyst containing: (a) compound based on a metal selected from the group consisting of Nickel, cobalt, iron; (b) from 0.01 to 25, preferably from 0.1 to 5 wt.%, counting on (a), of a promoter selected from the group consisting of copper, silver, molybdenum, manganese, aluminum, phosphorus, silicon, and (C) up to 5, preferably from 0.1 to 3 wt.%, counting on (a), compounds based on alkali or alkaline earth metal, provided that the component (a) is not a compound based on iron and cobalt, if (b) is a promoter based on a metal selected from the group of manganese and molybdenum

The invention relates to the field of organic chemistry

The invention relates to a method of catalytic hydrogenation of NITRILES to amines
The invention relates to the field of catalytic hydrogenation of NITRILES to amines, and in particular dinitriles, such as adiponitrile to diamines, such as hexamethylenediamine were

The invention relates to a method of selective hydrogenation dinitrile compounds of General formula NC-(CH2)nCN, where n= 1-6, in the presence of a catalyst containing a metal of the 8th group of the Periodic system of the elements Nickel and a zeolite having a pore size diameter from 0.3 to 0.7 nm, preferably 0.3 to 0.5 nm

The invention relates to the field of organic chemistry, namely to a process for the preparation of aliphatic alpha, omega-aminonitriles partial hydrogenation of aliphatic alpha, omega-dinitriles at elevated temperature and elevated pressure in the presence of solvent and catalyst, consisting in the fact that the use of catalyst containing: (a) compound based on a metal selected from the group consisting of Nickel, cobalt, iron; (b) from 0.01 to 25, preferably from 0.1 to 5 wt.%, counting on (a), of a promoter selected from the group consisting of copper, silver, molybdenum, manganese, aluminum, phosphorus, silicon, and (C) up to 5, preferably from 0.1 to 3 wt.%, counting on (a), compounds based on alkali or alkaline earth metal, provided that the component (a) is not a compound based on iron and cobalt, if (b) is a promoter based on a metal selected from the group of manganese and molybdenum

The invention relates to the field of organic chemistry

The invention relates to a method for converting a first isomer to the second isomer, in which the first and second isomers are epimerase the same connection

The invention relates to a method of selective hydrogenation dinitrile compounds of General formula NC-(CH2)nCN, where n= 1-6, in the presence of a catalyst containing a metal of the 8th group of the Periodic system of the elements Nickel and a zeolite having a pore size diameter from 0.3 to 0.7 nm, preferably 0.3 to 0.5 nm

The invention relates to a new method of deriving biphenyl, namely 4-methyl-2'-cyanobiphenyl of formula (I)

< / BR>
4-Methyl-2'-cyanobiphenyl can find wide application as an intermediate product in the synthesis of derivatives of biphenylmethane described in applications EP-A-O 253310 and A

The invention relates to organic synthesis and can be used as a raw material for pharmaceuticals and other organic syntheses

The invention relates to a method for bridge mono and difterential General formula:< / BR>
where Y oxide /0/ or sulfide /S/ a bridge n 1 or 2

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing fluorinated dicyanobenzene represented by the formula (2): wherein m means a whole number from 1 to 4; n means 0 or a whole number from 1 to 3, and m + n = 4. This substance is useful as an intermediate and the parent compound for synthesis of medicinal and pharmaceutical products, agricultural reagents and polymers. Method involves interaction of tetrachlorodicyanobenzene represented by the formula (1): with a fluorinated agent at temperature from 80oC to 200oC in the presence of a non-protonic polar solvent taken in the amount from 0.1 to 3 parts by mass per 1 part by mass of indicated tetrachlorodicyanobenzene. Method involves carrying out the reaction with destruction of volume solid materials containing in the reaction mixture and/or by removing volume solid materials adhered inside of reaction vessel. Method provides preparing fluorinated dicyanobenzene with high yield at low temperature for short time.

EFFECT: improved preparing method.

13 cl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: process comprises hydrogen reduction of halogenated aromatic nitrile represented by general formula 1:

in which X denotes chlorine or fluorine atom, m integer from 1 to 5, n integer from 1 to 5, and m+n ≤ 5, provided than when n≥ 2, all X can be the same or different, using hydrogenation catalyst selected from group consisting of optionally modified porous nickel and optionally modified porous cobalt and in presence of organic acid in solvent to form halogenated aromatic methylamine represented by general formula 2: , in which X, m, and n are as defined above and "a" is integer from 1 to m).

EFFECT: enabled efficient large-scale production of desired product with high output.

20 cl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for semi-hydrogenation of dinitriles of the general formula: NC-R-CN (I) wherein R means linear or branched alkylene or alkenylene group comprising from 1 to 12 carbon atoms to the corresponding aminonitriles. Method involves using hydrogen in the presence of catalyst based on nickel, cobalt, Raney nickel or Raney cobalt comprising, possibly, an activating element that is taken among the 6 group of the Periodic system of element by the IUPAC nomenclature in the presence of strong mineral base representing a derivative of alkaline or earth-alkaline metal or ammonium hydroxide. In carrying out the hydrogenation process the parent mixture comprises water in the weight concentration at least 0.5 weight% of the total content of liquid components of the above said mixture, diamine and/or aminonitrile that can be form from the hydrogenating dinitrile and non-converted dinitrile wherein the weight concentration of all three indicated components is from 80% to 99.5%. The semi-hydrogenation reaction is carried out in the presence of at least one the selectivity-enhancing agent that is taken among the group comprising the following components: - compound comprising at least one cyano-group not bound with carbon atom that is taken among the group comprising hydrogen cyanide, lithium, sodium, potassium, copper cyanide, chelate cyanides of K3[Fe(CN)6], K4[Fe(CN)4], K3[Co(CN)6], K2[Pt(CN)6], K4[Ru(CN)6], ammonium or alkaline metal cyanides, tetrabutyl ammonium cyanide, tetramethyl ammonium thiocyanide, tetrapropyl ammonium thiocyanide; - organic isonitrile that is taken among the group including tert.-octylisonitrile, tert.-butylisonitrile, n-butylisonitrile, isopropylisonitrile, benzylisonitrile, ethylisonitrile, methylisonitrile and amylisonitrile; - tetraalkyl ammonium or tetraalkylphosphonium hydroxide or fluoride is taken among the group comprising tetramethyl ammonium, tetraethyl ammonium, tetrapropyl ammonium, tetrabutyl ammonium, tetrabutylphosphonium; - the chelate coordination compound formed by at least one metal atom and at least carbonyl radicals that is taken among the group comprising organic compounds including carbonyl, phosphine, arsine or mercapto-groups bound with metal and taken among the group comprising iron, ruthenium, cobalt, osmium, rhenium, iridium and rhodium. Method provides enhancing the selectivity by the aminonitrile group.

EFFECT: improved preparing method.

13 cl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for semi-hydrogenation of dinitrile of the general formula: NC-R-CN wherein R means linear or branched alkylene group comprising from 1 to 12 carbon atoms to the corresponding aminonitrile in the liquid medium. Method is carried out in the presence of a catalyst, such as nickel or Raney nickel comprising an activating element taken among rhodium or iridium wherein the weight ratio (Rh or Ir)/Ni is from 0.05% to 10%. Method provides enhancing yield of aminonitrile.

EFFECT: improved and enhanced method.

21 cl, 3 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to continuous process for hydrogenation of compounds containing nitrile and nitro groups to produce amino or aminonitrile compounds in presence of heterogeneous hydrogenation catalyst and a basic compound. Into reactor, at stirring, are fed: first stream of reactant to be hydrogenised, second stream of catalyst, third stream of alkali compound, fourth stream of hydrogen to maintain hydrogen pressure in reactor. From reactor is withdrawn at least fifth stream composed of reaction mixture and containing hydrogen bubbles dispersed therein. Fifth stream circulates in at least one circulation circuit coming out of lower section into top section of reactor. Fifth stream remove excess heat released in hydrogenation reaction and so temperature of reaction mixture is maintained below 150°C. Fifth stream circulating in one of circuits is passed through filter medium to produce sixth stream containing a part of hydrogenate separated from catalyst. From reactor and one of circulation circuit, seventh stream is picked and sent to liquid and solid phase separation stage to produce liquid phase comprised of hydrogenate without catalyst and catalyst-containing solid phase. The latter is subjected to reduction before being recycled into the second catalyst stream fed into reactor.

EFFECT: increased selectivity and productivity of hydrogenation process and enabled reduction and reuse of catalyst.

18 cl, 2 dwg

Up!