NL1013112C2 - Process for partial hydrogenation of a nitrile compound with two or more nitrile groups. - Google Patents

Description

- 1 -

METHOD FOR PARTIAL HYDROGENATION OF A 5 NITRIL COMPOUND WITH TWO OR MORE NITRIL GROUPS

The invention relates to a process for the preparation of a mixture of an amino nitrile and an amino compound with two or more amino groups by partial hydrogenation of a nitrile compound with two or more nitrile groups, with hydrogen in the presence of a Raney catalyst, lye and water and also relates to a mixture of an amino nitrile, an amino compound and a nitrile compound.

Such a method is known from WO-A-96 / 18,603.

This publication describes a process for partial hydrogenation of aliphatic dinitriles to the corresponding amino nitrile with hydrogen in the presence of a Raney nickel or a Raney cobalt catalyst, a strong mineral alkali or alkaline earth base and water.

Disadvantages of the method according to WO-A-96 / 18,603 are: - the reaction time is high; if a low content of the amino compound in the mixture is desired, the reaction must be stopped at a very low conversion of the nitrile compound; And - the reaction cannot be controlled in the ratios to be produced between the amino nitrile and the amino compound.

1013112 - 2 -

The object of the invention is to provide a method which does not have the above drawbacks.

The invention is characterized in that the caustic / catalyst weight ratio is greater than 0.05 and the water / catalyst weight ratio is less than 2.

This achieves a high reaction speed and a high conversion, while the yield of amino nitrile and amino compound can also be controlled.

The process of the invention is suitable for partial hydrogenation of a nitrile compound with two or more nitrile groups. The method of the present invention is preferably suitable for the partial hydrogenation of compounds with two to ten nitrile groups.

The hydrogenation of nitrile compounds is shown in the following reaction scheme: 20

(A) (B) (O

R - (C = N) x ------> (H - N - <%) * - R - (C s N) y + (H-N -CH2) X - R

1 I

25 H H

where 2 <x <10, 1 <y <9, 1 <z <9 and y + z = x; R can be a saturated or unsaturated, linear or branched hydrocarbon radical of 1-20 carbon atoms.

Examples of such hydrocarbon radicals are methylene, ethylene, propylene, 1-methylpropylene, butylene, pentylene, hexylene and decylene. R may also contain, in addition to or instead of carbon, one or more heteroatoms from group 14-17 of the Periodic Table of Elements. For example, R can be an N-containing group or a halogen. Compound (A) is a nitrile compound with a minimum of 2 and a maximum of 10 5 nitrile groups. By hydrogenation, compound (A) reacts to a mixture of compound (B), an amino nitrile and compound (C), an amino compound. If the nitrile compound contains more than two nitrile groups, i.e. x> 2, then compound B represents a mixture of all possible amino nitriles which can be formed by partial hydrogenation of that specific nitrile compound.

Preferably, α, alk-alkanedinitriles are suitable for being converted to a mixture of their corresponding amino nitriles and amino compounds by the method of the present invention. These alkaneditriles have a general formula NC- (CnH2n) -CN, where n is an integer from 1 to 12. Preferably n is an integer from 20 to 6. As examples may be mentioned: malonitrile (n = 1), succinonitrile (n = 2), adiponitrile (n = 4), 2-methylglutaronitrile (n = 4) and glutaronitrile (n = 3). The process according to the invention is particularly suitable for hydrogenating succinonitrile and adiponitrile.

The catalyst used according to the invention is a Raney catalyst. Examples are Raney nickel or Raney cobalt. Mixtures of Raney nickel and Raney cobalt can also be used. Raney catalysts and their preparation are described, for example, in US-A-1,628,190.

The Raney catalyst may contain small amounts of other metals in elemental or chemically bonded form 1013112-4 from Group 4, 6-10 of the Periodic Table of the Elements. Here, the Periodic Table of Elements is understood to mean the Periodic Table shown on the inside cover of the Handbook of Chemistry and Physics, 70th Edition, 1989/1999 (New IUPAC Notation). The amount of other metals can range from 0 wt% to 15 wt% relative to the weight of nickel or cobalt, and preferably from 0 to 10 wt%. This addition of other metals can increase the activity and selectivity for the hydrogenation of certain groups of compounds. These other metals are preferably chromium, titanium, molybdenum, iron, zinc and tungsten. Chromium, titanium and iron or mixtures of these are particularly suitable. These other metals are commonly referred to as promoters, the catalyst as promoted Raney catalyst. Promoters are described, for example, in S.R. Montgomery, Catalysis of Organic Reactions 5., pages 383-409.

The hydrogenation takes place with hydrogen gas (H2), in the presence of lye and water.

The caustic to be used can be selected from: LiOH, KOH, NaOH, RbOH, CsOH and NH4OH and their mixtures. In practice, NaOH and KOH are usually used because of their good price-quality ratio.

The hydrogenation according to the invention should be carried out with a caustic / catalyst weight ratio greater than 0.05 and a water / catalyst weight ratio of less than 30. Preferably the caustic / catalyst weight ratio is greater than 0.05 and less than 1.0 and in particular greater than 0.05 and less than 0.3. The 'O. C <; * O * \ J li ', -i * | The water / catalyst weight ratio is preferably greater than 0.1 and less than 2, and more preferably greater than 0.4 and less than 1.5.

The nitrile compound can be dissolved in a suitable solvent before hydrogenation. Examples of suitable solvents are: alcohols such as methanol and ethanol, liquid ammonia and diamines such as ethylene diamines. Preferably, the reaction mixture functions as a solvent during the reaction.

The temperature during the hydrogenation is 40-200 ° C and preferably 40-120 ° C. Within this preferred range, the higher the temperature during hydrogenation, the better the reaction proceeds.

The pressure during the hydrogenation is 0.5-20 MPa, preferably 4-8 MPa.

A mixture of an amino nitrile, an amino compound and a nitrile compound is also known from WO-A-96 / 18,603. The mixture obtained according to WO-A-20 96 / 18,603 contains at least 60 wt% aminonitrile.

A drawback of mixtures as obtained in WO-A-96 / 18,603 is that the mixture still contains more than 9 wt% nitrile compound, which makes inefficient use of the starting material and also makes it difficult to purify the amino nitrile or the amino compound to gain.

The object of the invention is to provide a mixture which does not exhibit said drawback.

The invention is characterized in that the mixture contains more than 40 wt% aminonitrile and less than 1013112-6-9 wt% of the nitrile compound.

This ensures that the starting material is used efficiently and that purification of the mixture to amino nitrile or amino compound is simpler.

The mixture preferably contains more than 50 wt% aminonitrile and less than 5 wt% nitrile compound.

The products which can be prepared according to the invention find wide application as a raw material for the production of, for example, lactams.

The invention will be elucidated below by way of examples without limiting the invention thereto.

15

Examples

In the examples, the following abbreviations have been frequently used: SN = succinonitrile 20 ABN = aminobutyronitrile DAB = diaminobutane

Example I

A Raney Nickel with 2.5 wt.% Cr and 2.5 wt.% Fe was used as the catalyst. An autoclave with a volume of 160 ml was used as the reactor.

8 grams of catalyst with the target amount of caustic and the target amount of water in 90 grams of ethylenediamine were autoclaved.

Then the pressure was brought to 7 MPa and the i) I 5 11 2 - 7 temperature was stirred (1000 rpm) to 80 ° C. After the correct temperature was reached, 8 grams of succinonitrile dissolved in 12 grams of ethylenediamine were injected. The insertion of succinonitrile counts as time zero (t = 0). The reaction was stopped after 6.5 minutes. The product was analyzed. The conversion of succinonitrile was 99.4 mol%. The reaction product consisted of 76.13 mol% aminobutyronitrile (ABN), 19.29 mol% diaminobutane (DAB) and 4.59 mol% other products. Other products include products such as pyrrolidine, pyrroline and other possible coupling products of DAB, ABN and pyrrolidine.

Example II-IV

Succinonitrile was hydrogenated as in Example I, with the only variation being the caustic used. The results are shown in Table 1.

Example V-VI

Succinonitrile was hydrogenated as in Example I, with variation of the amount of caustic. The results are shown in Table 1.

Example vil ^ mi

Succinonitrile was hydrogenated as in Example I, with variation of the amount of water. The results are shown in Table 1.

1013112 - 8 -

Example IX-XI

Succinonitrile was hydrogenated as in Example I, with variation of reaction time. The results are shown in Table 1.

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Claims (11)

A process for the preparation of a mixture of an amino nitrile and an amino compound with two or more amino groups by partial hydrogenation of a nitrile compound with two or more nitrile groups, with hydrogen in the presence of a Raney catalyst, lye and water, characterized in: that the caustic / catalyst weight ratio is greater than 0.05 and the water / catalyst weight ratio is less than 2. 2. Process according to claim 1, characterized in that the caustic / catalyst weight ratio is greater than 0.05 and less than 1. Process according to claim 1, characterized in that the caustic / catalyst weight ratio is greater than 0.05 and less than 0.3. 4. Process according to any one of claims 1-3, characterized in that the water / catalyst weight ratio is greater than 0.1 and less than 2. 5. Process according to any one of claims 1-3, characterized in that the weight ratio water / catalyst is greater than 0.4 and less than 1.5. Process according to any one of claims 1 to 5, characterized in that the alkali used is KOH and / or NaOH. Process according to any one of claims 1-6, characterized in that the Raney catalyst is a Raney nickel or a Raney cobalt catalyst. 8. Process according to any one of claims 1-7, characterized in that the nitrile compound with two or more nitrile groups is an α, alk-alkanedinitrile Process according to claim 8, characterized in that the α, alk-alkanedinitrile is succinonitrile or adiponitrile. 10. A mixture of an amino nitrile, an amino compound 10 with two or more amino groups and a nitrile compound with two or more nitrile groups, characterized in that the mixture contains more than 40 wt% amino nitrile and contains less than 9 wt% of the nitrile compound. Mixture according to claim 10, characterized in that the mixture contains more than 50 wt% aminonitrile and contains less than 5 wt% nitrile compound. 1 ^ ^ ~ nnuitiH IlcnMIiUrfv Liiunnu \ i o · /> -. REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE I NATIONAL APPLICATION IDENTIFICATION Feature of the applicant or authorized representative for International Research (ISA) granted to a request for an international type study 'no. SN 33816 EN I. CLASSIFICATION OF THE SUBJECT MATTER (bi) application of different classifications, specify all classification symbols) According to International Classification (IPC) Int. Cl. 7: C 07 C 253/30, C 07 C 255/24 II. FIELDS OF TECHNIQUE EXAMINED _ Minimum documentation examined _ Classification system_ Classification symbols Int. Cl. 7: C 07 C Documentation examined other than the minimum documentation insofar as such documents are included in the areas investigated. comments on supplement sheet) Form FCT / ISA / 20Ha) 07.1979