Process for preparing primary amines using an unsupported cobalt catalyst

Patent metadata

Field	Value
Publication number	US-9981904-B2
Application number	US-201515505803-A
Country	US
Kind code	B2
Filing date	Aug 25, 2015
Priority date	Aug 28, 2014
Publication date	May 29, 2018
Grant date	May 29, 2018

Abstract

The invention relates to a process for preparing primary amines, which comprises hydrogenating at least one nitrile in an apparatus (V1) in the presence of an unsupported cobalt catalyst to obtain at least one primary amine, with recurrent or continuous addition of at least one compound (I) to the apparatus (V1), said compound (I) comprising at least one component selected from alkali metal, alkaline earth metal and rare earth metal.

First claim

The invention claimed is:

1. A process for preparing a primary amine, the process comprising:
hydrogenating at least one nitrile in an apparatus (V1) in the presence of an unsupported cobalt catalyst to obtain at least one primary amine, with recurrent or continuous addition of at least one compound (I) to the apparatus (V1),
wherein said compound (I) comprises at least one component selected from the group consisting of an alkali metal, an alkaline earth metal, and a rare earth metal.

2. The process according to claim 1 , wherein said compound (I) is an oxide, a hydroxide, a salt, or an aqueous solution.

3. The process according to claim 2 , wherein said compound (I) is an aqueous solution of an oxide, a hydroxide or a salt of lithium, potassium, cesium, magnesium, calcium, lanthanum, or cerium.

4. The process according to claim 2 , wherein said compound (I) is an aqueous solution of lithium hydroxide.

5. The process according to claim 1 , wherein
i) the nitrile comprises 0.01% to 10% by weight of water, or
ii) the compound (I) is added to the apparatus (V1) as soon as a proportion of a secondary amine formed as a by-product is greater than 0.5 GC area %, or
iii) added to the apparatus (V1) via the addition of the compound (I) is 0.01 to 500 ppm of an alkali metal, an alkaline earth metal, or a rare earth metal, based on g atoms of nitrile in the apparatus (V1), as soon as the proportion of the secondary amine formed as the by-product in the apparatus (V1) is greater than 0.5 GC area %, at a catalyst space velocity of 0.01 to 10 kg of reactant per L of catalyst and hour.

6. The process according to claim 1 , wherein the hydrogenating is conducted in the absence of ammonia.

7. The process according to claim wherein
the apparatus (V1) is a reactor, and
a superficial velocity being 5 to 50 kg of mass flow per m 2 of cross-sectional reactor area and second.

8. The process according to claim 1 , wherein the hydrogenating is conducted at a pressure of 1 to 300 bar.

9. The process according to claim 1 , wherein the unsupported cobalt catalyst is used in the apparatus (V1) as a fixed bed catalyst.

10. The process according to claim 1 , wherein the nitrile is an aliphatic mono-, di- or trinitrile, a cycloaliphatic mono- or dinitrile, an alpha-, beta- or omega-aminonitrile, or an alkoxynitrile.

11. The process according to claim 1 , wherein
the at least one primary amine is N,N-dimethylaminopropylamine (DMAPA) and the nitrile is N,N-dimethylaminopropionitrile (DMAPN), or
the at least one primary amine is isophoronediamine and the nitrile is isophoronenitrileimine, or
the at least one primary amine is hexamethylenediamine (HMD) or 6-aminocapronitrile (6-ACN) and HMD, and the nitrile is adiponitrile (ADN).

12. The process according to claim 1 , wherein the unsupported cobalt catalyst consists of catalytically active composition to an extent of at least 70% by weight.

13. The process according to claim 1 , wherein the unsupported cobalt catalyst comprises, as catalytically active composition:
i) cobalt (Co),
ii) optionally at least one element selected from the group consisting of iron (Fe), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt), or
iii) optionally at least one promoter selected from the group, consisting of chromium (Cr), manganese (Mn), molybdenum (Mo), titanium (Ti), zinc (Zn), tin (Sn), an alkali metal, an alkaline earth metal, a rare earth metal, and phosphorus (P).

14. The process according to claim 13 , wherein the catalytically active composition of the unsupported cobalt catalyst consists of 55% to 98% by weight of cobalt, 0.2% to 15% by weight of phosphorus, 02% to 15% by weight of manganese, and 0.2% to 15% by weight of an alkali metal, calculated as CoO, H 3 PO 4 , MnO 2 , and an alkali metal oxide prior to reduction with hydrogen, respectively.

15. The process according to claim 14 , wherein the unsupported cobalt catalyst is prepared by calcining the catalytically active composition first at a final temperature of 550 to 750° C. and then at a final temperature of 800 to 1000° C.

16. The process according to claim 1 , wherein the unsupported cobalt catalyst
i) has surface area of not more than 50 m 2 /g, or
ii) a proportion of support material is not more than 10% by weight, based on a total mass of the catalyst.

17. The process according to claim 16 , wherein the unsupported cobalt catalyst
i) has a surface area of not more than 40 m 2 /g, or
ii) a proportion of the support material is not more than 5% by weight, based on the total mass of the catalyst.

18. The process according to claim 1 , wherein a stream (S1) which is discharged from the apparatus (V1) comprises the primary amine and is returned at least partly to the apparatus (V1).

19. The process according to claim 18 , wherein the compound (I) is added at first to the returned portion of the stream (S1) and then fed into the apparatus (V1) as a constituent of the stream (S1).

20. The process according to claim 18 , wherein the compound (I) is added as an aqueous solution to the returned portion of the stream (S1).

21. The process according to claim 1 , wherein the unsupported cobalt catalyst consists of catalytically active composition to an extent of at least 80% by weight.

Assignees

• Basf Se

Inventors

• Wigbers Christof Wilhelm
• Maegerlein Wolfgang
• Krug Thomas
• Melder Johann-Peter
• Heidemann Thomas
• Stein Bernd

Classifications

• B01J23/78

  with alkali- or alkaline earth metals · CPC title

• B01J23/75

  Cobalt · CPC title

• C07C209/48 Primary

  by reduction of nitriles · CPC title

• C07C2523/75

  Cobalt · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title