Sources of fatty amines The natural reaction pathways of fatty amines Manufacture of hetero-alkyl amines tertiary amines quaternary amine salts Directional influence of H2, NH3 and H2O on: amine distribution conversion and reaction rate

1. Gerard B. Hawkins
Managing Director

2.  Sources of fatty amines
 The natural reaction pathways of fatty amines
 Manufacture of hetero-alkyl amines
◦ tertiary amines
◦ quaternary amine salts
 Directional influence of H2, NH3 and H2O on:
◦ amine distribution
◦ conversion and reaction rate

4. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

5. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

6. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

7. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

8. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

9. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

10. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

11. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

12. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

13. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

14. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

15. R
N
O
OH
NH3+
NH4
+
O
-
O
R
R
O
O
NH3+
R
O
H2N
R
OH
H
O
H
R
NH
R NH2
OH
R
O
R
NH3+
H
O
H
H2
H
O
H

17. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

18. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

19. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

20. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

21. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

22. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

23. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

24. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

25. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

26. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

27. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

28. R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
N
H H
R
R
HN
NH
R
R NH2
HNR
R
R
NH
N
R
R
H
N
R
R
R
NH2
N
R
R
R

29. dimethyl tertiary amines

30. R N
R NH2
O+
Primary amine
H
O
H
2
Leuckart reaction
N
O
R
Dimethylamide
H
O
H
Reduction
R NH2
OH+ 2
Alkylation
H
O
H2
R NH2
Cl+ 2
Alkylation
+ 2 NaOH
H
O
H + 2 NaCl
R OH
H
N
dimethylamine
+
H
O
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr

31. R N
R NH2
O+
Primary amine
H
O
H
2
Leuckart reaction
N
O
R
Dimethylamide
H
O
H
Reduction
R NH2
OH+ 2
Alkylation
H
O
H2
R NH2
Cl+ 2
Alkylation
+ 2 NaOH
H
O
H + 2 NaCl
R OH
H
N
dimethylamine
+
H
O
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr

32. R N
R NH2
O+
Primary amine
H
O
H
2
Leuckart reaction
N
O
R
Dimethylamide
H
O
H
Reduction
R NH2
OH+ 2
Alkylation
H
O
H2
R NH2
Cl+ 2
Alkylation
+ 2 NaOH
H
O
H + 2 NaCl
R OH
H
N
dimethylamine
+
H
O
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr

33. R N
R NH2
O+
Primary amine
H
O
H
2
Leuckart reaction
N
O
R
Dimethylamide
H
O
H
Reduction
R NH2
OH+ 2
Alkylation
H
O
H2
R NH2
Cl+ 2
Alkylation
+ 2 NaOH
H
O
H + 2 NaCl
R OH
H
N
dimethylamine
+
H
O
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr

34. R N
R NH2
O+
Primary amine
H
O
H
2
Leuckart reaction
N
O
R
Dimethylamide
H
O
H
Reduction
R NH2
OH+ 2
Alkylation
H
O
H2
R NH2
Cl+ 2
Alkylation
+ 2 NaOH
H
O
H + 2 NaCl
R OH
H
N
dimethylamine
+
H
O
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr

35. Non dimethyl tertiary amines

36. R NH
O
R N
+
Leuckart reaction
H
O
H
Secondary amine
N
+
R
R
R N
R
CN
R N
R
NH2
Acrylonitrile

37. R NH
O
R N
+
Leuckart reaction
H
O
H
Secondary amine
N
+
R
R
R N
R
CN
R N
R
NH2
Acrylonitrile

38. quaternary amine salts

39. R NH2
Cl+ 3
2 NaOH 2 NaCl
R N +
Cl-
R NH
R
Cl+ 2
R N
R
+
Cl-
R N
Alkylations:
+ S
O
O
O
O
dimethylsulphate
R N
S
O
O
O
O
+-
R N +
Cl
benzylchloride
R N
+-
Cl
NaOH NaCl

40. R NH2
Cl+ 3
2 NaOH 2 NaCl
R N +
Cl-
R NH
R
Cl+ 2
R N
R
+
Cl-
R N
Alkylations:
+ S
O
O
O
O
dimethylsulphate
R N
S
O
O
O
O
+-
R N +
Cl
benzylchloride
R N
+-
Cl
NaOH NaCl

41. R NH2
Cl+ 3
2 NaOH 2 NaCl
R N +
Cl-
R NH
R
Cl+ 2
R N
R
+
Cl-
R N
Alkylations:
+ S
O
O
O
O
dimethylsulphate
R N
S
O
O
O
O
+-
R N +
Cl
benzylchloride
R N
+-
Cl
NaOH NaCl

42. R NH2
Cl+ 3
2 NaOH 2 NaCl
R N +
Cl-
R NH
R
Cl+ 2
R N
R
+
Cl-
R N
Alkylations:
+ S
O
O
O
O
dimethylsulphate
R N
S
O
O
O
O
+-
R N +
Cl
benzylchloride
R N
+-
Cl
NaOH NaCl

43. Saturated fatty nitrile hydrogenation

44.  Saturated Fatty nitrile feedstock
 p Hydrogen: 25, 33 and 41 bar
 p Ammonia: 6, 9 and 12 bar
 Temperature: 140°C
 Catalyst loading: Proprietary
 Water loading: 1%
 Full hydrogenation

47. Saturated fatty nitrile hydrogenation

48.  Saturated Fatty nitrile feedstock
 p Hydrogen: 25 bar
 p Ammonia: 6 bar
 Temperature: 140°C
 Catalyst loading: Proprietary
 Water loading: 0, 1, 2.5, 5%
 Full hydrogenation

52.  Saturated Fatty nitrile feedstock
 p Total: 34 bar
 p Ammonia: 12, 18 and 20.4 bar
 Temperature: 140°C
 Catalyst loading: Proprietary
 Water loading: 0
 Full hydrogenation

53. Comparison of Two Commercially Available Catalyst, in
the hydrogenation of saturated nitriles