fatty amines chemistry
Post on 14-Jul-2015
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Gerard B. Hawkins Managing Director
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
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
O
OHNH3+
NH4+
O
-O
R
R
O
ONH3+
R
O
H2N
R
OH
HO
H
R
NH
R NH2
OH
R
O
R
NH3+
HO
H
H2
HO
H
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
R
N
R
NH
R NH2
R
N
R
NH
R
NH2
R
HN
R
R
N
H H
R
R
N
R
NH 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
dimethyl tertiary amines
R N
R NH2
O+
Primary amine
HO
H2
Leuckart reaction
N
O
R
Dimethylamide
HO
H
Reduction
R NH2OH+ 2
Alkylation
HO
H2
R NH2Cl+ 2
Alkylation
+ 2 NaOH
HO
H + 2 NaCl
R OHHN
dimethylamine
+
HO
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr
R N
R NH2
O+
Primary amine
HO
H2
Leuckart reaction
N
O
R
Dimethylamide
HO
H
Reduction
R NH2OH+ 2
Alkylation
HO
H2
R NH2Cl+ 2
Alkylation
+ 2 NaOH
HO
H + 2 NaCl
R OHHN
dimethylamine
+
HO
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr
R N
R NH2
O+
Primary amine
HO
H2
Leuckart reaction
N
O
R
Dimethylamide
HO
H
Reduction
R NH2OH+ 2
Alkylation
HO
H2
R NH2Cl+ 2
Alkylation
+ 2 NaOH
HO
H + 2 NaCl
R OHHN
dimethylamine
+
HO
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr
R N
R NH2
O+
Primary amine
HO
H2
Leuckart reaction
N
O
R
Dimethylamide
HO
H
Reduction
R NH2OH+ 2
Alkylation
HO
H2
R NH2Cl+ 2
Alkylation
+ 2 NaOH
HO
H + 2 NaCl
R OHHN
dimethylamine
+
HO
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr
R N
R NH2
O+
Primary amine
HO
H2
Leuckart reaction
N
O
R
Dimethylamide
HO
H
Reduction
R NH2OH+ 2
Alkylation
HO
H2
R NH2Cl+ 2
Alkylation
+ 2 NaOH
HO
H + 2 NaCl
R OHHN
dimethylamine
+
HO
H
Aminolysis
Ni Cu/Cr
Alumina
Cu/Cr
Non dimethyl tertiary amines
R NH
O
R N
+
Leuckart reaction
HO
H
Secondary amine
N
+
RR
R N
R
CN
R N
R
NH2
Acrylonitrile
R NH
O
R N
+
Leuckart reaction
HO
H
Secondary amine
N
+
RR
R N
R
CN
R N
R
NH2
Acrylonitrile
quaternary amine salts
R NH2Cl+ 3
2 NaOH 2 NaCl
R N +Cl-
R NH
R
Cl+ 2R N
R
+Cl-
R N
Alkylations:
+ SO
OO
O
dimethylsulphate
R N
S
O
O
O
O+-
R N +
Cl
benzylchloride
R N+-
Cl
NaOH NaCl
R NH2Cl+ 3
2 NaOH 2 NaCl
R N +Cl-
R NH
R
Cl+ 2R N
R
+Cl-
R N
Alkylations:
+ SO
OO
O
dimethylsulphate
R N
S
O
O
O
O+-
R N +
Cl
benzylchloride
R N+-
Cl
NaOH NaCl
R NH2Cl+ 3
2 NaOH 2 NaCl
R N +Cl-
R NH
R
Cl+ 2R N
R
+Cl-
R N
Alkylations:
+ SO
OO
O
dimethylsulphate
R N
S
O
O
O
O+-
R N +
Cl
benzylchloride
R N+-
Cl
NaOH NaCl
R NH2Cl+ 3
2 NaOH 2 NaCl
R N +Cl-
R NH
R
Cl+ 2R N
R
+Cl-
R N
Alkylations:
+ SO
OO
O
dimethylsulphate
R N
S
O
O
O
O+-
R N +
Cl
benzylchloride
R N+-
Cl
NaOH NaCl
Saturated fatty nitrile hydrogenation
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
Saturated fatty nitrile hydrogenation
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
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
Comparison of Two Commercially Available Catalyst, in the hydrogenation of saturated nitriles
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