Fatty Amines Chemistry
-
Upload
gerard-b-hawkins -
Category
Technology
-
view
376 -
download
0
Transcript of Fatty Amines Chemistry
![Page 1: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/1.jpg)
Gerard B. Hawkins Managing Director
![Page 2: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/2.jpg)
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
![Page 3: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/3.jpg)
![Page 4: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/4.jpg)
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
![Page 5: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/5.jpg)
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
![Page 6: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/6.jpg)
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
![Page 7: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/7.jpg)
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
![Page 8: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/8.jpg)
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
![Page 9: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/9.jpg)
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
![Page 10: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/10.jpg)
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
![Page 11: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/11.jpg)
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
![Page 12: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/12.jpg)
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
![Page 13: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/13.jpg)
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
![Page 14: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/14.jpg)
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
![Page 15: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/15.jpg)
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
![Page 16: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/16.jpg)
![Page 17: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/17.jpg)
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
![Page 18: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/18.jpg)
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
![Page 19: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/19.jpg)
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
![Page 20: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/20.jpg)
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
![Page 21: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/21.jpg)
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
![Page 22: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/22.jpg)
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
![Page 23: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/23.jpg)
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
![Page 24: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/24.jpg)
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
![Page 25: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/25.jpg)
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
![Page 26: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/26.jpg)
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
![Page 27: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/27.jpg)
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
![Page 28: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/28.jpg)
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
![Page 29: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/29.jpg)
dimethyl tertiary amines
![Page 30: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/30.jpg)
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
![Page 31: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/31.jpg)
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
![Page 32: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/32.jpg)
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
![Page 33: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/33.jpg)
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
![Page 34: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/34.jpg)
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
![Page 35: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/35.jpg)
Non dimethyl tertiary amines
![Page 36: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/36.jpg)
R NH
O
R N
+
Leuckart reaction
HO
H
Secondary amine
N
+
RR
R N
R
CN
R N
R
NH2
Acrylonitrile
![Page 37: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/37.jpg)
R NH
O
R N
+
Leuckart reaction
HO
H
Secondary amine
N
+
RR
R N
R
CN
R N
R
NH2
Acrylonitrile
![Page 38: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/38.jpg)
quaternary amine salts
![Page 39: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/39.jpg)
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
![Page 40: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/40.jpg)
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
![Page 41: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/41.jpg)
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
![Page 42: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/42.jpg)
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
![Page 43: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/43.jpg)
Saturated fatty nitrile hydrogenation
![Page 44: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/44.jpg)
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
![Page 45: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/45.jpg)
![Page 46: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/46.jpg)
![Page 47: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/47.jpg)
Saturated fatty nitrile hydrogenation
![Page 48: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/48.jpg)
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
![Page 49: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/49.jpg)
![Page 50: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/50.jpg)
![Page 51: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/51.jpg)
![Page 52: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/52.jpg)
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
![Page 53: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/53.jpg)
Comparison of Two Commercially Available Catalyst, in the hydrogenation of saturated nitriles
![Page 54: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/54.jpg)
![Page 55: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/55.jpg)
![Page 56: Fatty Amines Chemistry](https://reader037.fdocuments.net/reader037/viewer/2022102712/55a4d1901a28abb9758b4763/html5/thumbnails/56.jpg)