fatty amines – a commercial overview

Gerard B. Hawkins Managing Director

Most uses depend on the cationic nature of the amine

Fatty Amines

Corrosion Inhibitors

Fabric Softeners

Lubricant Additive

Organoclays

Sanitizing Agents

H

H N R

Primary amine

Secondary amine

Tertiary amine

Which amines are produced depends on: reaction conditions ◦ NH3 pressure ◦ Temperature

Catalyst choice ◦ Raney Ni ◦ Supported Ni powders

Fatty nitriles Fatty acids Al2O3 NH3

Unsaturated primary amine

Saturated primary amine

Saturated and unsaturated secondary

amines

Dialkyl monomethyl

tertiary amine

Ni(P)

Sponge

Ni(D)

Ni(D) Formaldehyde

Batch slurry phase most common Fixed bed or continuous slurry phase also used

Product Temp (C) Pressure

(bar) Catalysts Special Conditions

Primary 80-150 10-550 nickel, raney nickel, cobalt

Ammonia added to feed to suppress secondary and tertiary amine formation

Secondary 150-200 50-200 nickel, cobalt Ammonia removed by purging with hydrogen

Tertiary 160-230 7 - 14 nickel, cobalt Secondary Amine used as feed; hydrogen purge necessary to remove ammonia

Unsaturated

copper chromite,

nickel powder

similar to abovesimilar to above

R-COOH + NH3 R-COONH4

R-COONH4 R-CONH2 + H2O

ammonium salt

amide

R-CONH2 R-CN + H2O nitrile

R-CN + 2H2 FATTY AMINES

R-C≡N + H2

R-CH=NH imine

First reaction step

R-CH=NH + H2 imine

Primary amine formation

R-CH2NH2

Secondary amine formation

R-CH=NH + R-CH2NH2 imine

R-CH-NH-CH2-R

NH2 1-aminodialkylamine

Secondary amine formation

R-CH-NH-CH2-R

NH2 1-aminodialkylamine

R-CH=N-CH2-R

- NH3

imine

Secondary amine formation

R-CH2-NH-CH2-R secondary amine

R-CH=N-CH2-R imine

+H2

Secondary amine formation via hydrogenolysis

R-CH-NH-CH2-R

NH2 1-aminodialkylamine

R-CH2-NH-CH2-R

- NH3

secondary amine

+H2

Tertiary amine formation proceeds via the same route as with the secondary amine formation. However, secondary amine condenses with imine to yield tertiary intermediates.

Amine Catalyst

Saturated Primary Amine Sponge Ni type catalyst

Unsaturated Primary Amine Supported Ni powder catalysts, Supported Co tablet catalysts

Saturated Secondary Amines Supported Ni powder catalysts

Unsaturated Secondary Amines Supported Ni powder catalysts

Tertiary Amines Supported Ni powder catalysts