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Gerard B.

Hawkins
Managing Director

Chemical intermediates and products derived from


natural triglycerides

5 basic oleochemicals:

fatty acids
fatty alcohols
fatty methyl esters
fatty amines
glycerine

esterification

Partial glycerides

Glycerine

Triacetine

splitting

esterification

Fatty Acid esters

ethoxylation

Oils
&
Fats

Fatty
Acids

neutralization

Soaps

amination

Fatty Amines

esterification

a
hydrogenation

trans-esterification

F.A. ethoxylates

Fatty Acid
Methyl
Esters

Fatty
Alcohol

Adapted from: Zoeblein, INFORM, Vol 3. no.6

c
d

amidation
direct hydrogenation

Alkyl chlorides
F. OH ethoxylates
F.OH sulfates
Esters
F.A. Alkanolamides
Fatty Alcohols

Lubricants
Detergents
Plasticizer
Cosmetics

Where do they come from?

Soyabean Oil (SO)- Primarily derived from the


major soya states in the US, Brazil and Argentina.

Palm Oil (PO)- Primarily derived from the palm oil plantations
in Malaysia and Indonesia is the major feedstock in Asia.

Canola/Rapeseed - Predominantly grown in Canada and


northern Europe. Typically has higher poisons than soya.

Coconut - Major source Philippines. Declining in use.

Fish oil (FH) - Predominantly used in Chile/Peru.


Whales
- major
of oleochemicals
for
Was popular
insource
UK, Norway,
Japan.
many years - oils, waxes, ester, spermaceti,
squaleen. No longer available due to overhunting
Tallow - animal fat, usually a by-product of
rendering. Lard from pigs also used.

Carboxylic Acids
R

COOH

C
OH

Alcohols
OH

Amines
NH2

OH

H
R

COOR1

Esters
R

C
H

R1

Intermediates
Soap
Plasticizer
Fatty Acids

Lubricants

Cosmetics
O
R

C
OH

Splitting
Hydrogenation
Distillation

Different Process
Twitchell
used catalyst

Continuos
Colgate-Emery higher T & P than Twitchell

Enzymatic
lipases
limited interest to date

Usually to full saturatiuon


i.e. break all double bonds

Catalysts used
Ni on silica powder; slurry phase
Pd on C powder; slurry phase
Pd on C; fixed bed

Reactor systems

Batch Dead End reactors


Continuous Plug flow continuous reactors
Loop reactors
typical conditions 200C & 20bar

Typically a 22-25% Ni on silica or kieselguhr


support
Used by the majority of the market
Particle diameter 6-14 microns
Narrow pores to prevent Ni dissolution
Used once and then must be discarded
Dissolved Ni soaps end up in distillate residues

low pressure/
hydrogen shortage
Ni(fa)2 + H2

Ni + 2 ffa
high pressure/
abundance of hydrogen

Equilibrium is determined by hydrogen concentration !

Fate of nickel crystallites:


Nickel dissolution is chemically reversible, but catalytic
surface vanishes drastically thereby (loss of Nickel
dispersion):
fresh
catalyst

100 m/g Ni
+ ffa
+ Ni-soaps
- ffa

used
catalyst

10-20 m/g Ni

Dissolved Ni (ppm)

25
20

Ni + 2H+ = Ni2+ + H2

15
10

Ni2+ = K.(H+)2/H2

5
0
0
30 bar

0.1
10 bar

0.2

0.3

0.4

1/H2 pressure (bar-1)

0.5

0.6

2 bar

Note Ni dissolution decreases by factor 100 for every pH unit rise!


(data based on fatty acid hydrogenation 180 C)

Smaller pore sizes impede diffusion of larger


molecules, i.e. triglycerides (Gly(fa)3) or nickel
soaps (Ni(fa)2)

final iodine
value
100

10

presumable
course

1
1

10
pore size diameter (nm)
Soybean soap stock fatty acids, 15 bar, 200C

relative activity (%)

100
95
90
85
80
75
70
65
60
55
50

50
time (min)

100

tallow olein fatty acids


vacuum
140C
fast stirring
catalyst dosage
450 ppm Nickel

Loss of Nickel dispersion

Nickel soap formation

Residual Nickel in final product

Minimize contact time in absence of hydrogen


Dose Ni to reactor just before addition of H2 or when it is
already under H2 pressure
Filter catalyst from FA as quickly as possible

If melting of catalyst pellets required, melt in


triglyceride

Ni residues
Environment

Pd/C slurry phase


Typical 5% Pd on a carbon support
Can be re-used
Must have very efficient recovery
Current Pd price - $737/ounce
Financial management as important as
operational management

4
Fresh
Catalyst
5
Customers
process

3
Precious
metal
salt solution

1
Precious
metal

6
Spent
catalyst

2
Precious
metal
sponge

9
Precious
metal ash
refining

7
Incineration
spent
catalyst
8
Precious
metal ash

unsat FA

Pd/C fixed bed


Extrudates / Gauze
High working capital use
Efficient, continuous
production
Ni fixed bed has proved
difficult (basic supports,
posion resistance)
IV < 1

Surfactants
80%
Shampoo
Powders
Bath gels
etc

Fatty
Alcohols

Emulsifying
agents
Cosmetics

Lubricants
in polymer processing

O
R

C
OH

Natural fatty alcohols


Hydrogenation (hydrogenolysis) of fatty methyl esters
direct hydrogenation of fatty acids

Synthetic fatty alcohols


Oxo-Alcohols
Ziegler process

Catalysts used:

CuCr
CuZn
CuSi
Raney Cu

Fixed bed and slurry phase units in operation


Move to eliminate Cr

Feed: methyl esters

Gas phase FB
2900-3600psi; 230-250C

Trickle-bed
2900-4350psi; 250 C

Higher cat consumption than FB


Greater flexibility
Vertical plug-flow reactor
3600psi; 250-300C

Direct hydrogenolysis of fatty acids (Lurgi)


Acid-resistant catalyst required
Excess of fatty OH and loop employed
4350psi; 300C

Carbonyls in fatty OH can give unwanted


color, odor, etc
Can be removed by hydrogenation with Ni
e.g. fixed bed process with PRICAT HTC
Ni impregnated alumina trilobe extrudate

100-150C; 20-50bar

Intermediates
Fatty
M.E.
Biodiesel
O
R

C
H

R1

Usually manufactured directly from oils via


methanolysis with alkaline catalysts (e.g.
sodium methylate)

RCOOCH2
RCOOCH
RCOOCH2

CH2OH
+ 3CHOH

NaOCH3

3RCOOCH3 + CHOH
methyl ester

CH2OH

Lower energy consumption


Less corrosive -> less expensive equipment
More concentrated glycerine
Easier to distill
Superiority in some reactions
However the use of MeOH can have its
downsides

3-armed high viscosity molecule broken down to


single chain low viscous fuel
Similar to cetane (C16)

cetane (C16)

biodiesel
Growth industry due to:
green movement and agricultural incentives in Europe
agricultural lobby and aim for domestic fuel production in
USA

H
R
Most uses depend on the cationic nature of the amine

Corrosion
Inhibitors

Fatty
Amines

Sanitizing
Agents

Organoclays

Fabric
Softeners
Lubricant
Additive

Primary amine

R-NH2

Secondary amine

R2NH

Tertiary amine

R3N

Which amines are produced depends on:


reaction conditions
NH3 pressure
temperature

Catalyst choice
Raney Ni
Supported Ni powders

NH3
Fatty nitriles

Al2O3

Fatty acids

Raney

Saturated
primary amine

Ni(P)

Unsaturated
primary amine
Saturated and
unsaturated
secondary
amines

Ni(D)

Dialkyl
monomethyl
tertiary amine

Ni(D)

Formaldehyde

Batch slurry phase most common


Fixed bed or continuous slurry phase also used
Product

Temp (C)

Pressure
(bar)

Primary

80-150

10-550

nickel, raney Ammonia added to feed to suppress


nickel, cobalt 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

Unsaturated

similar to above

Catalysts

copper
chromite,
nickel
powder

Special Conditions

Secondary Amine used as feed; hydrogen


purge necessary to remove ammonia
similar to above

R-COOH + NH3

R-COONH4
ammonium salt

R-COONH4

R-CONH2 + H2O

amide

R-CONH2

R-CN + H2O

R-CN + 2H2

FATTY AMINES

nitrile

First reaction step

R-CN + H2

R-CH=NH
imine

Primary amine formation

R-CH=NH + H2
imine

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

- NH3
R-CH=N-CH2-R
imine

Secondary amine formation

R-CH=N-CH2-R
imine

+H2
R-CH2-NH-CH2-R
secondary amine

Secondary amine formation via hydrogenolysis

R-CH-NH-CH2-R
NH2
+H2

1-aminodialkylamine

- NH3

R-CH2-NH-CH2-R
secondary amine

Tertiary amine formation


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

By-product during manufacture of


fatty acid
methyl esters & bio-diesel
fatty alcohols

Also synthetic manufacturing


Supply-Demand balance always difficult
What to do with it all?

Personal Care

Food
Glycerine

Explosives
Pharmaceutical

Tobacco

Supply will increase


increasing production of biodiesel and use of oils and fats
as industrial feedstock

New demands must be found/created


some of these may involve catalytic processes
e.g. glycerine to glyceric acid over gold catalyst