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

Glycerine

Fatty Acids

Fatty Acid Methyl Esters

Fatty Alcohol

Oils &

Fats

splitting

esterification

trans-esterification

Partial glycerides

Triacetine

Fatty Acid esters

F.A. ethoxylates

Soaps

Fatty Amines

Alkyl chlorides

F. OH ethoxylates

F.OH sulfates

Esters

F.A. Alkanolamides

Fatty Alcohols

esterification

esterification

ethoxylation

neutralization

amination

hydrogenation

amidation

direct hydrogenation

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

a

b

c

d

Lubricants Detergents Plasticizer Cosmetics

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

• Coconut - Major source Philippines. Declining in use.

• Fish oil (FH) - Predominantly used in Chile/Peru. Was popular in UK, Norway, Japan.

• Canola/Rapeseed - Predominantly grown in Canada and northern Europe. Typically has higher poisons than soya.

• Soyabean Oil (SO)- Primarily derived from the major soya states in the US, Brazil and Argentina.

• Tallow - animal fat, usually a by-product of rendering. Lard from pigs also used.

Where do they come from?

• Whales - major source of oleochemicals for many years - oils, waxes, ester, spermaceti, squaleen. No longer available due to over-hunting

Alcohols ◦ OH

OH

O C R

OH

H

C R

H

H

H N R

O

O

C R

H

R1

• Amines – NH2

• Esters – COOR1

• Carboxylic Acids – COOH

Fatty Acids

Soap

Cosmetics Lubricants

Plasticizer

Intermediates

OH

O C R

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 200°C & 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

Equilibrium is determined by hydrogen concentration !

Ni(fa)2 + H2

low pressure/ hydrogen shortage

high pressure/ abundance of hydrogen

Ni + 2 ffa

Fate of nickel crystallites: Nickel dissolution is chemically reversible, but catalytic surface vanishes drastically thereby (loss of Nickel dispersion):

+ ffa

- ffa

+ Ni-soaps

fresh catalyst 100 m²/g Ni

used catalyst 10-20 m²/g Ni

0

5

10

15

20

25

0 0.1 0.2 0.3 0.4 0.5 0.6

1/H2 pressure (bar-1)

Dis

solv

ed N

i (pp

m)

2 bar 10 bar 30 bar

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

Ni + 2H+ = Ni2+ + H2

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)

Soybean soap stock fatty acids, 15 bar, 200°C

1

10

100

1 10pore size diameter (nm)

final iodine value

presumablecourse

tallow olein fatty acids vacuum 140°C fast stirring catalyst dosage 450 ppm Nickel

50556065707580859095

100

0 50 100

time (min)

rela

tive

activ

ity (%

)

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

6 Spent

catalyst

7 Incineration

spent catalyst

8 Precious metal ash

2 Precious

metal sponge

3 Precious

metal salt solution

1 Precious

metal

5 Customers

process

9 Precious metal ash refining

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

unsat FA

Fatty Alcohols

Surfactants 80%

Shampoo Powders Bath gels

etc Cosmetics

Lubricants in polymer processing

Emulsifying agents

OH

O C R

“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; 230-250°C

Trickle-bed ◦ 2900-4350psi; 250 °C

Higher cat consumption than FB Greater flexibility Vertical plug-flow reactor ◦ 3600psi; 250-300°C

Direct hydrogenolysis of fatty acids (Lurgi) ◦ Acid-resistant catalyst required ◦ Excess of fatty OH and loop employed ◦ 4350psi; 300°C

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 ◦ 100-150°C; 20-50bar

Fatty M.E.

Intermediates

Biodiesel

O

O

C R

H

R1

Usually manufactured directly from oils via methanolysis with alkaline catalysts (e.g. sodium methylate)

CH2OH

CHOH

CH2OH

3CHOH 3RCOOCH3

RCOOCH2

RCOOCH

RCOOCH2

NaOCH3 + +

methyl ester

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)

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

USA

cetane (C16)

biodiesel

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

R-NH2

R2NH

R3N

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)

Raney

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.

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

Glycerine

Tobacco

Pharmaceutical

Food

Explosives

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