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ETHANOX Fuel Antioxidants

October 2005

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Types Of Fuel
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Butane and Lighter Gas Processing Straight-Run Gasoline Naphtha Distillation Crude Kerosene LGO HGO Catalytic Cracking Straight-Run Residue Flashing

Gasoline
Motor Gasoline Blending Catalytic Reforming Hydrotreating Distillate Fuel Blending

Jet Fuel

Diesel

Fuel Oil

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Autoxidation Mechanism Role of Antioxidants

RH O2 R CB-A RO 2 RH R + ROOH CB-D PD, MDA CB-D

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metals RH RO + OH

CB-A = Chain-breaking Acceptor e.g. quinones, galvinoxyl CB-D = Chain-breaking Donor e.g. phenols, amines PD = Peroxide Decomposer e.g. phosphites, sulfur compounds, ZDDP

alcohols, aldehydes

ketones, acids

insolubles

MDA = Metal Deactivator e.g. Ethanox 4705

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Mechanism Of Antioxidant Function In Fuels

Primary antioxidant
OH ROO O

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.
+ ROOH

+
stable phenoxy radical

reactive peroxy radical

Metal deactivator
HO N OH N

Cu2+
O

N Cu

N O

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Albemarles Fuel Antioxidant Products

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Hindered Phenolics
Ethanox 4701, Ethanox 4733, Ethanox 4735 Ethanox 4737, Ethanox 4545, Ethanox 4775, Ethanox 4776, Ethanox 4778

Phenylenediamines
Ethanox 4720

Metal Deactivators
Ethanox 4705

Hindered Phenolic / Phenylenediamine Blends

Ethanox 4740, Ethanox 4742

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Most Common Albemarle Antioxidants Used In Fuels

Hindered Phenolics
OH
N

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Metal Deactivators
HO N

Ethanox 4701, Ethanox 4733 Phenylenediamines

OH

Ethanox 4705

HN

NH

Ethanox 4720
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Ethanox 4733 Antioxidant

OH OH OH

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75% 13%
Form / Appearance Melting Point Viscosity @ 40C TGA 50% Wt. Loss Temp. Uses Clear yellow liquid 17C* 6.3 cSt 112C

10%

Antioxidant for motor and aviation gasolines, jet fuel, diesel fuel, industrial oils.

* Tends to supercool
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Ethanox 4701 Antioxidant

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OH

> 99+ %
Form / Appearance Melting Point Pour Point Viscosity @ 40C TGA 50% Wt. Loss Temp. Uses Straw to light yellow solid 36C -6.6 cSt 136C Antioxidant for motor and aviation gasolines, jet fuel, diesel fuel, industrial oils

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Properties Comparison Between Ethanox 4701 and Ethanox 4733

Property Activity, % Melting Point, oC Viscosity @ 40oC, cSt Flash Point, COC, oC Density @ 20oC, g/mL 50% TGA loss temp., oC TTBP, ppm Ethanox 4701 Ethanox 4733 100 36 6.6 92 0.91 130 <5 100 17 6.3 93 0.94 136 130,000

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Ethanox 4701 is an excellent replacement for Ethanox 4733 in fuels applications where a TTBP-free antioxidant is required

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Ethanox 4701 Versus Ethanox 4733 (Performance)

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Ethanox 4733 has been the fuel antioxidant standard for over three decades because of its lower freeze point Both Ethanox 4701 and Ethanox 4733 are 100% active hindered tert-butylphenols The fuels industry has generally accepted the interchangeability of Ethanox 4701 and Ethanox 4733

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Ethanox 4720 Antioxidant

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HN

NH
97% min.

F o rm / A p p e a ra n c e M e ltin g P o in t V is c o s ity @ 4 0 C U ses

B ro w n to re d liq u id 1 8 C 1 1 .3 c S t A n tio x id a n t fo r m o to r g a s o lin e s .

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Ethanox 4705 Antioxidant

OH N N OH

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50% active
F o rm / A p p e a ra n ce V isco sity @ 4 0 C U se s A m b e r liq u id 9 .9 cS t A n tio xid a n t (m e ta l d e a ctiva to r) fo r g a so lin e , d ie se l fu e l a n d je t fu e l

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Fuel Degradation
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Gasoline
Reaction of fuel with oxygen to form peroxides and gums. Autoxidation reaction. Catalyzed by some metals. Peroxides are pro-knocks and can degrade plastic and elastomeric fuel system parts. Soluble gums can be precursors to engine deposits. Insoluble gums can plug filters. Degradation inhibited by hindered phenols, phenylenediamines and metal deactivators.

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Fuel Degradation
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Jet Fuel
Reaction of fuel with oxygen to form peroxides and gums. Autoxidation reaction. Catalyzed by some metals. Peroxides can degrade plastic and elastomeric fuel system parts. Soluble gums can be precursors to nozzle and fuel line deposits. Insoluble gums can plug filters. Degradation inhibited by hindered phenols and metal deactivators.

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Jet Fuel Antioxidants

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Hindered Phenol

Ethanox 4733, Ethanox 4701 Ethanox 4705

Metal Deactivator

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Fuel Degradation
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Diesel Fuel and Home Heating Oil

Acid catalyzed combination of certain unstable compounds. Important in high and low-sulfur diesel fuels and home heating oils. Inhibited by alkyl amines which neutralize catalyst acids. Dispersants prevent sedimentation. Mechanism different in ultra-low sulfur fuels?

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Diesel Fuel Antioxidants / Stabilizers

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Metal Deactivator - Ethanox 4705

Hindered Phenols - Ethanox 4733,

Ethanox 4701

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General Fuel AO Recommendations

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Gasoline (motor and aviation)

Hindered phenolic, phenylenediamine and metal deactivator Ethanox 4733/4701, Ethanox 4720 and Ethanox 4705

Jet fuel (turbine)

Hindered phenolic and metal deactivator Ethanox 4733/4701 and Ethanox 4705

Diesel & fuel oils

Hindered phenolic and metal deactivator Ethanox 4733/4701 and Ethanox 4705

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Performance Comparison In Various Fuels*

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Percent reduction in mass of total gum formed compared to fuel with no additive. Fuel aged at 100oC under 100 psig oxygen for 4 hours. All antioxidants added at 25 ppm (v/v).
Ethanox Name 4720 4712 4701 Antioxidant Type PDA BHT DTBP FCC Naphtha 1 91.7 97.2 97.1 FCC Naphtha 2 91.1 94.5 88.2 Visbreaking Visbreaking Naphtha 1 37.0 79.6 48.7 Naphtha 2 74.7 94.6 95.4 Coker Naphtha 92.8 98.4 99.2

*J. M. Nagpal, G. C. Joshi and S. N. Rastogi, Stability of Cracked Naphthas From Thermal and Catalytic Processes. Part II. Composition and Effect of Olefinic Structures, Fuel, 74(5), 714 (1995)

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Performance Comparison In Various Fuels*

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Percent reduction in mass of total gum formed compared to fuel with no additive. Fuel aged at 43oC at ambient air pressure for 13 weeks. All antioxidants are added at 10 ppm (v/v).
Ethanox Name 4720 4712 4701 Antioxidant Type PDA BHT DTBP FCC Naphtha 1 26.5 95.5 95.2 FCC Naphtha 2 87.2 93.1 95.7 Visbreaking Visbreaking Naphtha 1 37.8 50.6 78.1 Naphtha 2 24.4 94.5 95.8 Coker Naphtha 15.5 53.8 90.4

*J. M. Nagpal, G. C. Joshi and S. N. Rastogi, Stability of Cracked Naphthas From Thermal and Catalytic Processes. Part II. Composition and Effect of Olefinic Structures, Fuel, 74(5), 714 (1995)

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Effect of Additives on Induction Period, Visbreaking Naptha

1500

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Induction Period, minutes

1200 900 600 300 0 0 10 20 30 40 50 60 70 Additive, ppm

*J. M. Nagpal, G. C. Joshi and S. N. Rastogi, Stability of Cracked Naphthas From Thermal and Catalytic Processes. Part II. Composition and Effect of Olefinic Structures, Fuel, 74(5), 714 (1995)

Ethanox 4701 (DTBP) Ethanox 4712 (BHT) Ethanox 4720 (PDA)

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Effect of Additives on Induction Period, FCC Naptha A

2500

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Induction Period, minutes

2000 1500 1000 500 0 0 10 20 30 40 50 60 70 Additive, ppm

*J. M. Nagpal, G. C. Joshi and S. N. Rastogi, Stability of Cracked Naphthas From Thermal and Catalytic Processes. Part II. Composition and Effect of Olefinic Structures, Fuel, 74(5), 714 (1995)

Ethanox 4701 (DTBP) Ethanox 4712 (BHT) Ethanox 4720 (PDA)

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ASTM D525 Performance Ethanox 4701 to 4733

Canadian Light Cat Cracked Naphtha
D525 Induction Period (min.)
500

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400 E-4701 E-4733 2,4,6 TTP

300

200

100 0 2 4 6 8 10

Antioxidant Treat Rate (PTB)

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Antioxidant Blend For Gasoline and Jet Fuel Ethanox 4740

Low melting point (-14C). Effective in all bench tests. Hindered Phenol / PDA synergy. Often most cost effective.

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ASTM D525 Performance

Cat Cracked Naphtha
D525 Induction Period (min.)

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500 400 300 200 100 0 2 4 6 8 10 Antioxidant Treat Rate (PTB) 4740 4720 4733

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Fuel Antioxidant/Stabilizer Use Table

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Product Chemistry
Hindered Phenol

Ethanox #(s)
4733

Mainly Used In:

Jet fuels (military and civilian), ultralow sulfur diesel fuels and relatively stable gasolines. Very unstable gasolines. Most gasolines. Military jet fuels, gasolines and distillate fuels with dissolved metals. Refineries which cannot heat trace additive injection lines. Cold climates.

Phenylenediamine (PDA) Hindered Phenol/ PDA Mixtures Metal Deactivator

4720 4740 4705

AO Dilutions

Various

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The Future - More use of Ethanol

Gasoline
Little

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effect on induction period. Effect on potential gums is fuel dependent. Increases potential for peroxide buildup.

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Effect of Ethanol on Potential Gum

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4-Hour ASTM D873

120

Potential Gum (mg/100ml)

Base Gasoline
100

10% Ethanol
80 60 40 20 0 FCCN Fuel A Fuel B Fuel C

+ 5 PTB HiTEC 4740 AO

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Effect of Ethanol on Peroxide Formation

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1000

Peroxide Number (ppm)

800
Base Gasoline

600 400

10% Ethanol + 5 PTB HiTEC 4740 AO

200 0 FCCN Fuel A Fuel B Fuel C

Peroxides measured after ASTM D873.

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Effect of Antioxidants and Oxygenates On Peroxide Formation in ASTM D 873

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Testing Performed In Unleaded Gasoline, 100 psi O2, 100oC, 4 hours aging
600
Peroxide Number (ppm)

500 400 300 200 100 0

O X 3 0 A 47 3 47 4 47 2 0
No Oxygenate 15% MTBE 10% Ethanol

No

Antioxidant (14.3 mg/L)

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Effect of Antioxidants and Oxygenates On Storage Stability in ASTM D 4625

Testing Performed In Unleaded Gasoline, 43oC, 13 weeks aging
700 600
Total Gum (mg)

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500 400 300 200 100 0

OX 33 40 47 47 No A 47 20
No Oxygenate 15% MTBE 10% Ethanol

Antioxidant (14.3 mg/L)

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Effect of Antioxidants and Oxygenates On ASTM D 873 Performance

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Testing Performed In Unleaded Gasoline, 100 psi O2, 100oC, 4 hours aging
70
Potential Gum (mg/100 mL)

60 50 40 30 20 10 0
OX No A H H47 40 H47 20 -47 33

No Oxygenate 15% MTBE 10% Ethanol

Antioxidant (14.3 mg/L)

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The Future - Sulfur Reduction

Gasoline

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Increases induction period. Decreases potential gums. May increase potential for peroxide buildup. Increases storage and thermal stability (resistance to sediment formation). May increase potential for peroxide buildup.

Diesel Fuel

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Peroxide Formation in ULSD

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120 100
Base Diesel

Peroxide Number (ppm)

80
+ 10 PTB HiTEC 4733 AO

60 40 20 0

Peroxides measured after ASTM D6468.

LSD A LSD B ULSD

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Antioxidants For Fuel Applications

Albemarle Corporation Baton Rouge, LA 70820 USA Vince Gatto 225-768-5656 FAX 225-768-5607 vince_gatto@albemarle.com Albemarle Europe SPRL Louvain-la Neuve, Belgium Didier De Schampheleer 32 10 48 1772 FAX 32 10 48 3921 didier.de.schampheleer@albemarle.com

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