www.albemarle.
com
ETHANOX Fuel Antioxidants
October 2005
Strictly confidential - proprietary information of Albemarle Corporation
Types Of Fuel
www.albemarle.com
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
Strictly confidential - proprietary information of Albemarle Corporation
Autoxidation Mechanism Role of Antioxidants
RH O2 R CB-A RO 2 RH R + ROOH CB-D PD, MDA CB-D
www.albemarle.com
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
3 Strictly confidential - proprietary information of Albemarle Corporation
Mechanism Of Antioxidant Function In Fuels
Primary antioxidant
OH ROO O
www.albemarle.com
.
+ ROOH
+
stable phenoxy radical
reactive peroxy radical
Metal deactivator
HO N OH N
Cu2+
O
N Cu
N O
Strictly confidential - proprietary information of Albemarle Corporation
Albemarles Fuel Antioxidant Products
www.albemarle.com
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
Strictly confidential - proprietary information of Albemarle Corporation
Most Common Albemarle Antioxidants Used In Fuels
Hindered Phenolics
OH
N
www.albemarle.com
Metal Deactivators
HO N
Ethanox 4701, Ethanox 4733 Phenylenediamines
OH
Ethanox 4705
HN
NH
Ethanox 4720
6 Strictly confidential - proprietary information of Albemarle Corporation
Ethanox 4733 Antioxidant
OH OH OH
www.albemarle.com
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
7 Strictly confidential - proprietary information of Albemarle Corporation
Ethanox 4701 Antioxidant
www.albemarle.com
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
Strictly confidential - proprietary information of Albemarle Corporation
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
www.albemarle.com
Ethanox 4701 is an excellent replacement for Ethanox 4733 in fuels applications where a TTBP-free antioxidant is required
Strictly confidential - proprietary information of Albemarle Corporation
Ethanox 4701 Versus Ethanox 4733 (Performance)
www.albemarle.com
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
10
Strictly confidential - proprietary information of Albemarle Corporation
Ethanox 4720 Antioxidant
www.albemarle.com
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 .
11
Strictly confidential - proprietary information of Albemarle Corporation
Ethanox 4705 Antioxidant
OH N N OH
www.albemarle.com
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
12
Strictly confidential - proprietary information of Albemarle Corporation
Fuel Degradation
www.albemarle.com
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.
13
Strictly confidential - proprietary information of Albemarle Corporation
Fuel Degradation
www.albemarle.com
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.
14
Strictly confidential - proprietary information of Albemarle Corporation
Jet Fuel Antioxidants
www.albemarle.com
Hindered Phenol
Ethanox 4733, Ethanox 4701 Ethanox 4705
Metal Deactivator
15
Strictly confidential - proprietary information of Albemarle Corporation
Fuel Degradation
www.albemarle.com
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?
16
Strictly confidential - proprietary information of Albemarle Corporation
Diesel Fuel Antioxidants / Stabilizers
www.albemarle.com
Metal Deactivator - Ethanox 4705
Hindered Phenols - Ethanox 4733,
Ethanox 4701
17
Strictly confidential - proprietary information of Albemarle Corporation
General Fuel AO Recommendations
www.albemarle.com
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
18
Strictly confidential - proprietary information of Albemarle Corporation
Performance Comparison In Various Fuels*
www.albemarle.com
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)
19
Strictly confidential - proprietary information of Albemarle Corporation
Performance Comparison In Various Fuels*
www.albemarle.com
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)
20
Strictly confidential - proprietary information of Albemarle Corporation
Effect of Additives on Induction Period, Visbreaking Naptha
1500
www.albemarle.com
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)
21
Strictly confidential - proprietary information of Albemarle Corporation
Effect of Additives on Induction Period, FCC Naptha A
2500
www.albemarle.com
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)
22
Strictly confidential - proprietary information of Albemarle Corporation
ASTM D525 Performance Ethanox 4701 to 4733
Canadian Light Cat Cracked Naphtha
D525 Induction Period (min.)
500
www.albemarle.com
400 E-4701 E-4733 2,4,6 TTP
300
200
100 0 2 4 6 8 10
Antioxidant Treat Rate (PTB)
23 Strictly confidential - proprietary information of Albemarle Corporation
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.
www.albemarle.com
24
Strictly confidential - proprietary information of Albemarle Corporation
ASTM D525 Performance
Cat Cracked Naphtha
D525 Induction Period (min.)
www.albemarle.com
500 400 300 200 100 0 2 4 6 8 10 Antioxidant Treat Rate (PTB) 4740 4720 4733
25
Strictly confidential - proprietary information of Albemarle Corporation
Fuel Antioxidant/Stabilizer Use Table
www.albemarle.com
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
26
Strictly confidential - proprietary information of Albemarle Corporation
The Future - More use of Ethanol
Gasoline
Little
www.albemarle.com
effect on induction period. Effect on potential gums is fuel dependent. Increases potential for peroxide buildup.
27
Strictly confidential - proprietary information of Albemarle Corporation
Effect of Ethanol on Potential Gum
www.albemarle.com
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
28
Strictly confidential - proprietary information of Albemarle Corporation
Effect of Ethanol on Peroxide Formation
www.albemarle.com
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.
29
Strictly confidential - proprietary information of Albemarle Corporation
Effect of Antioxidants and Oxygenates On Peroxide Formation in ASTM D 873
www.albemarle.com
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)
30 Strictly confidential - proprietary information of Albemarle Corporation
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)
www.albemarle.com
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)
31 Strictly confidential - proprietary information of Albemarle Corporation
Effect of Antioxidants and Oxygenates On ASTM D 873 Performance
www.albemarle.com
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)
32 Strictly confidential - proprietary information of Albemarle Corporation
The Future - Sulfur Reduction
Gasoline
www.albemarle.com
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
33
Strictly confidential - proprietary information of Albemarle Corporation
Peroxide Formation in ULSD
www.albemarle.com
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
34
Strictly confidential - proprietary information of Albemarle Corporation
www.albemarle.com
Antioxidants For Fuel Applications
Albemarle Corporation Baton Rouge, LA 70820 USA Vince Gatto 225-768-5656 FAX 225-768-5607
[email protected] Albemarle Europe SPRL Louvain-la Neuve, Belgium Didier De Schampheleer 32 10 48 1772 FAX 32 10 48 3921
[email protected]Strictly confidential - proprietary information of Albemarle Corporation
