Mercaptans in Crude Oil

Larry Kremer & Weldon Cappel

Baker Hughes

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Agenda

• Mercaptan properties
• Mercaptan Scavengers
• Effect of temperature and time
 Odor of Mercaptans

Odor Detection Odor Detection

Hazard Threshold Hazard Threshold
Hydrogen Sulfide 0.0047 ppm Carbon Disulfide 0.21 ppm

Methyl Mercaptan 0.0021 ppm Methyl Alcohol 100 ppm

Ethyl Mercaptan 0.001 ppm Kerosene 1 ppm
n-Propyl Mercaptan 0.00075 ppm Ammonia 46.8 ppm

n-Butyl Mercaptan 0.001 ppm Sulfur Dioxide 3.0 ppm

*Data taken from “Hazardous Chemicals Data Book” by G. Weiss (1980)

 Properties of Mercaptans

Vapor Toxicity By
Physical State Boiling Point Specific Inhalation Toxicity by
Hazard @ 15°C, 1 atm (°C) Gravity (TLV) Ingestion
Hydrogen Sulfide Gas -60.4 1.2 10 ppm NA
Methyl Mercaptan Gas 6.2 1.66 0.5 ppm NA
Hydrogen Cyanide Liquid 25.7 0.9 10 ppm LD50 = < 0.05 g/kg

Ethyl Mercaptan Liquid 34.4 2.1 0.5 ppm LD50 = 0.682 g/kg
Carbon Disulfide Liquid 46.3 2.6 20 ppm LD50 = 0.1 to 0.99
g/kg
n-Propyl Mercaptan Liquid 67 2.6 NA LD50 = 1.79 g/kg

n-Butyl Mercaptan Liquid 98.5 3.1 0.5 ppm LD50 = 1.5 g/kg
Automotive Liquid 60 to 199 3.4 NA LD50 = 0.5 to 5.0
Gasoline g/kg
Kerosene Liquid 200 to 260 NA 200 ppm LD50 = 5.0 to 15.0
g/kg
 Mercaptan Scavengers

• Mercaptans are less acidic and less reactive than H2S

• Typical hydrogen sulfide scavengers are ineffective at

removing mercaptans from hydrocarbons

• Specialized chemistry with greater reactivity needed

– SULFIXTM 9281
– SULFIXTM 9284
– SULFIXTM 9286

SULFIX is a trademark of Baker Hughes Incorporated

Mercaptan Scavengers

• Rapid reaction with lower molecular weight

mercaptans
• Longer reaction time for longer chain or branched
mercaptans
• Removal of other sulfur species:
– Limited removal of carbonyl sulfide (COS) and dialkyl
sulfides (RSR)
– Some removal of carbon disulfide (CS2)
 Mercaptan Scavenger Test Methods

• ASTM D-3227, UOP-163

– Titration methods using silver nitrate titrant
• Draeger Tubes (headspace measurement)
• Doctor Test
– Lead solution & elemental sulfur used
Mercaptan Scavengers
Untreated ppm RSH ppm RSH
Mercaptan
RSH (ppm) Treated Treated
Methane
115 24 67
Thiol
Ethane
84 32 74
Thiol
2-Propane
48 25 44
Thiol
2 Methyl -2-
Propane 6.5 4.7 6.1
Thiol
2-Methyl-1-
Propane 4 2.2 4.5
Thiol
Tengiz Crude Oil, 1 Hr @ 50°C, 7,500 ppm Additive
 Mercaptan Scavengers

Scavenger Speed As A Function of Temperature

400
350 30 °C
ppm Methane Thiol

300 50 °C
250 60 °C
200 70 °C
150 90 °C
100
50
0
0 5 10 15 20 25 30 35 40 45 50
Time (Min)

Tengiz Crude, SULFIX 9281 @ 1,540 ppm

Mercaptan Scavenger Performance

120
Methane Thiol
100 Ethane Thiol
ppm Mercaptan

104

80 2-Propane Thiol
85

60 56
58

40
45

34

20
29
25

20
18
21

10
0
0 5 60 120
Time (Minutes)

Tengiz Crude, 50°C, 1,000 ppm SULFIX 9281

Summary

• Mercaptans have low odor threshold

• Scavengers have partial success
• Scavenging improves with temperature and time