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

Hazard

Odor Detection
Threshold

Hazard

Odor Detection
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

0.00075 ppm

Ammonia

46.8 ppm

Sulfur Dioxide

3.0 ppm

n-Propyl Mercaptan

n-Butyl Mercaptan

0.001 ppm

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

Properties of Mercaptans

Hazard
Hydrogen Sulfide
Methyl Mercaptan
Hydrogen Cyanide

Physical State
@ 15C, 1 atm
Gas
Gas
Liquid

Boiling Point
(C)
-60.4
6.2
25.7

Vapor
Specific
Gravity
1.2
1.66
0.9

Toxicity By
Inhalation
(TLV)
10 ppm
0.5 ppm
10 ppm

Toxicity by
Ingestion
NA
NA
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

n-Propyl Mercaptan

Liquid

67

2.6

NA

LD50 = 0.1 to 0.99

g/kg
LD50 = 1.79 g/kg

n-Butyl Mercaptan
Automotive
Gasoline
Kerosene

Liquid
Liquid

98.5
60 to 199

3.1
3.4

0.5 ppm
NA

Liquid

200 to 260

NA

200 ppm

LD50 = 1.5 g/kg

LD50 = 0.5 to 5.0
g/kg
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
Mercaptan
Methane
Thiol
Ethane
Thiol
2-Propane
Thiol
2 Methyl -2Propane
Thiol
2-Methyl-1Propane
Thiol

Untreated
RSH (ppm)

ppm RSH
Treated

ppm RSH
Treated

115

24

67

84

32

74

48

25

44

6.5

4.7

6.1

2.2

4.5

Tengiz Crude Oil, 1 Hr @ 50C, 7,500 ppm Additive

Mercaptan Scavengers

ppm Methane Thiol

Scavenger Speed As A Function of Temperature

400
350
300
250
200
150
100
50
0

30 C
50 C
60 C
70 C
90 C

10

15

20

25

30

Time (Min)

Tengiz Crude, SULFIX 9281 @ 1,540 ppm

35

40

45

50

Mercaptan Scavenger Performance

100

85

80

Methane Thiol
Ethane Thiol
2-Propane Thiol

104

60
56

58

40

60

10

20
18

20

25
29
21

34

45

ppm Mercaptan

120

120

Time (Minutes)

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

Summary
Mercaptans have low odor threshold
Scavengers have partial success
Scavenging improves with temperature and time