Hydrogen Sulfide in Petroleum Hydrogen Sulfide in Petroleum

Hydrogen Sulfide in Petroleum

Mike Nicholson/Tim O
Mike Nicholson/Tim O

Brien
Brien
Baker Petrolite Corporation
Baker Petrolite Corporation
Hydrogen Sulfide Hydrogen Sulfide
Hydrogen Sulfide

Toxic, Colorless Gas

Toxic, Colorless Gas

Rotten Egg Odor

Rotten Egg Odor

Detectable at >10
Detectable at >10
ppb
ppb

Paralyzes olfactory system
Paralyzes olfactory system

LC50 = 713 ppm
LC50 = 713 ppm

Weak Acid, Air Oxidized, Absorbs On

Weak Acid, Air Oxidized, Absorbs On
Metals
Metals

Solubility Depends On Temperature,

Solubility Depends On Temperature,
Fuel, & Henry
Fuel, & Henry

s Law
s Law
Hydrogen Sulfide Toxicity Hydrogen Sulfide Toxicity
Hydrogen Sulfide Toxicity
Concentration (ppm) Health Effect
< 0.02 Olfactory Detection Limit
10 8 Hr Exposure Limit
15 15 Min. STEL
100 Common Ship Headspace
Spec.
300 Considered Immediately
Hazardous
713 LC50 Concentration
1000 Common Tank, Ship
Headspace Concentration

Hydrogen Sulfide Concerns Hydrogen Sulfide Concerns
Hydrogen Sulfide Concerns
H
H
2
2
S
S

Toxic
Toxic

Employee exposure
Employee exposure
Storage tanks Storage tanks
Barges, ships Barges, ships

Corrosive
Corrosive

Fuel specs.
Fuel specs.

Tank roof
Tank roof

Pipelines
Pipelines

Odor Control
Odor Control

Storage tank vents
Storage tank vents

Sewers
Sewers
Odor Issues Odor Issues
Odor Issues
Detection Limits for Common
Odorants
ODORANT DETECTION LIMIT (PPM V/V)
ETHYL MERCAPTAN 0.0003
METHYL MERCAPTAN 0.0008
HYDROGEN SULFIDE 0.002
DIMETHYL SULFIDE 0.002
PHENOL 0.05
P-XYLENE 0.05
TOLUENE 2.0
BENZENE 5.0
AMMONIA 50
Hydrogen Sulfide Hydrogen Sulfide
Hydrogen Sulfide

Crude Oil
Crude Oil

Asphalt
Asphalt

Residual Fuel & Components
Residual Fuel & Components

Mid
Mid
-
-
Distillates & Blend Components
Distillates & Blend Components

Gasoline & Blend Components
Gasoline & Blend Components

Natural Gas, Propane, LPG
Natural Gas, Propane, LPG
Petroleum Streams Where H
Petroleum Streams Where H2 2
S Found
S Found
Crude Oil Crude Oil
Crude Oil

High Sulfur Crudes

High Sulfur Crudes

Mexico
Mexico
Maya Maya 100ppm liquid 100ppm liquid
Olmeca Olmeca 116ppm liquid 116ppm liquid

Middle East
Middle East
Eocene Eocene 90ppm liquid 90ppm liquid
Ratawi Ratawi 80ppm liquid 80ppm liquid

Africa
Africa
Soyo Soyo 16ppm liquid 16ppm liquid
H2S Partitioning H2S Partitioning
H2S Partitioning
200
800
0
100
200
300
400
500
600
700
800
p
p
m

H
e
a
d
s
p
a
c
e

H
2
S
Fuel A
Fuel B
2 ppm liquid phase H2S content 2 ppm liquid phase H2S content
60 F with sample mixing 60 F with sample mixing
Partition Coefficients Partition Coefficients
Partition Coefficients

Crude Oil
Crude Oil

80
80
-
-
300
300
vppm
vppm
per 1lppm
per 1lppm

Residual Oil
Residual Oil

80
80
-
-
400
400
vppm
vppm
per 1lppm
per 1lppm

Gas Oil
Gas Oil

30
30
-
-
150
150
vppm
vppm
per 1lppm
per 1lppm

Gasoline
Gasoline

50
50
-
-
200
200
vppm
vppm
per 1lppm
per 1lppm
Partitioning of H2S Partitioning of H
Partitioning of H
2
2
S
S

1 ppm in liquid can equate to > 50

1 ppm in liquid can equate to > 50
ppm in vapor space
ppm in vapor space

100 ppm in liquid can equate to

100 ppm in liquid can equate to
20,000 ppm in vapor space
20,000 ppm in vapor space
Hydrogen Sulfide Concentrations Hydrogen Sulfide Concentrations
Hydrogen Sulfide Concentrations

Levels of H2S Can be Extremely High

Levels of H2S Can be Extremely High
if Cargoes Are Over Heated
if Cargoes Are Over Heated

Eocene Crude H2S Production After

Eocene Crude H2S Production After
Heating 1 Hour @ Specified
Heating 1 Hour @ Specified
Temperature
Temperature

100 Deg. F
100 Deg. F
400 ppm
400 ppm

200 Deg F
200 Deg F
16,000 ppm
16,000 ppm

300 Deg F
300 Deg F
>80,000 ppm
>80,000 ppm
Factors Affecting Partitioning Factors Affecting Partitioning
Factors Affecting Partitioning

Temperature
Temperature

Viscosity
Viscosity

Pressure
Pressure

Agitation
Agitation

Basic compound in oil

Basic compound in oil
HEAD SPACE H2S VARIATION WITH TIME HEAD SPACE H2S VARIATION WITH TIME
HEAD SPACE H2S VARIATION WITH TIME
0
200
400
600
800
1000
1200
1400
0 0.5 1 1.5 2 2.5
TIME (HOURS)
V
A
P
O
R

S
P
A
C
E

H
2
S

(
P
P
M
)
H2S Specifications H
H
2
2
S Specifications
S Specifications

Regulatory Bodies
Regulatory Bodies
LA harbor, < 70 ppm in liquid LA harbor, < 70 ppm in liquid

Terminals
Terminals
Variable Variable
None to 0 ppm None to 0 ppm
50 50- -200 ppm in vapor typical 200 ppm in vapor typical

Processing Facilities
Processing Facilities
Variable Variable
< 50 ppm in Can Test to None < 50 ppm in Can Test to None

Pipelines
Pipelines
Only one encountered, < 50 ppm in can test Only one encountered, < 50 ppm in can test
Hydrogen Sulfide Test Methods Hydrogen Sulfide Test Methods
Hydrogen Sulfide Test Methods

Vapor Space
Vapor Space

Gas detection tubes
Gas detection tubes

Monitor Electronically
Monitor Electronically

Fuel Sample
Fuel Sample

ASTM D
ASTM D
-
-
5705
5705

Can Test
Can Test

Liquid
Liquid

Sparge
Sparge
test,
test,

ASTM D
ASTM D
-
-
3227, UOP
3227, UOP
-
-
163
163

New ASTM method
New ASTM method
Can Test Method

Can Test
Can Test

Method
Method

Advantages
Advantages

Quick & easy
Quick & easy

1
1
-
-
80,000 ppm
80,000 ppm

Industry standard
Industry standard

Disadvantages
Disadvantages

Loss of H
Loss of H
2 2
S
S

Poor repeatability &
Poor repeatability &
reproducibility
reproducibility

Results influenced
Results influenced
by temp. & shaking
by temp. & shaking
Step 1 Step 1
Add 500 ml Add 500 ml
Sample to Sample to
can can
Step 2 Step 2
Equilibrate Equilibrate
Temp. Agitate Temp. Agitate
Step 3 Step 3
Measure H Measure H
2 2
S S
With Gas With Gas
Detection Tube Detection Tube
Hydrogen Sulfide Scavengers
D-5705 Test Conditions
Hydrogen Sulfide Scavengers
Hydrogen Sulfide Scavengers
D
D
-
-
5705 Test Conditions
5705 Test Conditions

140 F Test Temp

140 F Test Temp

1/2 Full Liter Bottle

1/2 Full Liter Bottle

3 Minutes @ 150 RPM on

3 Minutes @ 150 RPM on
Orbital Shaker
Orbital Shaker

Drager
Drager
Tube Detection
Tube Detection
Liquid Phase Sparge Test Liquid Phase
Liquid Phase
Sparge
Sparge
Test
Test

Multi
Multi
-
-
step Procedure
step Procedure

Advantages
Advantages
Results not dependent on Results not dependent on
temp., temp., vol vol., etc... ., etc...
Field method Field method
Works with a variety of Works with a variety of
hydrocarbons hydrocarbons

Disadvantages
Disadvantages
Wet chemistry analysis Wet chemistry analysis
150 150 F Water F Water
Bath Bath
H H
2 2
S S H H
2 2
S S
H H
2 2
S S
H H
2 2
S S
H H
2 2
S S
H H2 2
S S
GTD* Tube GTD* Tube
Nitrogen (150 ml/min.) Nitrogen (150 ml/min.)
Glass Jar Glass Jar
Stopper Stopper
Total H Total H
2 2
S = (GDT* Reading x 1.42) / Sample wt. S = (GDT* Reading x 1.42) / Sample wt.
*Gas Detection Tube with n=10 scale *Gas Detection Tube with n=10 scale
Hydrogen Sulfide Scavengers
Additional Test Methods
Hydrogen Sulfide Scavengers
Hydrogen Sulfide Scavengers
Additional Test Methods
Additional Test Methods

Vapor Space Methods
Vapor Space Methods

Esso
Esso
Can Test
Can Test

Shell Can Test
Shell Can Test

Baker Petrolite Can Test
Baker Petrolite Can Test

Liquid Test Methods
Liquid Test Methods

UOP 163
UOP 163

ASTM D
ASTM D
-
-
3227
3227

ASTM D
ASTM D
-
-
6021 (New Method)
6021 (New Method)
H2S Analysis H2S Analysis
H2S Analysis

Good sampling critical for good results
Good sampling critical for good results

Common mistakes
Common mistakes

cooling of samples before analysis
cooling of samples before analysis

excessive pouring, transfer of samples
excessive pouring, transfer of samples

storage of oil before analysis
storage of oil before analysis

Test influences
Test influences

Vapor phase test
Vapor phase test

agitation, temperature, vapor/liquid ratio
agitation, temperature, vapor/liquid ratio

Liquid phase test
Liquid phase test

coating of electrodes,
coating of electrodes,
interferences
interferences
Hydrogen Sulfide Scavengers Hydrogen Sulfide Scavengers
Hydrogen Sulfide Scavengers
1999 Baker Petrolite 1999 Baker Petrolite
Hydrogen Sulfide Scavengers
Additive Treatments
Hydrogen Sulfide Scavengers
Hydrogen Sulfide Scavengers
Additive Treatments
Additive Treatments

Chemistry
Chemistry

Oxidizers
Oxidizers

Neutralizers
Neutralizers

Reactants
Reactants

Process Considerations
Process Considerations

Temperature gradients
Temperature gradients

Weathering
Weathering

Additive mixing
Additive mixing
Hydrogen Sulfide Scavengers
Organic Bases
Hydrogen Sulfide Scavengers
Hydrogen Sulfide Scavengers
Organic Bases
Organic Bases

Advantages:
Advantages:

Fast reaction
Fast reaction

No sodium
No sodium

Oil soluble/dispersible
Oil soluble/dispersible

DISADVANTAGES:
DISADVANTAGES:

Reaction is Reversible
Reaction is Reversible

Weak acid/base equilibrium
Weak acid/base equilibrium

Not specific for H
Not specific for H
2 2
S
S
Typically Amines (e.g. MEA)
Typically Amines (e.g. MEA)
H
H
2 2
S + Neutralizer Salt
S + Neutralizer Salt
Hydrogen Sulfide Scavengers
Inorganic Neutralizers
Hydrogen Sulfide Scavengers
Hydrogen Sulfide Scavengers
Inorganic Neutralizers
Inorganic Neutralizers

Advantages
Advantages

Fast reaction, cheap
Fast reaction, cheap

Use alone or in combination
Use alone or in combination

Thermally stable products (
Thermally stable products (
NaHS
NaHS
)
)

Disadvantages
Disadvantages

Non
Non
-
-
selective for H
selective for H
2 2
S
S

Ash forming
Ash forming

Increases fuel
Increases fuel
Na
Na
content
content
. Reversible
. Reversible

Limited Safe Injection Temperature
Limited Safe Injection Temperature
Inorganic Bases:
Inorganic Bases:
NaOH
NaOH
, KOH Or Blends
, KOH Or Blends
H
H
2 2
S +
S +
NaOH
NaOH
Salt
Salt
H2S REDUCTION WITH CAUSTIC,
50 PPM NaOH
H2S REDUCTION WITH CAUSTIC,
H2S REDUCTION WITH CAUSTIC,
50 PPM
50 PPM
NaOH
NaOH
60 MIN REACTION TIME
0
200
400
600
800
1000
1200
1400
FUEL A FUEL B FUEL C FUEL D
V
A
P
O
R

S
P
A
C
E

H
2
S
INITIAL FINAL
EFFECT OF TEMPERATURE AND CONCENTRATION ON
CAUSTIC SODA SERVICE APPLICATION
EFFECT OF TEMPERATURE AND CONCENTRATION ON EFFECT OF TEMPERATURE AND CONCENTRATION ON
CAUSTIC SODA SERVICE APPLICATION CAUSTIC SODA SERVICE APPLICATION
CORROSION DATA SURVEY; NACE, 1968, p 4
0
50
100
150
200
250
300
0 10 20 30 40 50
CONCENTRATION OF NaOH %
T
E
M
P
E
R
A
T
U
R
E

F
AREA "C" AREA "C"
NICKEL ALLOYS TO BE CONSIDERED NICKEL ALLOYS TO BE CONSIDERED
IN THIS AREA IN THIS AREA
AREA "A" CARBON STEEL AREA "A" CARBON STEEL
NO STRESS RELIEF NECESSARY NO STRESS RELIEF NECESSARY
AREA "B" AREA "B"
CARBON STEEL CARBON STEEL
STRESS RELIEVE WELDS & BENDS STRESS RELIEVE WELDS & BENDS
H
2
S Scavengers
Reactive/Conversion Additives
H
H
2
2
S Scavengers
S Scavengers
Reactive/Conversion Additives
Reactive/Conversion Additives

Advantages:
Advantages:

Non
Non
-
-
reversible
reversible
Rapid reaction
Rapid reaction

Selective for H
Selective for H
2 2
S
S
Wide range of fuels
Wide range of fuels

Oil Soluble Additives &
Oil Soluble Additives &
Rxn
Rxn
. Products
. Products

May be used at high temperature & with
May be used at high temperature & with
caustic
caustic
Organic Compounds
Organic Compounds
H
H
2 2
S + Sulfix product alkyl sulfides
S + Sulfix product alkyl sulfides
(RSR)
(RSR)
H2S Scavenger Application H2S Scavenger Application
H2S Scavenger Application

Scavenger/hydrocarbon mixing important
Scavenger/hydrocarbon mixing important

Injection quill
Injection quill

Injection up
Injection up
-
-
stream of sample point
stream of sample point

Continuous injection
Continuous injection

Storage tank mixing, blending
Storage tank mixing, blending

Transportation vessel effects

Transportation vessel effects

Steam coils, temperature
Steam coils, temperature

Compartment seals
Compartment seals

Soda bottle
Soda bottle

effect
effect