Fundamental and Practical Aspects of the Claus

Sulfur Recovery Process

P.D. Clark
Professor of Chemistry, University of Calgary
Technical Manager, Alberta Sulphur Research Ltd.
and N.I. Dowling and M. Huang, ASRL
H
2
S + O
2
S
8
+ H
2
O + HEAT
Looks simple enough actually very complex
The Topsoe Catalysis Forum 2007
REACTION
FURNACE
CONDENSER CONDENSER
WASTE
HEAT
BOILER
CONDENSER
Liq. S
8
Liq. S
8
AIR
THERMAL STAGE
Liq. S
8
Liq. S
8
Al
2
O
3
CATALYTIC STAGES
Simplified Process Scheme for the Claus Sulfur Recovery Process
RE-HEATER
Al
2
O
3
RE-HEATER
2H
2
S: SO
2
N
2
, H
2
O
2H
2
S: SO
2
N
2
, H
2
O
Tail gas
H2S/
CO2
HIGH TEMP.
a
b
c
LOW TEMP.
CLAUS PLANT STRAIGHT-THROUGH CONFIGURATION
30% & H
2
S
CONV 3
205
o
C
CONV 2
225
o
C
CONV 1
305
o
C
WHB F
THERMAL STAGE
CATALYTIC
STAGE
TGCU
PRACTICAL
LIMIT
Claus Sulfur Recovery
T
H
E
O
R
E
T
I
C
A
L

R
E
C
O
V
E
R
Y

O
F

S
U
L
F
U
R

(
%
)
(S
8
)
N
2
, H
2
O, H
2
S / SO
2
,
S
2
, CS
2
, COS, CO,
N
2
, NO, NH
3
, SO
3
Equilibrium Composition of Sulfur Vapour
S=S
> 95%
S
S
S
S S
S
S
S
The Overall Chemistry of the Claus Furnace
Air or O
2
900 - 1300C
H
2
S / CO
2
(acid gas)
10 H
2
S + 5 O
2
2 H
2
S + SO
2
+
7
/
2
S
2
+ 8 H
2
O + Heat
Condenser
Liquid S
8
H
2
S / SO
2
ratio can be
altered by controlling
O
2
input
Claus Furnace - Primary Combustion Processes (Fast)
acid gas
(H
2
S/CO
2
/H
2
O/CH
4
)
O
2
(N
2
)
Combustion chamber
2500
o
C 1300
o
C
WHB
600
o
C
flame zone
Anoxic zone
Products
H
2
S + 3/2 O
2
SO
2
+ H
2
O (1)
2 H
2
S + 5/2 O
2
2 SO
2
+ H
2
O + H
2
(2)
2 H
2
S + O
2
S
2
+ 2 H
2
O (3)
2 H
2
S + 1/2 O
2
S
2
+ H
2
O + H
2
(4)
H
2
S/O
2
Ratio
0.66
0.80
2.0
4.0
Claus Furnace - Anoxic, High T Processes (Sulfur Species)
acid gas
O
2
(N
2
)
Combustion chamber
2500
o
C 1300
o
C
WHB
600
o
C
flame
zone
Anoxic zone
Products
3/2 S
2
+ 2 H
2
O 2 H
2
S + SO
2
S
2
+ 2 H
2
O H
2
S + H
2
+ SO
2
(favoured)
2 H
2
S 2 H
2
+ S
2
2 H
2
+ SO
2
2 H
2
O + 1/2 S
2
Claus Furnace - Anoxic, High T Processes (Hydrocarbons)
acid gas
(H
2
S/CO
2
/CH
4
/H
2
O)
O
2
(N
2
)
Combustion chamber
2500
o
C 1300
o
C
WHB
600
o
C
flame
zone
Anoxic zone
Products
minor
component
CH
4
C + 2 H
2
C + H
2
O CO + H
2
CO + H
2
O CO
2
+ H
2
CH
4
+ 2 H
2
O CO
2
+ 4 H
2
Overall:
endothermic
a source of hydrogen
Also: CH
4
+ 2S
2
CS
2
+ 2H
2
S
C + S
2
CS
2
Note: Other hydrocarbons also lead to CS
2
Claus Furnace - Anoxic, High T Processes (CO
2
Chemistry)
acid gas
O
2
(N
2
)
Combustion chamber
2500
o
C 1300
o
C
WHB
600
o
C
flame
zone
Anoxic zone
Products
Explains increasing
COS at increased t
(res)
CO
2
+ H
2
CO + H
2
O
CO
2
+ H
2
S COS + H
2
O
2 CO + S
2
2 COS
2 CO
2
+ S
2
CO + COS + SO
2
Ammonia Destruction in the Claus Furnace
acid gas
O
2
(N
2
)
Combustion chamber
2500
o
C 1300
o
C
WHB
600
o
C
flame
zone
Anoxic zone
Products
(H
2
S / CO
2
)
SWSG
H
2
S / NH
3
/ H
2
O
2 NH
3
+ 3/2 O
2
N
2
+ 3 H
2
O
2 NH
3
+ O
2
N
2
+ H
2
+ 2 H
2
O
2 NH
3
+ O
2
N
2
+ 2 H
2
+ H
2
O
2 NH
3
N
2
+ 3 H
2
Exothermic
Endothermic
More O
2
must be added to the combustion chamber
Effect of Rates of Oxidation on Ammonia Destruction
acid gas
O
2
(N
2
)
Combustion chamber
2500
o
C 1300
o
C
WHB
600
o
C
flame
zone
Anoxic zone
Products
SWSG
H
2
S / NH
3
/ H
2
O
Oxidation rates: H
2
S >> NH
3
CH
4
Consequences: H
2
S + 3/2 O
2
SO
2
+ H
2
O
(excess)
4 NH
3
+ 3 SO
2
2 N
2
+ 6 H
2
O + 3/2 S
2
2 NH
3
+ SO
2
N
2
+ 2 H
2
O + 1/2 S
2
+ H
2
CONV 3
205
o
C
CONV 2
225
o
C
CONV 1
305
o
C
WHB F
THERMAL STAGE
CATALYTIC
STAGE
TGCU
PRACTICAL
LIMIT
Claus Sulfur Recovery
T
H
E
O
R
E
T
I
C
A
L

R
E
C
O
V
E
R
Y

O
F

S
U
L
F
U
R

(
%
)
(S
8
)
N
2
, H
2
O, H
2
S / SO
2
,
S
2
, CS
2
, COS, CO,
N
2
, NO, NH
3
, SO
3
Claus Sulfur Recovery
CONV 3
205
o
C
CONV 2
225
o
C
CONV 1
305
o
C
WHB F
THERMAL STAGE
CATALYTIC
STAGE
TGCU
PRACTICAL
LIMIT
150 305C
(Direct O
2
)
(Indirect heat
exchange)
Claus Converter Chemistry - Main Reaction
ALUMINA CATALYST BED
2H
2
S + SO
2
[CS
2
]
200
O
C - 315
O
C
SULFUR
CONDENSER
R
S
2H
2
O + 3/8S
8
Al-O S
O
O
+ 2H
2
S
ads
2H
2
S + SO
2
2H
2
O + 3/8 S
8
CS
2
+ 2 H
2
O 2 H
2
S + CO
2
Al
2
O
3
speeds up reaction
Note: SO
2
adsorbed preferentially along with water
Sulfate on Claus Catalysts - Commercial Observations
Al
2
O
3
Al
2
O
3
liquid S
8
2 : 1 H
2
S/SO
2
, N
2
, H
2
O (trace impurities)
2 : 1 H
2
S/SO
2
(lower concentration)
1
st
Converter 2
nd
Converter 3
rd
Converter
1 - 2 3 - 4 > 4
Sulfate (wt%)
on catalyst
T (
o
C,
o
F) 320, 608 260, 500 220, 428
Conclusion: sulfate is always found on alumina catalysts
Evidence for Sulfur Oxy Anions on Alumina
1. Lavalley et al. (France)
FTIR on recovered catalyst: Sulfate and polythionates (S
n
O
y
2-
)
Conclusion: Sulfate and other species were thought to arise
by ingress of O
2
into the reactor
Consequence: When sulfate was discovered on commercial
catalyst, it was replaced (lower CS
2
conversion)
How Is Sulfur Formed on an Al
2
o
3
Claus Catalyst?
The Claus Reaction
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
SO
2
+ H
2
O [H
2
SO
3
] 2H
+
+ SO
3
2-
SO
3
2-
+ 1/8 S
8
S
2
O
3
2-
S
2
O
3
2-
+ SO
2
S
3
O
5
2-
S
3
O
5
2-
+ H
2
S H S
4
O
4
+ OH
H S
4
O
4
+ H
2
S [S
3
] + H
2
O + H S
2
O
3
H S
2
O
3
+ OH H
2
O + S
2
O
3
2-
H S
2
O
3
+ OH SO
4
2-
+ H
2
S
SO
4
2-
+ H
2
S H
2
O + S
2
O
3
2-
OR
2 [ S
3
] S
6
~ S
6
S
x
x = 6, 7, 8, 26
predominant species
S
8
Formation
The formal mechanism
Can the Formal Mechanism for the Claus Reaction Be Justified?
1. SO
3
2-
+ S
8
S
2
O
3
2-
[2]
Where does the sulfur come from?
H
2
S or SO
2
in N
2
S
8
(vap)
320C
[No O
2
]
Key Points:
1. Sulfur can be detected in the gas phase
2. Sulfate and thiosulfate can be detected on the surface [IC]
Al
2
O
3
[oxide sites] SO
4
2-
S
2
O
3
2-
Deductions from the Sulfur Formation Mechanism
1. Thiosulfate (S
2
O
3
2-
) or a related surface species initiates
cycles of H
2
S/SO
2
conversion.
2. Sulfate (SO
4
2-
) is part of the catalytic cycle.
3. Sulfate should be reduced by H
2
S.
4. Sulfate should reach a steady state concentration on
the catalyst surface, its concentration being a function
of the H
2
S/SO
2
ratio amongst other factors.
5. Catalyst re-juvenations at high H
2
S/SO
2
ratio likely have
no effect on long term catalyst sulfate contents.
Prediction
A Claus catalyst which does not form sulfate will not work.
Average Bed Weight % SO
4
2-
as a Function of H
2
S:SO
2
Ratio in the
Sulfating Environment at 320
o
C
higher ratio = less sulfate
Steady State CS
2
Conversion as a Function of H
2
S:SO
2
Ratio in the
Sulfating Environment at 320
o
C
higher sulfate lower sulfate
Al
2
O
3
catalyst was pre-aged
at H
2
S/SO
2
= 0.5 [high sulfate]
Laboratory Testing of Claus Catalysts
Sulfate reduced by H
2
S
[Clark, Kijlstra, van Grinsven, Dowling, Huang]
Pre-aged at
2:1 H
2
S / SO
2
ratio
Al
2
O
3
How Does Surface Sulfate Inhibit CS
2
Conversion?
Suggestion
H
2
O H
2
S S=C=S N
2
H
+
SO
4
2-
H
+
H
+
SO
4
2-
[HOS=O]
+
O=S=O
May be
1. SO
2
strongly chemisorbed to sulfate sites
2. High H
2
S partial pressure enables reduction
of sulfate sites reducing degree of sulfate coverage
2 : 1
H
2
S / SO
2
(N
2
, H
2
O,
other components)
S
8
Downstream
units
Consequences of SO
2
Adsorption
Al
2
O
3
SO
2
adsorbed preferentially
H
2
S/SO
2
< 2 during start-up
Al
2
O
3
and TiO
2
possess oxide sites
that convert H
2
S and SO
2
to sulfate
(no O
2
required)
Sulfate is part of the catalytic cycle for
H
2
S/ SO
2
conversion
CS
2
conversion is controlled by
sulfate on the catalyst [H
2
S/ SO
2
, T]

a. Reducing Methods
H
2
S, SO
2
, S
8 (vap)
,
CS
2
, COS
Catalyst
H
2
O, CO
H
2
H
2
S Recycle
b. Direct Oxidation
H
2
S
O
2
Catalyst
H
2
O + 1/8 S
8
c. Sub-dewpoint
2H
2
S + SO
2
3/8 S
8
+ 2 H
2
O
Al
2
O
3
d. Wet Claus
Tail Gas Clean - Up
e. SO
2
capture, recycle
Typical Tail Gas Composition
N
2
H
2
O
H
2
S
SO
2
S
8(vap)
CS
2
COS
H
2
CO
}
}
}
}
major
10 : 1 to 2 : 1 ratio
function of condenser T
may be present due to incomplete
hydrolysis on the catalytic bed
formed in the reaction furnace --
utilized in the reduction processes
Tail Gas Clean-up: Reduction to H
2
S
Reheater
Hydrogenation
reactor
Quench
column
condensate
to SWS
Claus tail gas
air
fuel gas
steam
Gas cooler
Tail Gas Clean Up: Reduction to H
2
S (Continued)
Air/Fuel Gas Chemistry
CH
4
+ 1/2 O
2
CO + 2 H
2
(other rxns also occur)
partial
combustion
CO Shift
CO + H
2
O [HC OH] CO
2
+ H
2
Al
2
O
3
-
CoS/MoS
2
O
reactive intermediate
Hydrogenation Reactions (Al
2
O
3
CoS/MoS
2
)
SO
2
+ 3 H
2
H
2
S + 2 H
2
O
S
x
+ x H
2
x H
2
S
catalyst
Hydrolysis Reactions (Al
2
O
3
)
CS
2
+ 2 H
2
O CO
2
+ 2 H
2
S
COS + H
2
O CO
2
+ H
2
S
H
2
S Recycle
from quench
H
2
S/CO
2
/N
2
(H
2
O)
Selective
Amine
H
2
S
N
2
/CO
2
Tail Gas Clean-up: Reduction to H
2
S (Continued)
Low Temperature Tail Gas Reduction
Hydrogenation
reactor
Quench
column
condensate
to SWS
Claus tail gas
steam
Gas cooler
Indirect re-heater
> 300 240C
Catalyst active at lower temperatures
Low Temperature Reducing Tail Gas Chemistry
Al
2
O
3
MoS
2
CoS
Hydrogenation and
CO shift sites
Claus sites
Claus chemistry (equilibrium favored at low temperatures)
Hydrogenation chemistry
Shift chemistry
Hydrolysis chemistry
2 H
2
S + SO
2
[S
3
] + 2 H
2
O
S
3
+ 3 H
2
3 H
2
S
SO
2
+ 3 H
2
H
2
S + 2 H
2
O
CO + H
2
O CO
2
+ H
2
CS
2
+ 2 H
2
O CO
2
+ 2 H
2
S
COS + H
2
O CO
2
+ H
2
S
Can the Modified Claus Process Be Modified?
Current technology
Overall:
Thermodynamics:
10 H
2
S + 5 O
2
7
/
2
S
2
+ 8 H
2
O + 2 H
2
S + SO
2
+ HEAT
Adiabatic temperature is ~ 1400C,
equilibrium calculations show SO
2
is a major product which is observed.
New approach [Clark and ConocoPhillips, independently]
Overall:
Thermodynamics:
Experimentally:
4 H
2
S + O
2
2 S
2
+ H
2
O + H
2
+ HEAT
Adiabatic temperature is ~ 1100C,
virtually no SO
2
is predicted.
Gas phase reactions produce lots
of SO
2
- a kinetic product.
SCT Catalytic Oxidation of H
2
S
V
2
O
5
/ Al
2
O
3
Al
2
O
3
H
2
S + O
2
S
8
+ H
2
O
H
2
S +
3
/
2
O
2
SO
2
+ H
2
O
2 H
2
S + SO
2
S
8
+ 2 H
2
O
H
2
S/ CO
2
O
2
Steam
H
2
O (l)
2 H
2
S + O
2
S
2
+ H
2
+ H
2
O
SV = 10
5
h
-1
O
2
inlet controlled
Liq. S
8
~ 80%
H
2
S, H
2
, H
2
O
CO
2
, CO
O
2
H
2
S (SO
2
), H
2
, CO
CO
2
, H
2
O
Tail gas
treatment
H
2
O
(5%)
H
2
S recycle)
H
2
, CO
2
Liq. S
8
(15%)
Al
2
O
3
H
2
S Assisted Partial Oxidation of Ethane
CH
2
=CH
2
+ by-products
Gaspers Work
(Not specified)
C
2
H
6
/ H
2
S/O
2
/ He
700 C, ~10secs
Cd/SiO
2
/Al
2
O
3
1/1.5/0.75/10
2H
2
S + O
2
S
2
+ H
2
O + Heat
Fast Kinetics
H
2
S + CH
2
=CH
2
CH
3
CH
3
+ S
2
Heat
Gasper, Can. J. Chem. Eng. 49, 248 (1971)
Originally studied by Imperial Oil in Sarnia, Ontario
An adiabatic process, H
2
S would act as an O
2
transfer agent.
Data collected at high dilution, Cd-based catalysts deemed
environmentally unacceptable, process residence time
(10 seconds) much too long
ASRL decided to re-examine this chemistry when natural gas prices
spiked in 1999-2000
2H
2
S + O
2
2H
2
O + S
2
- 314 KJ/mol
S
2
+ 2 CH
3
CH
3
2 H
2
S + 2 CH
2
=CH
2
2 (+ 51. 5KJ/mol)
Rapid consumption of O
2
by H
2
S limits the formation of CO
and CO
2
S
2
oxidizes ethane selectively to ethylene while H
2
S is
reformed
Oxidation of H
2
S supplies heat for the thermal cracking of
ethane process
Fast kinetics
H
2
S regenerated
Chemistry Advantage:
CH
3
CH
3
H
2
+ CH
2
=CH
2
+ 136.9KJ/mol
Simplified Mechanism of H
2
S Promoted ODHE
Enthalpy of reaction
Formation of Ethylene, H
2
S and H
2
in the Sulfur Assisted ODH of Ethane
Ethylene and H
2
H
2
Sand Ethylene
CH
3
CH
3
+ S
2
CH
3
CH
2
+ HS
2
HS
2
+ CH
3
CH
2
CH
2
=CH
2
+ [H
2
S
2
]
[H
2
S
2
] H
2
+ S
2
OR
CH
3
CH
3
H
2
+ CH
2
=CH
2
[H
2
S
2
] 2 HS
2 HS + CH
3
CH
3
CH
2
=CH
2
+ 2 H
2
S

Production of Ethylene Using Elemental Sulfur

Air
Acid gas
(H
2
S/SO
2
)
Converter train/
Tail gas unit
Liq. S
8
S
2
vap.
(800
o
C)
CH
3
CH
3
Liq. S
8
CH
2
=CH
2
(79.6%)
CS
2
(1.0%)
CH
3
CH
3
(11.9%)
H
2
S, hydrogen
CH
2
=CH
2
separation, purification
CS
2
, return to Claus furnace
CH
3
CH
3
(recycle)
H
2
S, return to Claus furnace
850
o
C
Packing or
Catalyst
CH
3
CH
3
1
/
2
S
2
CH
2
=CH
2
+ H
2
S
Claus furnace
1000C
Current Processes for the Production
of Propylene and Butylenes
1. Catalytic cracking of gas oils in refineries
Propylene (CH
2
=CHCH
3
) is isolated as a by-product from the off-gases
Zeolite catalytic cracking catalysts can be tailored to maximize propylene
production [at the expense of other products (gasoline)]
2. Dehydrogenation processes, e.g. CATOFIN
The catalyst CrO
3/
Al
2
O
3
has to be regenerated frequently to remove coke
Multiple reactors are used in a commercial plant
Some butylene processes work at reduced pressure
R
Propane
Heat
Propylene + by-products + coke
Catalytic Partial Oxidation of Propane in the Presence of H
2
S
Feed (moles)
Propane 12.9
H
2
S 27.0
N
2
47.1
O
2
13.0
10 ms
750
o
C
V
2
O
5
/SiO
2
%Selectivity %Yield
CH
3
CH=CH
2
65 61
CH
2
=CH
2
20 19
CH
4
9 9
CO
2
0.5 0.5
CO 2.0 2.0
Note: Small quantities of CO,
CO
2
, COS, CS
2
, S
2
and SO
2
(trace) are also formed. Overall conversion: ~ 94 95%
(Y. Li and P.D. Clark)
Observations:
Yield of propylene (61%) vastly exceeds any other result
reported for ODH of propane
Total olefin yield ~ 80% in single pass
Effect of TOS on Catalytic ODH of Propane over 10%V
2
O
5
/SiO
2
Catalyst at 725 C and 10 ms Contact Time
Time on stream / min
C
o
n
v
e
r
s
i
o
n

(
%
)
The conversion of C
3
H
8
was maintained at 94-95%
in 8 h time on stream at 725 C.
0
10
20
30
40
50
60
70
80
90
100
0 100 200 300 400 500
C3H8 conversion
H2S conversion
Effect of TOS on Catalytic ODH of Propane over 10%V
2
O
5
/SiO
2
Catalyst at 725 C and 10 ms Contact Time
1. The selectivity to C
3
H
6
was maintained at 63-66% in
8 h time on stream at 725 C.
2. Overall, no loss of reactivity of the catalyst was observed
in the 8 h experiment.
Time on stream / min
S
e
l
e
c
t
i
v
i
t
y

o
r

Y
i
e
l
d

(
%
)
50
55
60
65
70
75
80
85
90
0 100 200 300 400 500
Selectivity to C3H6
Yield of C3H6
Yield of C3H6+C2H4
Oxidative Dehydrogenation of Butane
in the Presence of H
2
S
CH
3
CH
2
CH
2
CH
3
+ O
2
/H
2
S CH
3
CH=CHCH
3
+ H
2
O[H
2
S] + Heat
Butane 2-Butylene
Potentially a very attractive process in comparison to commercial processes
as it is an autothermal process requiring no external fuel
Preliminary results:
Butane/catalyst/700
o
C 10 1 1.5 3.3 1.1 5.9
Butane/O
2
/catalyst/700
o
C 42 6.5 9.2 17.6 5.1 31.8
Butane/O
2
/H
2
S/catalyst/700
o
C 93.5 10.3 12.8 25.4 31.3 69.5
Butane/O
2
/H
2
S/700
o
C 74.0 9.3 9.7 22.6 20.8 53.1
Butane conv.(%) %Methane %Ethylene %Propylene %Butenes %Olefins (Total)
CH
3
CH
2
CH
2
CH
3
+ N
2
/O
2
+ H
2
S
1: 8:2: 1
(air)
V
2
O
5
/SiO
2
, T=700
o
C, t
(res)
=10ms.
Conceptual Mechanism for the Partial Oxidation of Propane
over V
2
O
5
/SiO
2
in the Presence of H
2
S
2 V
5+
+ H
2
S 2 V
4+
+ 2 H
+
+ S
2
2 V
4+
+ 2 H
+
+ O
2
H
2
O + 2 V
5+
1/2 S
2
+ 2 V
4+
2 V
5+
+ S
2-
H
2
S + O
2-
H
2
O + S
2-
2 V
5+
+ S
2-
+ CH
3
CH
2
CH
3
2 V
4+
+ H
2
S + CH
3
CH=CH
2
2 V
4+
+ H
2
S S
2-
+ 2V
5+
+ H
2
Major products are propene, water, hydrogen and hydrogen sulfide
Acknowledgements
Dr. Minming Huang
Dr. Norman Dowling
Dr. Yingwei Li PDF
Dr. Shunlan Liu
Senior Research
Scientists
All colleagues at ASRL
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