ALBERTA SULPHUR RESEARCH LTD.

Cent er f or Appl i ed Cat al ysi s and Indust ri al Sul f ur Chemi st ry
Uni ver si t y Resear ch Cent r e, #6 – 3535 Resear ch Road N. W.
Cal gar y, Al ber t a, Canada T2L 2K8
Count ry Code: 001 Of f i ce: 403 - 220 – 5346 Fax: 403 - 284 – 2054
E-mai l : asr i nf o@ucal gar y. ca
Websi t e: www. chem. ucal gar y. ca/ asr /


ASRL CORE RESEARCH PROGRAM
April 1
st
, 2011 – March 31
st
, 2012




The research program described in the following pages has been compiled with input of the member
companies and research staff of ASRL. The research projects were evaluated by the members of the
Technical Advisory Committee (TAC) (listed below) and are compiled in the priority as per the TAC
evaluation.




MEMBERS OF THE TAC

 Leslie May - BAKER PETROLITE.
 J.K. Chen - CHEVRON ENERGY TECHNOLOGY COMPANY.
 Michael Choi – CONOCOPHILLIPS COMPANY
 Robert Mann - HAZCO ENVIRONMENTAL AND DECOMMISSIONING
SERVICES.
 Jon Gorrie - HUSKY ENERGY INC.
 Sander Kobussen - JACOBS /COMPRIMO SULFUR SOLUTIONS.
 David Stevens - KPS TECHNOLOGY & ENGINEERING LLC.
 Bruce Klint – SULPHUR EXPERTS INC.
 Gavin Proudfoot – SUNCOR ENERGY
 Ken Sourisseau - SHELL CANADA LTD.
 Mark Mazerolle - SULTRAN LTD.
 Mahin Rameshni – WORLEYPARSONS.
 Paul Davis – ALBERTA SULPHUR RESEARCH LTD.
 Peter Clark - ALBERTA SULPHUR RESEARCH LTD.
 Norm Dowling - ALBERTA SULPHUR RESEARCH LTD.
 Rob Marriott - ALBERTA SULPHUR RESEARCH LTD.
 Alex Primak- ALBERTA SULPHUR RESEARCH LTD.


ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

1
LIST OF CORE RESEARCH PROJECTS

1. A Re-examination of Liquid Sulfur Vapour Pressure

Commercial Objective: To re-examine the vapour pressure for elemental sulfur at
temperatures just above the melt to improve models for sulfur deposition and sub-dewpoint
catalysis.

By comparison to experimentally-calibrated models developed at ASRL, the sulfur content
determination can be used to forecast sulfur deposition during the lifecycle of a well. This
information can be used to design and implement sulfur solvent strategies for production of the gas
as well as to calculate gas flow rates that will maximize ultimate gas recovery. Through
development of those models, it was discovered that there must be a large systematic error in the
available sulfur vapour pressure. Because the error likely existed in the liquid data (only one data
set available, West and Menzies, 1929), it is proposed that new measurements of the vapour
pressure are required. These measurements will be used to improve several sulfur phase behavior
models, including those used to estimate sulfur deposition and those used within sub-dewpoint
catalysis.

Specific Objectives

(a) To measure the sulfur vapour pressure of liquid elemental sulfur.
(b) Improve the calculation for the standard state fugacity of elemental sulfur (vapour pressure
equation).
(c) Recalibrate ASRL’s sulfur solubility model.

VAPOUR PRESSURE OF LIQUID ELEMENTAL SULFUR
(THE CALCULATED VAPOUR PRESSURE OF THE LIQUID AT
THE MELT HAS BEEN FORCED TO EQUAL THE SOLID)
-10
0
10
20
30
40
50
350 450 550 650 750 850 950 1050 1150 1250 1350
T / K
1
0
0
·
[
(
p
l
,
v
p

p
l
,
v
p
c
a
l
c
)

/

p
l
,
v
p
c
a
l
c
]

FIGURE 2. The differences between reported vapor pressures of elemental sulfur and
the vapor pressure calculated using Equation (9). ●, experimental data of Baker [1971];
◊, experimental data of Rau et al. [1973]; ○, experimental data of West and Menzies
[1929];
________
, calculated using the Wagner equation of Peng and Zhao [2001];
__ __ __ __
,
calculated from the equation of Rau et al. [1973];
_ _ _ _ _ _
, calculated using the equations
of Shuai and Meison [1995].



ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

2
2. Improved Liquid Sulfur Degassing Technologies

Commercial objective: To examine the technology for solid catalyst liquid sulfur degassing

Over the last year, our studies have shown that alumina and silica-based materials are effective
agents for the decomposition of H
2
S
x
and when used in combination with a sparge gas, lead to very
effective sulfur degassing. In addition to use of inert sparge gases (e.g. nitrogen), it was found that
air could be used in combination with silica without producing excessive SO
2
and Claus tail gas
was very effective despite its H
2
S content. Claus tail gas is an especially interesting sparge gas as
the degasser effluent could be recombined with the process gas entering the tail gas clean-up unit.

All of the objectives of the 2010-2011 program have been met and published at ASRL Chalk Talks
although most of this material remains to be written up. Initial studies using monolith ceramic
structures as the degassing catalyst have resulted in deep degassing. This observation is a key one
as the mechanical strength of mullite-based monoliths should allow development of a robust
degassing system.

Specific Objectives

(a) Complete work with monolith catalysts.
(b) Publish degassing data accumulated over the last two years in the ASRL QB and commercial
journals.

IMPROVED LIQUID SULFUR DEGASSING TECHNOLOGIES
H
2
S
x
Formation Kinetics as a
Function of Temperature
(Uncatalyzed/Catalyzed)
H
2
S/H
2
S
x
Degassing of Liquid Sulfur over Solid Catalysts with Co-current Gas Sparge
Degassing Kinetics over Metal Oxide Catalysts
(0.05 – 5.0 wt% Fe
2
O
3
/Al
2
O
3
, ¸-Al
2
O
3
, SiO
2
, TiO
2
)
Sparge Gas
Selection
(N
2
, Air, Tail Gas)
Catalyzed H
2
S/H
2
S
x
Degassing as a
Function of
Temperature
(130 – 170 °C)
Flowing Liquid Sulfur
H
2
S/H
2
S
x
Degassing
over an Immobilized
Catalyst Bed with
Simultaneous Gas
Sparging
(Catalyst Particles/Pellets )






ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

3
3. Catalytic Tail Gas Incineration

A gold-based titania catalyst prepared in the ASRL laboratories has been demonstrated for
conversion of all sulfur species to SO
2
as well as for conversion of CO to CO
2
and H
2
to H
2
O. This
catalyst may represent a considerable advance for Claus tail gas incineration as it would eliminate
the use of methane in classic thermal incineration. It is composed of titania nano-fibres which are
modified with gold and lanthanum oxide. Since this preparation may be expensive to produce
commercially, it is recommended that studies be performed using titania – lanthanum oxide
composites which are not of nano-dimensions, a suggestion supported by calculations performed in
our laboratories.

It will also be useful to demonstrate to what degree, if any, that SO
3
is produced during catalytic
incineration with the gold-titania catalyst.

Specific Objectives

(a) Preparation and testing of titania – lanthanum oxide composites for gold-based catalytic
incineration.
(b) Determination of SO
3
formation during catalytic incineration

Claus Tail Gas
Au supported on
La-Ti mixed
oxide nanofibres
STACK
T: 300 – 400
o
C
S.V. = 5000 h
-1
(H
2
O)
Steam(~300
o
C)
Tail Gas Component Mole%
Nitrogen, N
2
60 – 40
Water Vapour, H
2
O 40 - 20
Carbon Dioxide, CO
2
30 - 1
Sulfur Dioxide, SO
2
0.5 – 0.1
Hydrogen Sulphide, H
2
S 1 – 0.2
Sulfur, S
8
(vap.) <1
Carbon Disulfide, CS
2
<0.5
Carbonyl Sulphide, COS <0.5
Hydrogen, H
2
3 – 1.0
Carbon Monoxide, 2 – 0.5 CO
100%
Conversions for
the full oxidation
of all these species
PRE-HEAT
CATALYTIC TAIL GAS INCINERATION: A BREAK
THROUGH IN YEAR OF 2010



4. Measurement of Acid Gas Properties at High Pressure

Commercial Objectives: To provide needed density and viscosity data for designing projects
that require handling and injection of high pressure H
2
S/CO
2
and CO
2
/SO
2
mixtures.

ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

4
Density and viscosity are two fundamental properties which are required to design compression
and injection into a target reservoir. Data for acid gas and sour gas injectate fluids are sparsely
available in the open literature due to (i) the difficulty in dealing with H
2
S mixtures and (ii) the low
range of viscosities for gaseous, liquid and supercritical fluids. ASRL has been using an Anton
Paar mPDS Vibrating Tube Density Cell and a VISCO pVT High Pressure Viscometer to measure
these two properties over a broad range of conditions and concentration:

Composition matrix proposed for investigations at T = 0, 50, 100 & 150°C and p = 10, 20, 50, 100,
200, 500 & 1000 bar (145, 290, 725, 1450, 2900, 7550, 14500 psia)
Mixture A B C D E F G H I
H
2
S / mol% 100 25 50 75 25 50 0
CO
2
/ mol% 100 75 50 25 25 0 50
CH
4
/ mol% 100 50 50 50
The shaded compositions have been completed.

Over 40% of the target matrix was completed in the first year of the investigation. For the next
year, the aim is to complete the matrix and investigate some semi-empirical models which can be
used to accurately calculate the viscosity of the mixtures.

Specific Objectives

(a) Complete densities and viscosities for the proposed matrix
(b) Explore semi-empirical correlations for calculating the viscosity of acid gas mixtures

MEASUREMENT OF ACID GAS PROPERTIES AT HIGH PRESSURE
1
10
100
-50 0 50 100 150 200
200 μPa s (0.200 cP) 100 μPa s
50 μPa s
25 μPa s
20 μPa s
17.5 μPa s
15 μPa s
(0.015 cP)
p
/

M
P
a
T / °C
p-n-T Plots for H
2
S
(T
c
, p
c
)
Viscosity Deviation for H
2
SViscosities from
Schmidt et al.
(3)
-20.0
-15.0
-10.0
-5.0
0.0
5.0
10.0
15.0
0 100 200 300 400 500 600 700 800 900
T = 150 °C
T = 100 °C
T = 50°C
T = 0 °C
1
0
0
-
(
n
(
e
x
p
)
-
n
(
c
a
l
c
)
)

/

n
(
c
a
l
c
)
p(calc) / (kg m
-3
)
T = 150 °C
T = 100 °C
T = 50°C
T = 0 °C
1
0
0
-
(
n
(
e
x
p
)
-
n
(
c
a
l
c
)
)

/

n
(
c
a
l
c
)
p(calc) / (kg m
-3
)




ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

5
5. Ceramic-Packed Claus Furnaces

Commercial objective: to develop a simplified process for acid gas combustion and low
quality acid gas treatment

The standard Claus furnace consists of a ceramic brick-lined chamber and a burner to introduce
acid gas and air. Careful design of the burner allows efficient heat and mass transfer but, when
such systems malfunction, as may be the case through unanticipated corrosion, the flame may
impinge on the side walls or tube sheet causing significant damage. In the case of low H
2
S content
acid gas, flame instability and low temperatures result in poor acid gas combustion with
undesirable consequences to downstream equipment.

It is possible that these undesirable outcomes might be avoided by packing the furnace chamber
with ceramic bricks or rubble (see diagram). A methane burner would be used to bring the system
to a temperature of (ca. 500⁰C) well above “light-off” temperature (ca. 250⁰C) and then acid gas
would be introduced and impinge with air on the hot brick. Oxidation will occur at the hot-brick
surface with, overall, the temperature of the brick attaining the adiabatic value for that system. The
methane supply would be shut down or turned down to achieve the desired temperature for poor
quality acid gas cases. Advantages of this arrangement include an “isothermal” operation, no
flame impingement, large heat capacity and probable catalytic conversion of aromatics (BTX) and
other hydrocarbons. In the case of low quality acid gas, the catalytic effect of the brick should
greatly reduce fuel gas use and eliminate the need for acid gas enrichment.

Specific Objectives

(a) Demonstrate the packed chamber approach for acid gas light off and acid gas conversion.
(b) Determine catalytic effects for BTX and hydrocarbon conversion.
(c) Examine ammonia destruction at the adiabatic temperature for this system

THE ISOTHERMAL CLAUS FURNACE
P.D. Clark
S
8
Products
Converters
CH
4
+
Air
• CH
4
/ Air used as pre-heat only
• Packing is catalytic / no CS
2
formation, full BTX and NH
3
destruction
• Furnace operates “isothermally”
• Large heat capacity – no thermal run-away possible
• Refractory and WHB protected by ceramic packing
• CH
4
co-firing built in for low H
2
S content AG
Pre-
heat
Ceramic
Packing
AG
AG
WHB

ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

6
6. Low Pressure Sulfur-Promoted Bitumen Coking

Commercial Objective: To examine a low severity bitumen coking process for the production
of value-added products

Bitumen upgrading processes include a combination of coking and hydro-treating technologies
yielding coke, gases, synthetic crude oil and, in some plants, premium transportation fuels.
Recently, we have discovered that addition of elemental sulfur to bitumen accelerates coking
chemistry allowing rapid conversion to products at a relatively low temperature (ca. 450⁰C). In
addition, the off-gases of the SAC contained large quantities of ethane, propane and butanes
potentially giving this product stream enhanced value. The initial experiment indicates that all of
the added sulfur was converted to H
2
S.

The accelerating effect of sulfur likely involves formation of sulfur free-radicals which initiate
bitumen coking below the standard coking temperature. The objective of this project would be to
delineate conditions for SAC and determine the detailed product composition of gaseous and liquid
products. One commercial benefit of this process would be a lower energy requirement to conduct
the coking step.

Specific Objectives

(a) Examine conditions required to promote sulfur coking.
(b) Determine product composition of liquid and gaseous products

“LOW TEMPERATURE” SULFUR-PROMOTED BITUMEN
COKING
P. D. Clark, P.L. Blais and A. Primak
Oils Sands
Bitumen
451⁰C
Liquids
(Yield = 55 wt%)
Coke
(Yield = 24 wt%)
Gases 21 wt%
[Composition mol%:
H
2
: 2.30, N
2
: 4.55, CO; 0.15,
CO
2
: 1.03, H
2
S: 10.59, C
1
: 45.39,
C
2
: 22.36, C
3
: 9.78, C
4
+
: 4.65]
Liquid S
8
(1.4 wt% S
8
as solid)
High T (450⁰)




ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

7
7. New and Extended Uses of Elemental Sulfur

Commercial Objective: To facilitate use of elemental sulfur in commercial applications
At present, sulfur is required in a variety of industrial applications with fertilizer production
making up the majority use via consumption of the sulfur as sulfuric acid. In the future, it is
expected that the requirements for sulfur will expand considerably through use of sulfuric acid to
extract nickel from nickel oxide ores. Such technology has been in use for at least 3 decades in
Cuba and new projects are under construction or in operation in several other countries. In some of
these projects, due to factors such as the mineral makeup of the local ores and the quality of the
process water, the sulfuric acid leaching step has not been very economical and in some cases has
failed to meet nickel production expectations.
Since nickel oxides represent most of the World’s remaining nickel reserves, some kind of
improved leaching technology will be required.
Specific Objectives
(a) Conduct research to improve nickel extraction from oxide ores.
(b) Review the chemistry of acid leaching for production of uranium and thorium

New Research Direction
nickel ore
Sulfur Solubilizednickel Nickel sulfide
[O]
nickel ore
Sulfur Sulfuric Acid
Solubilizednickel
and other metals
Current Process
T > 200°C
Nickel metal
limestone
landfill
Sulfuric acid
waste
CaSO₄ and 
other solids
Acid mine 
drainage



8. Improved Tail Gas Treatment Processes

Commercial Objective: To examine SO
2
adsorption as the basis for a high efficiency tail gas
process for Claus sulfur recovery systems.

Over the last 2 years, research data obtained suggest that the type of scheme shown in the Figure is
feasible from a chemical viewpoint with demonstration that a modified alumina is suitable for
application in the SO
2
adsorption step. Regeneration of the SO
2
-loaded adsorbent with off-gas
ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

8
from the second converter returned the material to a steady state condition with reproducible SO
2

uptake.
Further studies have shown that use of the adsorbent in a fluidized bed is considerably more
efficient in terms of SO
2
uptake (mass transfer). This approach may also be preferred from an
engineering perspective as the uptake and regeneration temperatures would be held at constant
temperature, so increasing the thermal efficiency of the system. It is suggested that the fluidized
bed approach be examined in a technical and economic evaluation.

Specific Objectives

(a) Test new SO
2
adsorption materials if they become available.
(b) In cooperation with ASRL members or the University Engineering faculty, conduct an
engineering and economic evaluation.

IMPROVED TAIL GAS TREATMENT PROCESSES
ASRL CLAUS TAIL PROCESS


0
0.2
0.4
0.6
0.8
1
1.2
1.4
1 2 3 4 5 6 7 8 9 10
number of cycles
Modif ied-Alumina-A
Modif ied-Alumina-B
Gamma-Alumina
A COMPARISON OF SO
2
ADSORPTION CAPACITIES
Uptake: 80 °C, 1.0% SO
2
, 27.8% H
2
O, 3.5%
CO
2
, 2.0% O
2
and 65.7% N
2
Regen: 350 °C, 1.00% H
2
S, 0.25% SO
2
,
30.00% H
2
O and 68.75% N
2
S.V.= 500h
-1
Fixed Bed
Fluidized Bed
Captured SO
2
: 1.70-1.83 mmol/g
Uptake: 150 °C, 0.54% SO
2
and 7.62%
H
2
O, balanced N
2
S.V.= 3585h
-1

ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

9
9. Primary Upgrading of Oil Sands Bitumen

Commercial Objective: To develop efficient and green technology for upgrading
bitumen/heavy oil using donor solvent chemistry.

Novel methods for primary upgrading of oil sands bitumen are being sought to produce low
viscosity product directly amenable to either hydro-treating to synthetic crude oil or for pipeline
transportation without further addition of diluent. In particular, elimination of the coking step from
bitumen conversion would greatly alleviate environmental concerns and simplify an upgrading
facility. Over the last 2 years, research in our laboratories has demonstrated that sulfur-assisted
donor solvent upgrading can accomplish the goal of producing pipeline viscosity oil with
approximately 25% reduction in sulfur content. The donor solvent would consist of part of the gas
oil fraction produced in the bitumen upgrading facility. The upgraded product should also be
suitable for hydro-treatment to synthetic crude oil. The results obtained to date have been
published at the January 2009 Chalk Talks and have been published in the ASRL QB.

Research now underway is aimed at optimizing the distillate yield and removal of trace metals
from the distillate product by manipulating the process conditions (temperature/sulfur additive
quantity). When this work is complete, ASRL will attempt to have an overall process evaluated
from engineering/economic viewpoints.

Specific Objectives

(a) Delineate process conditions to optimize primary upgrading conditions (donor solvent type and
quantity, process conditions).
(b) Characterize upgraded products to ascertain impact on downstream upgrading units.
(c) Work with ASRL member companies and Alberta Innovates to determine interest to conduct a
field pilot study.

PRIMARY UPGRADING OF OIL SANDS BITUMEN
THE NEW ROAD MAP FOR BITUMEN UPGRADING AND USE
Bitumen
Feed
Sulfur
ASRL Primary Upgrading
Off gases
< 1 wt%
Distillation
Naphtha LGO MGO HGO Residue
Gasification
H
2
To hydrotreaters (HT)
Synthetic crude oil
* C
1
– C
5
and H
2
S / NH
3
recovery systems not shown
S= 4.6wt%
S= 3.6wt%
API= 15 - 20
* *
*
*
* *
(H
2
S, C
1
– C
5
)
HT HT HT
~ 400°C
CO
2
Capture
Electricity
H - Donor


ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

10

PRIMARY UPGRADING OF OIL SANDS BITUMEN
Primary upgrading of bitumen
• Bitumen samples were heated up to
425°C for ~1h with or without the
addition of a hydrogen donor and
sulfur
• Upgrading is observed in the
samples without sulfur
• It was determined that sulfur
promotes coking at these conditions
In-situ upgrading of oil sands
• Samples heated at 200 and 300°C for
one month with and without the
addition of a hydrogen donor and
sulfur
• 300°C showed significant upgrading
while 200°C showed no reaction
• Will perform at least one more set of
experiments to determine the best
way to introduce the additives
0
20
40
60
80
100
120
140
Oil Sand Only OS + H-donor OS + H-donor + S8
V
is
c
o
s
it
y
(
c
p
x
1
0
0
0
)
Viscosity Results of In-situ Upgraded Bitumen
Unreacted
200°C
300°C
0
0.5
1
1.5
2



10. Acid Gas Injection: Water Holding Capacity for Acid Gas Mixtures

Commercial objective: To aid acid gas injection design projects by providing data for the
water carrying capacity of acid gases at conditions up to reservoir injection.

Accurate prediction of the water carrying capacity of acid gas is needed to engineer and operate
acid gas re-injection plants.
Over the past 6 to 7 years ASRL has developed reliable methods for measurement of water
dissolved in sour and acid gases. With this capability in-hand, the literature values for water
carrying capacity of pure H
2
S and CO
2
were surveyed and it was noted that there are very little
water content data for pure H
2
S in the liquid region and CO
2
at typical reservoir conditions (see
figure below). Experimental data for the pure H
2
S species are warranted at conditions that might
be experienced for re-injection of acid or sour gas for disposal or enhanced oil recovery schemes.

In the past year, further developments in capabilities have provided the water content of H
2
S at T =
50°C and up to p = 75 MPa. In the next year H
2
S water contents will be measured at T = 100 and
150°C.

Specific Objectives

(a) Measure the water carrying capacity for pure H
2
S at T = 100 and 150°C.
(b) Time permitting, determine effect of condensable hydrocarbons on water carrying capacity of
acid gas and sour gas mixtures.


ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

11
Helium
(0.2MPa)
GC
Load Position Inject Position
HP Vessel (up to 75Mpa (~11,000psi))
2µL
Loop
50µL Loop
Caustic
Heated Box
Helium
(0.2MPa)
GC
2µL
Loop
50µL Loop
Caustic
Heated Box
HP Vessel (up to 75Mpa (~11,000psi))
ASRL’S CURRENT HIGH PRESSURE WATER
CONTENT VALVE SYSTEM



11. Sulfur Recovery by Direct Oxidation Using Gold-Based Catalysts

Commercial objective: to develop new technologies for low tonnage sulfur recovery and
Claus tail gas processing

Recently, ASRL has demonstrated that gold supported on a mixture of titania and lanthanum oxide
is an effective catalyst for tail gas incineration facilitating rapid conversion of sulfur species to SO
2

at > 150⁰C. This catalyst is also able to oxidize CO and H
2
to CO
2
and H
2
O at typical tail gas
incineration temperatures. It is expected that at lower temperatures, sulfur would be formed by
reaction of SO
2
with un-consumed H
2
S thus providing a catalytic system for conversion of H
2
S to
sulfur when only low quantities of H
2
S are present in the feed gas. An initial experiment confirms
the production of sulfur.

Consequently, it may be possible to use the gold-based catalyst in small scale sulfur recovery, in
removal of trace amounts of H
2
S from shale gases, odour control in bio-gas treatment and in sub-
dew point Claus tail gas treatment. In addition, since this catalyst converts H
2
to water, it may be
possible to use the catalyst as an O
2
scavenger.

Specific Objectives

(a) To determine the ability of the gold-based catalyst to convert H
2
S to sulfur in small scale sulfur
recovery opportunities.
(b) Examine application of the catalyst for O
2
scavenging in natural gas systems.

ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

12
SULFUR RECOVERY BY DIRECT OXIDATION WITH GOLD
P. D. Clark
125-
250⁰C
H
2
S / CH
4
Claus Tail Gas ( ? )
Au / La
2
O
3
- TiO
2
S
8
CHEMISTRY ?
H
2
S +
3
/
2
O
2
SO
2
2 H
2
S + SO
2
3
/
8
S
8
+ 2 H
2
O
Au
TiO
2
• ASRL Au-based incineration catalyst
is active for H
2
S S
8
< 150⁰C
• Applications:
a) Small scale sulfur recovery
b) Shale gas treatment
c) Odour control
d) Sub-dew point Claus TG direct
oxidation



12. Formation of H
2
S in Shale Gas Reservoirs and During SAGD Bitumen Recovery

Commercial objective: To understand mechanisms for formation of H
2
S in shale gas

Shale gas has now changed gas production dynamics in North America to the degree that LNG
terminals for export of methane from both the USA and Canada are now contemplated. However,
several challenges remain for expansion of this resource, including dealing with the small
quantities of H
2
S found in some shale gas. Research was to have been conducted in last year’s
program to determine the mechanism for formation of H
2
S from shale source materials as it was
thought that the H
2
S might arise during fracturing of the reservoir. However, no shale material
could be accessed for the study.
H
2
S production during SAGD recovery of bitumen is also an ongoing problem. This issue has
been examined in the ASRL laboratories since the early 1980’s and was summarized in the most
recent issue of the ASRL Quarterly Bulletin.

Specific Objective

(a) Determine conditions for production of H
2
S from shale source rock if it becomes available

ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

13
FORMATION OF H
2
S IN SHALE GAS RESERVOIRS
AND DURING SAGD RECOVERY OF HEAVY OIL
AND BITUMEN
FORMATION OF H
2
S IN HEAVY OIL-BITUMEN AND
SHALE GAS PRODUCTION
Heavy Oil / Bitumen Shale Reservoirs
CH
4
, C
2+
,CO
2
,
H
2
S, H
2
Organosulfur compounds
steam, 150-300°C
H
2
S + CO / CO
2
/ H
2
CH
4
, (C
2+
)
kerogen (organic sulfur)
CH
4
, C
2+
(trace H
2
S)
• Do stimulation procedures
produce H
2
S from kerogen?
Steam



13. Determination of the Kinetics of H
2
S Oxidation in Compression Systems

Commercial Objective: To determine the potential for sulfur formation in sour compression
systems.

The potential for sulfur deposition in sour compression systems due to trace O
2
is a function of H
2
S
oxidation kinetics and S8 solubility in the sour gas mixture. These kinetics have been investigated
in the temperature and pressure range from 50 – 140
o
C and 100 – 1000 psig for the uncatalyzed gas
phase reaction providing the pseudo-rate expression, rate = kʹ[O
2
], which is first order in O
2
and
contains the pseudo-rate constant, kʹ. In order to apply these kinetics more generally to sour
compression systems the order with respect to H
2
S is required to complete the rate expression.

Specific Objectives

(a) Collect rate data to determine the order with respect to H
2
S.
(b) Test the hypothesis that S8 acts as a catalyst for H
2
S oxidation (i.e. autocatalysis).
(c) Write up results of the laboratory work for publication in the ASRL QB.

ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

14
0.000001
0.00001
0.0001
0.001
0.01
Pressure (psi)
S
8

s
o
l
u
b
i
l
i
t
y

(
p
p
m
v
)
Determination of the Kinetics of H Determination of the Kinetics of H
2 2
S Oxidation in Compression Systems S Oxidation in Compression Systems
H
2
S + 1/2O
2
1/8S
8
+ H
2
O
T = 50 – 140
o
C
P = 100 – 1000 psig
rate = kʹ[O
2
]
Potential for S
8
deposition in sour compression systems is a function
of H
2
S oxidation kinetics and S
8
solubility in sour gas mixtures
0 500 1000 1500 2000 2500
0.01
)
10% H
2
S, 90% CH
4
100% H
2
S
S
8

s
o
l
u
b
i
l
i
t
y

(
p
p
m
v
)
uncatalyzed ; 1000 ppmv O
2
; time = 0.1 s ; 140
o
C
kinetics are much faster
in the presence of bare steel
S
8
formation exceeds sulfur solubility



14. H
2
S and SO
2
Solubility in Liquid Sulfur Updating and Checking FTIR Calibrations

Commercial Objective: Investigation of the uncatalysed Claus reaction in liquid sulfur by
FTIR and modified sulfur/H
2
S mixtures within hermetically sealed IR cells for remotely
checking IR calibrations.

H
2
S dissolved in liquid sulfur often must be degassed before safely transporting or forming. In the
past research year the Henry’s Law correlation for SO
2
solubility and absorption coefficient for
SO
2
was reported relative to H
2
S, so that instruments already in service could be modified to
measure SO
2
in addition to total dissolved H
2
S. While it is known that Claus reaction between SO
2

and H
2
S in liquid sulfur is slow, accurate kinetic rates are unkown. The first part of this research
will seek to follow the rate of reaction using IR. These rates will be used to understand the non-
diffusion limited and uncatalysed rate (chemical rate) which can be used to optimize degassing
and/or limit H2S dissolution.

ASRL has supplied remote IR users with ampoules containing conglomerate mixtures of elemental
sulfur and a hydrogen donor. These can be heated to produce a specific quantity of H
2
S and H
2
S
x

in liquid sulfur. While they are not used to calibrate IR instruments, they can be used to check that
the initial instrument calibration is correct. Recently, some hermetically sealed IR cells have been
investigated for an alternative calibration check; however, more investigations need to be
conducted to avoid breaking the cells upon melting the sulfur/H2S mixture.

ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

15
Specific Objectives

(c) Utilize the new absorption coefficient to determine rates of consumption of SO
2
and H
2
S in
liquid sulfur degassing systems and sulfur storage systems.
(d) Investigate modified sulfur/H
2
S mixtures which could be used to reproducibility melt mixtures
in hermetically sealed IR cells for remotely checking IR calibrations.

H
2
S AND SO
2
SOLUBILITY IN LIQUID SULFUR UPDATING
AND CHECKING FTIR CALIBRATIONS
PRELOADED/SEALED
CALIBRATION CELLS AMPOULE CALIBRATION CHECKS



15. Claus Catalyst Model

Commercial objective: To produce a model for Claus catalyst deactivation

The lifetime of a Claus catalyst depends on the conditions of operation, specifically the reaction
temperature and impurities that might be found in the process gas. For commercial operations, it is
important to know the lifetime of the catalyst in order to plan catalyst change-out frequency. It is
known that catalyst activity depends on carbon contamination, which leads to loss of surface area
and pore volume, and the process temperature and the amount of surface sulphate concentrations.
Specifically, catalyst activity is usually determined by CS
2
conversion.

It is suggested that studies be performed to determine catalyst activity and field lifetimes by
conducting experiments which determine loss of catalyst activity due to hydrocarbon and oxygen
ingress (sulphate production) using CS
2
conversion as the activity parameter. If field samples
become available, surface areas and pore volumes can be determined in tandem with CS
2

conversion activity.

Specific objectives

(a) Conduct laboratory studies to develop a model for deactivation of Claus catalysts.
(b) Analyze field samples for residual activity to relate to the laboratory model.
ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

16
DEACTIVATION MODELING FOR CLAUS CATALYSTS
Al
2
O
3
• How does BTX cause catalyst deactivation?
• Deactivation rates: BTX, hydrocarbons, carsul, sulfates
[carsul] [adsorbed species] BTX SO
4
2-
2 H
2
S + SO
2
3
/
8
S
8
+ 2 H
2
O



16. Kinetics and Mechanisms for Disposable Scavengers

Commercial Objective: To aid design of field application of triazine scavengers

Liquid triazine scavengers are used to remove small quantities of H
2
S from natural gas when total
sulfur tonnages are < 1 ton day. However, little information is available on the kinetics of H
2
S
uptake at typical field conditions, so hampering design of large sacle systems. The objective of this
project will be to make kinetic measurements at relevant, high pressure natural gas applications.

Specific Objective

(a) Determine kinetics for removal of H
2
S from high pressure natural gas using a generic triazine
formulation.

KINETICS AND MECHANISMS FOR DISPOSABLE
SCAVENGERES
R R
R
N N
N
N
N
N
R
S S
N
H
2
S / CO
2
[CH
4
]
• Rates of reaction? Low P, high P
• Effect of temperature; by products?


ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

17
17. Oxygen Consumption in Amine Systems

Commercial Objective: To examine the rate of reaction of oxygen with H
2
S in an amine
contactor

Ingress of oxygen into an amine contactor is known to accelerate the degradation of gas sweetening
amines, probably through oxidation of H
2
S to sulfur and oxy-sulfur anions which then react with
the amines. The rate at which oxygen reacts with H
2
S in an amine system has not been evaluated
and the actual mechanism for amine degradation under contactor conditions has not been reported.
The overall aim of this project would be to determine these aspects of oxygen ingress with respect
to amine degradation.

Specific Objectives
(a) Measurement of the rate of O₂ consumption under amine contactor conditions:
i. Amines evaluated: MEA, DEA, MDEA
ii. Temperature range: 50 to 120°C
iii. Effect of H₂S, CO₂, and SO₂ on the rate of O₂ consumption
iv. Effect of catalyst (eg. Fe³
+
)
(b) Determine lower level of oxygen required to cause amine degradation under conditions studied
in (a).
(c) Attempt to correlate degradation product formation (heat stable salts, bicine, etc.) with
conditions studied in (a) by analyzing reactor contents.




ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

18
18. Designer Hydrocarbon Sulfur Solvents for Sour Gas Production

Commercial objective: To evaluate regeneration options for enhanced, hybrid sulfur solvents

If present in a reservoir fluid, elemental sulfur can deposit when pressure and temperature
reductions occur during production. This deposition can cause flow assurance issues in the near
wellbore region, tubulars, gathering lines and conditioning facilities. Furthermore, solid sulfur
deposition provides for very aggressive sulfur contact corrosion. Traditionally, producers have
either repaired damaged zones or ensure flowing streams using physical hydrocarbon solvents or
chemical solvents, such as diaryldisulfides. In recent years, ASRL studies have shown that
unsaturated hydrocarbons can be used as reactants to form in situ solvents. Two examples are (i)
ethylene for remediation of sulfur in the near wellbore region and (ii) styrene addition to aromatic
hydrocarbons to generate enhanced uptake by formation of organic polysulfides. In the past
research year, the kinetics of sulfur uptake for mixtures of styrene have been conducted at various
temperatures in order to ascertain the chemical rate limitations of the reaction. Two methods for
solvent regeneration will now be investigated: (i) cooling of the solvent to reverse and release
physically and chemically dissolved sulfur and (ii) distillation of aromatic co-solvent to recover the
carrier solvent.

Specific Objectives:

(a) Reporting of sulfur uptake kinetics by addition of olefins (styrene and ethylene)
(b) Regeneration of the enhanced solvents.

DESIGNER SULFUR SOLVENTS FOR SOUR GAS PRODUCTION
Lean Solvent
Regeneration
CH
4
CO
2
S
8
H
2
S
CH
4
H
2
O
Lean Solvent
Regeneration
CH
4
CO
2
S
8
H
2
S
CH
4
H
2
O
Lean Solvent
Regeneration
CH
4
CO
2
S
8
H
2
S
CH
4
H
2
O
Sulfur Uptake by TEX/10%
Styrene/0.1% TEA Sampled
at T = 40°C
0 10 20 30 40 50 60 70 80 90 100
0
1
2
3
4
5
Time (hrs)
w
t
.

%
S
8
C-S-X
S
x



19. Effect of BTX on Reduction Catalysts Used In Tail Gas Processing

Commercial Objective: To determine if trace quantities of BTX can cause fouling of alumina
Co/Mo catalyst when used in Claus tail gas service.
ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

19
BTX is known to foul Claus catalysts (alumina or titania) as a result of oxidative processes which
occur between the hydrocarbon and sulfur and/or oxidized sulfur species. T and X are the most
destructive species in this case. It is also claimed that BTX can foul Co-Mo catalysts in reductive
Claus tail gas units but this observation would be contrary to what might be expected as the
reduction processes that occur mimic those in a classic HDS unit. Thus, T and X would be
expected to form benzene and benzene should be hydrogenated to gas phase products. Is fouling of
Co-Mo catalysts in Claus tail gas units a myth?

Specific Objective

(a) To determine the effect of BTX on an alumina Co-Mo catalyst when used at conditions found
in a reductive Claus tail gas unit.

EFFECT OF BTX ON AL
2
O
3
– CoS / MoS
2
CATALYSTS
MoS
2
CoS
Al
2
O
3
CH
3
CH
3
CH
3
• Are BTX converted to carsul ?
• OR
+ CH
4
Al
2
O
3
– CoS / MoS
2
H
2
- CO
• Does benzene produce carsul ?
B T X
H
2
, CO
H
2
O, N
2
, H
2
S
SO
2
, S
8 (vap)
H
2
S



20. Short Contact Time Claus Process

Commercial Objective: to develop a simplified sulfur recovery process

A thermodynamic analysis of the Claus process suggests that the preferred H
2
S – O
2
ratio is 4:1 as
at this condition sulfur, water and hydrogen are the preferred products.

4 H
2
S + O
2
→ 2 S
2
+ 2 H
2
+ 2 H
2
O

Previous research in our laboratories has shown that short contact time catalysis (SCT) allows
achievement of a product slate close to this ratio when the contact time is around 10 – 50 ms. As
depicted in the figure, pure O
2
could be used in two or more stages so limiting the temperature of
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is located within the Department of Chemistry, The University of Calgary

20
each stage to < 1000⁰C. The key advantages of this type of process is that all of the “usual”
catalytic stages are eliminated in favour of one tail gas stage that uses the standard hydrogenation
of any SO
2
and other sulfur species with return of H
2
S to the thermal stage. Excess H
2
and any CO
would be consumed in a final catalytic incineration stage.

To date, we have not demonstrated destruction of hydrocarbon impurities or ammonia conversion
by SCT so it proposed that these issues be examined in the core research program along with
demonstration of the tail gas stage using the high H
2
concentration produced by SCT.

Specific Objectives

(a) Determination of BTX and hydrocarbon conversion in SCT.
(b) Examination of ammonia destruction using SCT and typical sour water stripper gas
concentration.
(c) Confirmation of tail gas unit operation with species concentrations produced by


SHORT CONTACT - TIME CATALYTIC CLAUS
Liquid S
8
Acid
gas
O
2
O
2
water water
T
1
T
2
Water quench Sour water
Catalytic
incineration
H
2
S
recovery
O
2
O
2
Steam Steam
(SO
2
H
2
S)
H
2
, CO, CO
2
(H
2
O)
• T
1
and T
2
are approximately 800 and 600⁰C
respectively, t
(res)
≈ 10 – 50 ms.
• Reducing and catalytic conditions eliminate
BTX and CS
2
• Conversion to sulfur: 80 – 85% per cycle Atmosphere
H
2
S, H
2
, H
2
O
(SO
2
), (CO)



21. Sulfur Dust Properties

Commercial Objectives: To determine selected properties of sulfur dust pertaining to
handling and transportation of solid sulfur.

In the world of sulfur, sulfur dust poses a challenge in that air borne dust tends to remain
suspended because of the development of surface charges which cause the particles to repel one
another. Critically, air borne dust may spontaneously ignite with explosive force. To support the
hypothesis that sulfur dust is kinetically stable, like most aerosols or fogs, thermodynamic changes
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is located within the Department of Chemistry, The University of Calgary

21
can be investigated for small particle sizes. This involves showing that the melting temperature is
not substantially different for small particles. Finally, for small particles, surface adsorption
reduces the charge potential of a surface. CO
2
, SO
2
and H
2
S surface asorption isotherms for small
particles will be measured for small sulfur particles.

Specific Objective

(a) Characterize the physical properties of sulfur dust by making measurements in the following
areas:
a. Melting point
b. Surface-adsorbed species, e.g., SO
2
, H
2
S, H
2
S
x

c. Surface absorption capacity
d. Water/other boundary effects on sulfur dust vs. formed sulfur

SULFUR DUST MELTING POINTS
- Sulfur dust (lab-generated) melting point experiments have been initiated.
The objective is to heat the sulfur in a slow manner to obtain the physical
melting point which is lower than the observed melting point.



22. Low Tonnage Sulfur Recovery

Commercial Objective: To develop improved technologies for small scale sulfur recovery

Recent work has shown that a solid-phase Claus approach involving reaction of SO
2
with H
2
S in
high pressure natural gas results in effective H
2
S removal (see Figure). These results, presented at
the January 2011 Chalk Talks, demonstrated that bed switching and regeneration would be required
approximately every 60 hours when using basic Claus alumina, but, to date, experiments have not
been performed to validate capture of excess SO
2
using the two-bed system. These studies, and use
of materials designed specifically for SO
2
capture will be conducted to complete this research.

ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

22
An alternative approach is to remove H
2
S with a selective adsorbent/catalyst system followed by
conversion of H
2
S to sulfur off-line from the main gas production. This potential technology has a
distinct advantage in that the sulfur recovery step is decoupled from the gas treatment step so there
is no possibility that either SO
2
or O
2
, if it was used in the H
2
S conversion process, can
contaminate the methane product stream. In addition, it may be possible to transport the H
2
S
adsorbent reactor either by rail or road to a Claus sulfur recovery plant.

Specific Objectives

(a) Complete Claus-based solid sulfur recovery research examining the 2-bed system for SO
2

capture and examine a combined Claus catalyst/SO
2
adsorbent material.
(b) Examine the H
2
S adsorbent concept.

H
2
S REMOVAL BY “SOLID PHASE” CLAUS: THE OVERALL CONCEPT
Natural Gas
CH
4
, (H
2
S)
Filtration
Liq. S
8
O
2
(membrane
unit)
H
2
S: 50 – 5,000 ppmv
P : 250-1000 psi
A
B
C
A B
A, B, a
C
• Bed accumulates solid sullfur; bed acts as polishing reactor and
SO
2
scavenger
• Gas flows: bed when saturated with S
8
, is switched to bed nd bed
(regenerated) becomes SO
2
scavenging bed.
Regen gas (200⁰C)
SO
2
Claus catalyst
2H
2
S + SO
2
3
/
8
S
8
+ 2 H
2
O
Claus catalyst
(SO
2
removal)
(Particle removal)
S
8
(liq)
Dehydration Pipeline (<16 ppmv)



SMALL SCALE SULFUR RECOVERY - H
2
S REMOVAL
S
8
S
8
recovery
Air
HOT GAS
REGENERATION
• If adsorbent bed vessels are on “rail”, vessels can be
transferred to a Claus plant
UPTAKE
Shale gas
CH
4
– H
2
S (10-1000ppmv)
CH
4
(H
2
S < 4 ppmv)
H
2
S-
adsorbent

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is located within the Department of Chemistry, The University of Calgary

23
23. The Sulfur Carrying Capacity of Liquid and Supercritical CO
2


Commercial Objective: To examine the capacity of industrial CO
2
pipeline fluids to carry
dissolved elemental sulfur.

With the advent of CO
2
pipelines for enhanced oil recovery and sequestration, streams containing
sulfur or streams which may have sulfur produced by oxidation could be problematic. In these
cases, a critical parameter is how much sulfur can a CO
2
stream contain before the CO
2
fluid
releases the sulfur from solution (sulfur precipitation). While current ASRL sulfur solubility
models are capable of estimating saturation conditions, there have been no experimental data
available for calibration below T = 60°C. Some recently purchased equipment can be used to
measure sulfur solubility in liquid and supercritical CO
2
at T = 25°C, which is a more reasonable
temperature for surface pipelines.
Specific Objectives

(a) To measure the sulfur solubility in liquid CO
2
(T = 0 and 25°C) and supercritical CO
2
(T =
50°C) up to 2000 psi.
(b) Recalibrate ASRL’s sulfur solubility model to handle low temperature CO
2
fluids.
(c) Time permitting, investigate if the same method can be modified to look at low pressure and
low temperature sour gases (a noted region where no data exists and models are questionable).

ELEMENTAL SULFUR SOLUBILITY IN
HIGH-PRESSURE CO
2
FLUIDS
0
100
200
300
400
500
600
700
800
900
1000
0 5 10 15 20 25
[
S
8
]

/

(
m
g

S
m
3
)
p / MPa
[Exp] Serin et al. (2010)
T = 60°C
[Calc.] T = 60°C
[Calc.] T = 25°C
[Calc.] T = 0°C
[Exp] This Study;
T = 28°C
[Calc.] p
Sat
CO
2
CO
2
(l) 99.99%+
(PraxAir bone dry)
Dry gas meter
(Singer 802;
p = 0.09 MPa)
100 cm
3
Sulfur prill column
(7.67 MPa CO
2
(l); 1¼˝ i.d.)
0.2 um frit
Thermostated needle
valve (T = 30°C)
SFT-10 Supercritical / liquid CO
2
pump
(maintaining CO
2
(l) feed at at p = 7.67 MPa)
Glass-wool traps
First glass-wool trap
after experiment
Experimental sulfur solubility in
liquid/supercritical CO
2
Data requirement - there are no sulfur
saturation data at low temperature and
pressure (we interpolate)
(0<T<60°C; 1<p<1000 psi).
Would elemental sulfur in a CO
2
pipeline really pose a problem?



24. Rate of Decomposition of Polymeric Sulfur

Commercial Objective: To determine the rate of disappearance of polymeric sulfur in solid
sulfur to ascertain the potential for loss of mechanical strength in blocked sulfur.
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is located within the Department of Chemistry, The University of Calgary

24
The polymeric content of solid sulfur has been linked to the mechanical strength of the solid and
this correlation has been strengthened by recent testing using a load cell method. Since polymeric
sulfur is meta-stable with respect to the S8 form it would be expected that the decomposition of
polymeric sulfur in the solid could affect the mechanical strength and hence long-term viability of
blocked sulfur. This study would aim to determine the rate of decomposition of polymeric sulfur
under conditions relevant to the block storage of sulfur. Preliminary measurements at 20
o
C over an
extended time period (approaching 1 year) have shown that the loss of polymeric sulfur is too slow
at this temperature to be accurately determined by direct means. To overcome this issue,
experiments will be performed at higher temperatures, where the rate of decomposition is faster, as
a way of obtaining these data.

Specific Objectives

(a) To determine the rates of decomposition of polymeric sulfur at 70, 80 and 90
o
C.
(b) Using these rates determine the rate of decomposition of polymeric sulfur at conditions
relevant to block storage of sulfur.

0
5
10
15
20
25
30
0 0.5 1 1.5 2 2.5 3 3.5
Polymeric Content (wt %)
C
r
u
s
h

S
t
r
e
n
g
t
h

(
l
b
.

f
o
r
c
e
)
need
longer times
0
5
10
15
20
25
Start 4 mo 8 mo
EFFECT OF POLYMERIC SULFUR ON THE STRENGTH OF THE SOLID EFFECT OF POLYMERIC SULFUR ON THE STRENGTH OF THE SOLID
Crush Strength vs Polymeric Content
0
5
10
15
20
25
C
r
u
s
h
S
t
r
e
n
g
t
h
(
lb
f
o
r
c
e
)
20.65
P
o
l
y
m
e
r
i
c

C
o
n
t
e
n
t

(
w
t

%
)
3.08
longer
time
3.03 3.13
C
r
u
s
h

S
t
r
e
n
g
t
h

(
l
b

f
o
r
c
e
)



25. Recovery of Bitumen from a Subterranean Reservoir

Commercial Objective: to increase the efficiency of bitumen extraction

Steam assisted gravity drainage is used for bitumen recovery from deeply buried oil sands deposits
but suffers the disadvantage of producing large volumes of water with the bitumen along with
some H
2
S-containing gases. In addition, reservoir temperatures must be increased to > 200⁰C in
order to mobilize the highly viscous bitumen. It is suggested that instead of injecting steam, crude
oil be injected into the reservoir along with in situ heating of the reservoir by an indirect method.
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is located within the Department of Chemistry, The University of Calgary

25
The role of the crude oil would be to “dissolve” the bitumen at a temperature (ca. 100⁰C or,
perhaps lower) to produce a mobile phase that could be pumped to the surface, and be suitable for
pipeline transport without further addition of diluent. The advantage of this approach would be
lower overall energy input in comparison to steam injection techniques and reduced gas formation
and, hence, surface handling costs.

Since crude oil contains some “donor” hydrogen within its organic structures, some upgrading of
the bitumen could be anticipated if the reservoir temperature was raised above 250⁰C.

Specific Objectives

(a) Determine the amount of crude oil and temperature needed to reduce the bitumen viscosity to
values required for reservoir recovery
(b) Determine the potential for in situ upgrading at elevated temperatures (> 250⁰C)

RECOVERY OF BITUMEN FROM A SUBTERRANEAN
RESERVOIR
P. D. Clark
• Heating of reservoir by solar generated electricity
• Crude oil “dissolves” bitumen creating a “medium, low viscosity” crude oil
• If viscosity reduction is the key objective, the reservoir T needs to raised only
moderately”
• If higher (>200⁰C) reservoir T is used, some upgrading can be anticipated
(H – donor reactions)
e e e
Oil sands zone
Electric heating
Solar Cell
Light
crude
oil







ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

26
FUNDAMENTAL RESEARCH PROGRAMS

These projects include ongoing research (Graduate student and PDF) which has partial external
funding (University of Calgary and Natural Sciences Engineering Research Council of Canada)

A. Production of C
3
– C
6
Olefins, High Octane Alkylate and Valuable Petrochemicals (ongoing,
Ph.D. studies, Z. Premji)

Previous research in our laboratories has identified new, high efficiency technologies for
production of ethylene and propylene. The chemical principle behind these technologies is partial
oxidation of a hydrocarbon feed using sulfur as an oxygen transfer agent, a strategy that promotes
very selective oxidation and very high yields of the olefins (Figure FRP A). Assessments of this
work by ASRL members suggest that sulfur assisted olefin manufacture would be more efficient
than current technology and, in the case of propylene, represents the highest yield (60%) yet
reported. This work will be expanded as part of the Ph.D. program studies of Zahra Premji.

Specific Objectives

(a) Determine the feasibility of producing a mixed olefin product from a C
3
– C
6
feed.
(b) Use the mixed olefins to synthesize high octane alkane mixture so providing a direct route from
refinery alkane off-gases to gasoline pool mixtures.
(c) Use of the olefin mixture to alkylate benzene so providing a direct synthesis of ethyl, iso-propyl
and butylbenzenes.


FIGURE FRP A. SYNTHESIS OF MIXED OLEFINS AND UTILIZATION IN
ALKYLATE AND ALKYL BENZENE MANUFACTURE
C
3
– C
6
Alkanes CH
3
CH = CH
2
CH
3
CH
2
CH = CH
2
Pentenes
1. Alkylation
OR
2. Aromatics
(e.g. benzene)
High octane alkylate
R’
R = CH
3
CH
2
, C
3
H
2
S / Air




ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

27
B. Computational Modeling of Catalytic Systems (Dr. John Lo)

Commercial Objectives: Use of computational techniques to develop enhanced understanding
of catalytic processes for sulfur recovery.

Recently, density functional theory (DFT) has allowed calculation of more precise models for
surface catalyzed reactions. Much of the theoretical development has been conducted by Dr. T.
Zeigler and colleagues in the Chemistry Department of the University of Calgary. Recently, extra
funding was obtained though the ASRL-University connection to fund a 2 year position to examine
Claus catalysis at the mechanistic level using DFT. This research will also aid the development of
the research in projects # 1 and FRP A (Figure FRP B).

Specific Objectives

(a) Determine the mechanism of SO
2
and H
2
S adsorption at catalytic surfaces, defining the most
suitable materials for SO
2
adsorption.
(b) Examination of the Claus catalytic mechanism.
(c) Investigation of the mechanism of H
2
S assisted oxidation of alkanes to olefins.


FIGURE FRP B. SO
2
/H
2
S CO-ADSORPTION ON HYDRATED (110) C
SURFACE (PATH 2)



ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

28
ASRL is registered as a not-for-profit Company in the Province of Alberta and
is located within the Department of Chemistry, The University of Calgary

29
SPECIAL PROJECTS

Special projects are research efforts which aim to take ASRL core research work to the commercial
demonstration phase. There is currently one such project within the ASRL research portfolio.

1. Above Ground Sulfur Storage

Commercial objective: To develop techniques for long-term, environmentally benign solid
sulfur storage

Sulfur supply/demand cycles over the last 50 years have resulted in the need for temporary block
storage of many millions of tons worldwide. The most recent cycle produced prices of up to
$850/ton but “business as usual” was resumed with prices dropping to < $50/ton during the 2009
recession. “Post recession” pricing is showing some recovery. Potentially, new sour gas fields in
the Middle East and Central Asia, new production in China and oil sands-derived sulfur could
over-whelm the market requiring long term (50+ years) block storage. During the last two years,
ASRL has been working with its members to identify strategies for long term storage and to design
field pilot projects. In one case, laboratory work has been conducted to examine the viability of
spray-on coatings based on construction stucco. This work was reported at the January 2008 and
2009 Chalk Talks.

This project was established in the Fall of 2009, fully founded by four industrial sponsors. The test
blocks have been poured at the Shell Burnt Timber gas plant and instrumentation is being put in
place. Three types of protective coating were applied in the Spring of 2010.

LIST OF CORE RESEARCH PROJECTS 1. A Re-examination of Liquid Sulfur Vapour Pressure Commercial Objective: To re-examine the vapour pressure for elemental sulfur at temperatures just above the melt to improve models for sulfur deposition and sub-dewpoint catalysis. By comparison to experimentally-calibrated models developed at ASRL, the sulfur content determination can be used to forecast sulfur deposition during the lifecycle of a well. This information can be used to design and implement sulfur solvent strategies for production of the gas as well as to calculate gas flow rates that will maximize ultimate gas recovery. Through development of those models, it was discovered that there must be a large systematic error in the available sulfur vapour pressure. Because the error likely existed in the liquid data (only one data set available, West and Menzies, 1929), it is proposed that new measurements of the vapour pressure are required. These measurements will be used to improve several sulfur phase behavior models, including those used to estimate sulfur deposition and those used within sub-dewpoint catalysis. Specific Objectives (a) To measure the sulfur vapour pressure of liquid elemental sulfur. (b) Improve the calculation for the standard state fugacity of elemental sulfur (vapour pressure equation). (c) Recalibrate ASRL’s sulfur solubility model.
VAPOUR PRESSURE OF LIQUID ELEMENTAL SULFUR (THE CALCULATED VAPOUR PRESSURE OF THE LIQUID AT THE MELT HAS BEEN FORCED TO EQUAL THE SOLID)
50 40

100·[(pl,vp – pl,vpcalc) / pl,vpcalc]

30 20 10 0 -10 350 450 550 650 750 850 950 1050 1150 1250 1350

T/K
FIGURE 2. The differences between reported vapor pressures of elemental sulfur and the vapor pressure calculated using Equation (9). ●, experimental data of Baker [1971]; ◊, experimental data of Rau et al. [1973]; ○, experimental data of West and Menzies [1929]; ________, calculated using the Wagner equation of Peng and Zhao [2001]; __ __ __ __, calculated from the equation of Rau et al. [1973]; _ _ _ _ _ _, calculated using the equations of Shuai and Meison [1995].

ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry, The University of Calgary

2

g. SiO2. In addition to use of inert sparge gases (e. Initial studies using monolith ceramic structures as the degassing catalyst have resulted in deep degassing. All of the objectives of the 2010-2011 program have been met and published at ASRL Chalk Talks although most of this material remains to be written up.2. our studies have shown that alumina and silica-based materials are effective agents for the decomposition of H2Sx and when used in combination with a sparge gas. Specific Objectives (a) Complete work with monolith catalysts. Claus tail gas is an especially interesting sparge gas as the degasser effluent could be recombined with the process gas entering the tail gas clean-up unit. Air. -Al2O3. This observation is a key one as the mechanical strength of mullite-based monoliths should allow development of a robust degassing system. IMPROVED LIQUID SULFUR DEGASSING TECHNOLOGIES H2S/H2Sx Degassing of Liquid Sulfur over Solid Catalysts with Co-current Gas Sparge Degassing Kinetics over Metal Oxide Catalysts (0.05 – 5. Improved Liquid Sulfur Degassing Technologies Commercial objective: To examine the technology for solid catalyst liquid sulfur degassing Over the last year. The University of Calgary 3 . lead to very effective sulfur degassing. (b) Publish degassing data accumulated over the last two years in the ASRL QB and commercial journals. nitrogen). it was found that air could be used in combination with silica without producing excessive SO2 and Claus tail gas was very effective despite its H2S content.0 wt% Fe2O3/Al2O3. Tail Gas) Catalyzed H2S/H2Sx Degassing as a Function of Temperature (130 – 170 °C) Flowing Liquid Sulfur H2S/H2Sx Degassing over an Immobilized Catalyst Bed with Simultaneous Gas Sparging (Catalyst Particles/Pellets ) H2Sx Formation Kinetics as a Function of Temperature (Uncatalyzed/Catalyzed) ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. TiO2) Sparge Gas Selection (N2.

2 <1 <0.3. that SO3 is produced during catalytic incineration with the gold-titania catalyst.1 1 – 0. a suggestion supported by calculations performed in our laboratories. it is recommended that studies be performed using titania – lanthanum oxide composites which are not of nano-dimensions. Measurement of Acid Gas Properties at High Pressure Commercial Objectives: To provide needed density and viscosity data for designing projects that require handling and injection of high pressure H2S/CO2 and CO2/SO2 mixtures. CO 100% Conversions for the full oxidation of all these species 4.20 30 . It is composed of titania nano-fibres which are modified with gold and lanthanum oxide. Catalytic Tail Gas Incineration A gold-based titania catalyst prepared in the ASRL laboratories has been demonstrated for conversion of all sulfur species to SO2 as well as for conversion of CO to CO2 and H2 to H2O. This catalyst may represent a considerable advance for Claus tail gas incineration as it would eliminate the use of methane in classic thermal incineration.) Carbon Disulfide. if any.5 Au supported on La-Ti mixed oxide nanofibres Hydrogen Sulphide.5 3 – 1. H2S Sulfur.1 0. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. Carbon Dioxide. CS2 Carbonyl Sulphide. Sulfur Dioxide. COS Hydrogen. Since this preparation may be expensive to produce commercially.5 <0.5 – 0. Water Vapour. N2 H2O CO2 SO2 Mole% 60 – 40 40 . (b) Determination of SO3 formation during catalytic incineration CATALYTIC TAIL GAS INCINERATION: A BREAK THROUGH IN YEAR OF 2010 Steam(~300oC) Claus Tail Gas PRE-HEAT T: 300 – 400oC S. Specific Objectives (a) Preparation and testing of titania – lanthanum oxide composites for gold-based catalytic incineration. The University of Calgary 4 . It will also be useful to demonstrate to what degree. S8(vap.V. H2 Carbon Monoxide.0 2 – 0. = 5000 h-1 STACK (H2O) Tail Gas Component Nitrogen.

For the next year.0 10. Data for acid gas and sour gas injectate fluids are sparsely available in the open literature due to (i) the difficulty in dealing with H2S mixtures and (ii) the low range of viscosities for gaseous. 50. 290. 7550.Density and viscosity are two fundamental properties which are required to design compression and injection into a target reservoir. 20.0 -5.0 -15. 2900. 200. Over 40% of the target matrix was completed in the first year of the investigation. 100 & 150°C and p = 10. Specific Objectives (a) Complete densities and viscosities for the proposed matrix (b) Explore semi-empirical correlations for calculating the viscosity of acid gas mixtures MEASUREMENT OF ACID GAS PROPERTIES AT HIGH PRESSURE p--T Plots for H2S 100 200 μPa s (0. pc) p / MPa 10 50 μPa s 25 μPa s 20 μPa s 15 μPa s (0.200 cP) 100 μPa s (Tc. 50.5 μPa s 1 -50 0 50 100 150 200 T / °C Viscosity Deviation for H2S Viscosities from Schmidt et al.0 5.0 -10. 100.0 0 100 200 300 400 500 600 700 800 900 T = 100 °C T = 50°C T = 0 °C T = 150 °C (calc) / (kg m-3) ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. 500 & 1000 bar (145. liquid and supercritical fluids.(3) (exp)-(calc)) / (calc) 15. 1450.015 cP) 17. the aim is to complete the matrix and investigate some semi-empirical models which can be used to accurately calculate the viscosity of the mixtures. 14500 psia) A B C D E F G H I Mixture H2S / mol% 100 25 50 75 25 50 0 CO2 / mol% 100 75 50 25 25 0 50 CH4 / mol% 100 50 50 50 The shaded compositions have been completed. ASRL has been using an Anton Paar mPDS Vibrating Tube Density Cell and a VISCO pVT High Pressure Viscometer to measure these two properties over a broad range of conditions and concentration: Composition matrix proposed for investigations at T = 0. The University of Calgary 5 .0 -20.0 0. 725.

Advantages of this arrangement include an “isothermal” operation. when such systems malfunction. (b) Determine catalytic effects for BTX and hydrocarbon conversion. Clark AG Ceramic CH4 + Air Preheat Packing AG Products Converters WHB • • • • • • CH4 / Air used as pre-heat only Furnace operates “isothermally” Large heat capacity – no thermal run-away possible Refractory and WHB protected by ceramic packing CH4 co-firing built in for low H2S content AG S8 Packing is catalytic / no CS2 formation. (c) Examine ammonia destruction at the adiabatic temperature for this system THE ISOTHERMAL CLAUS FURNACE P. large heat capacity and probable catalytic conversion of aromatics (BTX) and other hydrocarbons. the catalytic effect of the brick should greatly reduce fuel gas use and eliminate the need for acid gas enrichment. overall. The methane supply would be shut down or turned down to achieve the desired temperature for poor quality acid gas cases. It is possible that these undesirable outcomes might be avoided by packing the furnace chamber with ceramic bricks or rubble (see diagram). 250⁰C) and then acid gas would be introduced and impinge with air on the hot brick. In the case of low quality acid gas. Oxidation will occur at the hot-brick surface with.5. 500⁰C) well above “light-off” temperature (ca.D. flame instability and low temperatures result in poor acid gas combustion with undesirable consequences to downstream equipment. the flame may impinge on the side walls or tube sheet causing significant damage. Specific Objectives (a) Demonstrate the packed chamber approach for acid gas light off and acid gas conversion. A methane burner would be used to bring the system to a temperature of (ca. In the case of low H2S content acid gas. as may be the case through unanticipated corrosion. full BTX and NH3 destruction ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. Careful design of the burner allows efficient heat and mass transfer but. no flame impingement. the temperature of the brick attaining the adiabatic value for that system. The University of Calgary 6 . Ceramic-Packed Claus Furnaces Commercial objective: to develop a simplified process for acid gas combustion and low quality acid gas treatment The standard Claus furnace consists of a ceramic brick-lined chamber and a burner to introduce acid gas and air.

C3: 9. The initial experiment indicates that all of the added sulfur was converted to H2S. P.78.15. synthetic crude oil and. Clark. C1: 45.59. The accelerating effect of sulfur likely involves formation of sulfur free-radicals which initiate bitumen coking below the standard coking temperature. Primak Oils Sands Bitumen Gases 21 wt% [Composition mol%: H2: 2.65] 451⁰C Liquid S8 (1. the off-gases of the SAC contained large quantities of ethane.03. One commercial benefit of this process would be a lower energy requirement to conduct the coking step. Low Pressure Sulfur-Promoted Bitumen Coking Commercial Objective: To examine a low severity bitumen coking process for the production of value-added products Bitumen upgrading processes include a combination of coking and hydro-treating technologies yielding coke.L. in some plants. gases.39.55. CO2: 1.6. we have discovered that addition of elemental sulfur to bitumen accelerates coking chemistry allowing rapid conversion to products at a relatively low temperature (ca. Specific Objectives (a) Examine conditions required to promote sulfur coking. The objective of this project would be to delineate conditions for SAC and determine the detailed product composition of gaseous and liquid products.30. D. Recently. (b) Determine product composition of liquid and gaseous products “LOW TEMPERATURE” SULFUR-PROMOTED BITUMEN COKING P. propane and butanes potentially giving this product stream enhanced value. C2: 22. N2: 4. The University of Calgary 7 . 0.4 wt% S8 as solid) High T (450⁰) Coke (Yield = 24 wt%) Liquids (Yield = 55 wt%) ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. H2S: 10. premium transportation fuels. CO. C4+: 4. Blais and A. 450⁰C). In addition.36.

sulfur is required in a variety of industrial applications with fertilizer production making up the majority use via consumption of the sulfur as sulfuric acid. due to factors such as the mineral makeup of the local ores and the quality of the process water. some kind of improved leaching technology will be required. Regeneration of the SO2-loaded adsorbent with off-gas ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. Improved Tail Gas Treatment Processes Commercial Objective: To examine SO2 adsorption as the basis for a high efficiency tail gas process for Claus sulfur recovery systems. the sulfuric acid leaching step has not been very economical and in some cases has failed to meet nickel production expectations. research data obtained suggest that the type of scheme shown in the Figure is feasible from a chemical viewpoint with demonstration that a modified alumina is suitable for application in the SO2 adsorption step. it is expected that the requirements for sulfur will expand considerably through use of sulfuric acid to extract nickel from nickel oxide ores. Over the last 2 years. Since nickel oxides represent most of the World’s remaining nickel reserves. In the future. (b) Review the chemistry of acid leaching for production of uranium and thorium Current Process Sulfur Sulfuric Acid nickel ore T > 200°C Acid mine  drainage landfill CaSO₄ and  other solids limestone Sulfuric acid waste Solubilized nickel and other metals Nickel metal New Research Direction Sulfur nickel ore Nickel sulfide [O] Solubilized nickel 8. Specific Objectives (a) Conduct research to improve nickel extraction from oxide ores. In some of these projects.7. New and Extended Uses of Elemental Sulfur Commercial Objective: To facilitate use of elemental sulfur in commercial applications At present. The University of Calgary 8 . Such technology has been in use for at least 3 decades in Cuba and new projects are under construction or in operation in several other countries.

7% N2 Regen: 350 °C. 30.75% N2 S.5% CO2. It is suggested that the fluidized bed approach be examined in a technical and economic evaluation.70-1. 1. 0.= 500h-1 Captured SO2: 1.4 Fluidized Bed 1. 3. (b) In cooperation with ASRL members or the University Engineering faculty. Further studies have shown that use of the adsorbent in a fluidized bed is considerably more efficient in terms of SO2 uptake (mass transfer). 27. IMPROVED TAIL GAS TREATMENT PROCESSES ASRL CLAUS TAIL PROCESS A COMPARISON OF SO2 ADSORPTION CAPACITIES Fixed Bed 1. conduct an engineering and economic evaluation.54% SO2 and 7.62% H2O.83 mmol/g Uptake: 150 °C.00% H2S.= 3585h-1 ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry.25% SO2.V.00% H2O and 68.from the second converter returned the material to a steady state condition with reproducible SO2 uptake.0% O2 and 65.V. 1.2 0 1 2 3 4 5 6 7 8 9 10 number of cycles Uptake: 80 °C.8 0.8% H2O. so increasing the thermal efficiency of the system.2 Modified-Alumina-A 1 Modified-Alumina-B Gamma-Alumina 0. 0. Specific Objectives (a) Test new SO2 adsorption materials if they become available. 2. This approach may also be preferred from an engineering perspective as the uptake and regeneration temperatures would be held at constant temperature.4 0.0% SO2.6 0. The University of Calgary 9 . balanced N2 S.

The results obtained to date have been published at the January 2009 Chalk Talks and have been published in the ASRL QB. Primary Upgrading of Oil Sands Bitumen Commercial Objective: To develop efficient and green technology for upgrading bitumen/heavy oil using donor solvent chemistry. Over the last 2 years.9.6wt% API= 15 . C1 – C5) ASRL Primary Upgrading S= 3. The donor solvent would consist of part of the gas oil fraction produced in the bitumen upgrading facility. process conditions). The University of Calgary 10 .20 Distillation * Naphtha HT * LGO HT * MGO HT * HGO Residue CO2 Capture * Gasification H2 Electricity Synthetic crude oil To hydrotreaters (HT) * C1 – C5 and H2S / NH3 recovery systems not shown ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. Specific Objectives (a) Delineate process conditions to optimize primary upgrading conditions (donor solvent type and quantity. (b) Characterize upgraded products to ascertain impact on downstream upgrading units. (c) Work with ASRL member companies and Alberta Innovates to determine interest to conduct a field pilot study. elimination of the coking step from bitumen conversion would greatly alleviate environmental concerns and simplify an upgrading facility. When this work is complete.Donor S= 4. ASRL will attempt to have an overall process evaluated from engineering/economic viewpoints. PRIMARY UPGRADING OF OIL SANDS BITUMEN THE NEW ROAD MAP FOR BITUMEN UPGRADING AND USE Sulfur Bitumen Feed H . Novel methods for primary upgrading of oil sands bitumen are being sought to produce low viscosity product directly amenable to either hydro-treating to synthetic crude oil or for pipeline transportation without further addition of diluent. research in our laboratories has demonstrated that sulfur-assisted donor solvent upgrading can accomplish the goal of producing pipeline viscosity oil with approximately 25% reduction in sulfur content.6wt% ~ 400°C * Off gases < 1 wt% (H2S. The upgraded product should also be suitable for hydro-treatment to synthetic crude oil. Research now underway is aimed at optimizing the distillate yield and removal of trace metals from the distillate product by manipulating the process conditions (temperature/sulfur additive quantity). In particular.

In the past year. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. The University of Calgary 11 . (b) Time permitting.5 1 0. Experimental data for the pure H2S species are warranted at conditions that might be experienced for re-injection of acid or sour gas for disposal or enhanced oil recovery schemes. Acid Gas Injection: Water Holding Capacity for Acid Gas Mixtures Commercial objective: To aid acid gas injection design projects by providing data for the water carrying capacity of acid gases at conditions up to reservoir injection. further developments in capabilities have provided the water content of H2S at T = 50°C and up to p = 75 MPa. Accurate prediction of the water carrying capacity of acid gas is needed to engineer and operate acid gas re-injection plants. the literature values for water carrying capacity of pure H2S and CO2 were surveyed and it was noted that there are very little water content data for pure H2S in the liquid region and CO2 at typical reservoir conditions (see figure below).5 0 20 0 Oil Sand Only OS + H-donor OS + H-donor + S8 In-situ upgrading of oil sands • Samples heated at 200 and 300°C for one month with and without the addition of a hydrogen donor and sulfur • 300°C showed significant upgrading while 200°C showed no reaction • Will perform at least one more set of experiments to determine the best way to introduce the additives 10. Over the past 6 to 7 years ASRL has developed reliable methods for measurement of water dissolved in sour and acid gases. With this capability in-hand. determine effect of condensable hydrocarbons on water carrying capacity of acid gas and sour gas mixtures. Specific Objectives (a) Measure the water carrying capacity for pure H2S at T = 100 and 150°C.PRIMARY UPGRADING OF OIL SANDS BITUMEN 140 Viscosity Results of In-situ Upgraded Bitumen 120 Unreacted ) 100 0 0 0 1 x 80 p c ( y t i s 60 o c s i V 40 200°C 300°C Primary upgrading of bitumen • Bitumen samples were heated up to 425°C for ~1h with or without the addition of a hydrogen donor and sulfur • Upgrading is observed in the samples without sulfur • It was determined that sulfur promotes coking at these conditions 2 1. In the next year H2S water contents will be measured at T = 100 and 150°C.

The University of Calgary 12 .ASRL’S CURRENT HIGH PRESSURE WATER CONTENT VALVE SYSTEM Load Position Caustic Inject Position Caustic Heated Box 50µL Loop 2µL Loop Heated Box 50µL Loop 2µL Loop Helium (0.000psi)) 11.2MPa) GC HP Vessel (up to 75Mpa (~11. sulfur would be formed by reaction of SO2 with un-consumed H2S thus providing a catalytic system for conversion of H2S to sulfur when only low quantities of H2S are present in the feed gas. An initial experiment confirms the production of sulfur. it may be possible to use the catalyst as an O2 scavenger. (b) Examine application of the catalyst for O2 scavenging in natural gas systems. in removal of trace amounts of H2S from shale gases. In addition. ASRL has demonstrated that gold supported on a mixture of titania and lanthanum oxide is an effective catalyst for tail gas incineration facilitating rapid conversion of sulfur species to SO2 at > 150⁰C. Consequently. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. it may be possible to use the gold-based catalyst in small scale sulfur recovery. Specific Objectives (a) To determine the ability of the gold-based catalyst to convert H2S to sulfur in small scale sulfur recovery opportunities. This catalyst is also able to oxidize CO and H2 to CO2 and H2O at typical tail gas incineration temperatures. odour control in bio-gas treatment and in subdew point Claus tail gas treatment.000psi)) HP Vessel (up to 75Mpa (~11. Sulfur Recovery by Direct Oxidation Using Gold-Based Catalysts Commercial objective: to develop new technologies for low tonnage sulfur recovery and Claus tail gas processing Recently. It is expected that at lower temperatures.2MPa) GC Helium (0. since this catalyst converts H2 to water.

SULFUR RECOVERY BY DIRECT OXIDATION WITH GOLD P. D. However. including dealing with the small quantities of H2S found in some shale gas. Specific Objective (a) Determine conditions for production of H2S from shale source rock if it becomes available ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. several challenges remain for expansion of this resource.TiO2 125250⁰C a) Small scale sulfur recovery b) Shale gas treatment c) Odour control S8 CHEMISTRY d) Sub-dew point Claus TG direct oxidation Au TiO2 ? H2S + 3/2 O2 2 H2S + SO2 SO2 3/ 8 S8 + 2 H2O 12. Formation of H2S in Shale Gas Reservoirs and During SAGD Bitumen Recovery Commercial objective: To understand mechanisms for formation of H2S in shale gas Shale gas has now changed gas production dynamics in North America to the degree that LNG terminals for export of methane from both the USA and Canada are now contemplated. However. H2S production during SAGD recovery of bitumen is also an ongoing problem. The University of Calgary 13 . Clark H2S / CH4 Claus Tail Gas ( ? ) • ASRL Au-based incineration catalyst is active for H2S S8 < 150⁰C • Applications: Au / La2O3 . This issue has been examined in the ASRL laboratories since the early 1980’s and was summarized in the most recent issue of the ASRL Quarterly Bulletin. no shale material could be accessed for the study. Research was to have been conducted in last year’s program to determine the mechanism for formation of H2S from shale source materials as it was thought that the H2S might arise during fracturing of the reservoir.

Determination of the Kinetics of H2S Oxidation in Compression Systems Commercial Objective: To determine the potential for sulfur formation in sour compression systems. (C2+) kerogen (organic sulfur) Organosulfur compounds steam. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. kʹ. C2+ (trace H2S) CH4.e. H2S. In order to apply these kinetics more generally to sour compression systems the order with respect to H2S is required to complete the rate expression. These kinetics have been investigated in the temperature and pressure range from 50 – 140oC and 100 – 1000 psig for the uncatalyzed gas phase reaction providing the pseudo-rate expression. rate = kʹ[O2]. (c) Write up results of the laboratory work for publication in the ASRL QB. The potential for sulfur deposition in sour compression systems due to trace O2 is a function of H2S oxidation kinetics and S8 solubility in the sour gas mixture. C2+. autocatalysis). The University of Calgary 14 .CO2. Specific Objectives (a) Collect rate data to determine the order with respect to H2S. (b) Test the hypothesis that S8 acts as a catalyst for H2S oxidation (i. 150-300°C H2S + CO / CO2 / H2 • Do stimulation procedures produce H2S from kerogen? 13. which is first order in O2 and contains the pseudo-rate constant. H2 Shale Reservoirs CH4.FORMATION OF H2S IN SHALE GAS RESERVOIRS AND DURING SAGD RECOVERY OF HEAVY OIL AND BITUMEN FORMATION OF H2S IN HEAVY OIL-BITUMEN AND SHALE GAS PRODUCTION Heavy Oil / Bitumen Steam CH4.

accurate kinetic rates are unkown. so that instruments already in service could be modified to measure SO2 in addition to total dissolved H2S. time = 0. Recently. 90% CH4 0. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry.001 500 1000 1500 2000 100% H2S 2500 kinetics are much faster in the presence of bare steel 10% H2S. In the past research year the Henry’s Law correlation for SO2 solubility and absorption coefficient for SO2 was reported relative to H2S.01 0 0. These can be heated to produce a specific quantity of H2S and H2Sx in liquid sulfur. 140oC S8 (ppmv) ) S8 solubility solubility (ppmv) 0.1 s .000001 Pressure (psi) 14. some hermetically sealed IR cells have been investigated for an alternative calibration check.0001 0. 1000 ppmv O2 . ASRL has supplied remote IR users with ampoules containing conglomerate mixtures of elemental sulfur and a hydrogen donor. While it is known that Claus reaction between SO2 and H2S in liquid sulfur is slow.Determination of the Kinetics of H2S Oxidation in Compression Systems H2S + 1/2O2 T = 50 – 140oC P = 100 – 1000 psig rate = kʹ[O2] 1/8S8 + H2O Potential for S8 deposition in sour compression systems is a function of H2S oxidation kinetics and S8 solubility in sour gas mixtures uncatalyzed . they can be used to check that the initial instrument calibration is correct. more investigations need to be conducted to avoid breaking the cells upon melting the sulfur/H2S mixture. While they are not used to calibrate IR instruments. H2S and SO2 Solubility in Liquid Sulfur Updating and Checking FTIR Calibrations Commercial Objective: Investigation of the uncatalysed Claus reaction in liquid sulfur by FTIR and modified sulfur/H2S mixtures within hermetically sealed IR cells for remotely checking IR calibrations. H2S dissolved in liquid sulfur often must be degassed before safely transporting or forming. The first part of this research will seek to follow the rate of reaction using IR. These rates will be used to understand the nondiffusion limited and uncatalysed rate (chemical rate) which can be used to optimize degassing and/or limit H2S dissolution. The University of Calgary 15 . however.00001 S8 formation exceeds sulfur solubility 0.

The University of Calgary 16 . H2S AND SO2 SOLUBILITY IN LIQUID SULFUR UPDATING AND CHECKING FTIR CALIBRATIONS PRELOADED/SEALED CALIBRATION CELLS AMPOULE CALIBRATION CHECKS 15. Specific objectives (a) Conduct laboratory studies to develop a model for deactivation of Claus catalysts. specifically the reaction temperature and impurities that might be found in the process gas. it is important to know the lifetime of the catalyst in order to plan catalyst change-out frequency. For commercial operations. (d) Investigate modified sulfur/H2S mixtures which could be used to reproducibility melt mixtures in hermetically sealed IR cells for remotely checking IR calibrations. Claus Catalyst Model Commercial objective: To produce a model for Claus catalyst deactivation The lifetime of a Claus catalyst depends on the conditions of operation. (b) Analyze field samples for residual activity to relate to the laboratory model. catalyst activity is usually determined by CS2 conversion. It is known that catalyst activity depends on carbon contamination. surface areas and pore volumes can be determined in tandem with CS2 conversion activity. which leads to loss of surface area and pore volume. If field samples become available. and the process temperature and the amount of surface sulphate concentrations. It is suggested that studies be performed to determine catalyst activity and field lifetimes by conducting experiments which determine loss of catalyst activity due to hydrocarbon and oxygen ingress (sulphate production) using CS2 conversion as the activity parameter. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. Specifically.Specific Objectives (c) Utilize the new absorption coefficient to determine rates of consumption of SO2 and H2S in liquid sulfur degassing systems and sulfur storage systems.

However. sulfates 16. The University of Calgary 17 . high P Effect of temperature.DEACTIVATION MODELING FOR CLAUS CATALYSTS 2 H2S + SO2 [carsul] [adsorbed species] Al2O3 3/ 8 S8 + 2 H2O BTX SO42- • How does BTX cause catalyst deactivation? • Deactivation rates: BTX. Specific Objective (a) Determine kinetics for removal of H2S from high pressure natural gas using a generic triazine formulation. so hampering design of large sacle systems. KINETICS AND MECHANISMS FOR DISPOSABLE SCAVENGERES R N H2S / CO2 N R [CH4] S R N RN S • • Rates of reaction? Low P. Kinetics and Mechanisms for Disposable Scavengers Commercial Objective: To aid design of field application of triazine scavengers Liquid triazine scavengers are used to remove small quantities of H2S from natural gas when total sulfur tonnages are < 1 ton day. carsul. high pressure natural gas applications. hydrocarbons. little information is available on the kinetics of H2S uptake at typical field conditions. by products? ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. The objective of this project will be to make kinetic measurements at relevant.

and SO₂ on the rate of O₂ consumption iv.) with conditions studied in (a) by analyzing reactor contents. Temperature range: 50 to 120°C iii. MDEA ii. etc. DEA. Fe³+) (b) Determine lower level of oxygen required to cause amine degradation under conditions studied in (a). Effect of H₂S. probably through oxidation of H2S to sulfur and oxy-sulfur anions which then react with the amines. Amines evaluated: MEA.17. The University of Calgary 18 . Effect of catalyst (eg. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. CO₂. The rate at which oxygen reacts with H2S in an amine system has not been evaluated and the actual mechanism for amine degradation under contactor conditions has not been reported. (c) Attempt to correlate degradation product formation (heat stable salts. bicine. Oxygen Consumption in Amine Systems Commercial Objective: To examine the rate of reaction of oxygen with H2S in an amine contactor Ingress of oxygen into an amine contactor is known to accelerate the degradation of gas sweetening amines. Specific Objectives (a) Measurement of the rate of O₂ consumption under amine contactor conditions: i. The overall aim of this project would be to determine these aspects of oxygen ingress with respect to amine degradation.

Two examples are (i) ethylene for remediation of sulfur in the near wellbore region and (ii) styrene addition to aromatic hydrocarbons to generate enhanced uptake by formation of organic polysulfides. elemental sulfur can deposit when pressure and temperature reductions occur during production. producers have either repaired damaged zones or ensure flowing streams using physical hydrocarbon solvents or chemical solvents. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. Effect of BTX on Reduction Catalysts Used In Tail Gas Processing Commercial Objective: To determine if trace quantities of BTX can cause fouling of alumina Co/Mo catalyst when used in Claus tail gas service. In the past research year. % 3 C-S-X 2 1 Sx CH4 H2S S8 CO2 H2O CH4 0 0 10 20 30 40 50 60 70 80 90 100 Time (hrs) 19. Furthermore. Specific Objectives: (a) Reporting of sulfur uptake kinetics by addition of olefins (styrene and ethylene) (b) Regeneration of the enhanced solvents. such as diaryldisulfides. Designer Hydrocarbon Sulfur Solvents for Sour Gas Production Commercial objective: To evaluate regeneration options for enhanced. hybrid sulfur solvents If present in a reservoir fluid. In recent years. tubulars. ASRL studies have shown that unsaturated hydrocarbons can be used as reactants to form in situ solvents. Two methods for solvent regeneration will now be investigated: (i) cooling of the solvent to reverse and release physically and chemically dissolved sulfur and (ii) distillation of aromatic co-solvent to recover the carrier solvent. DESIGNER SULFUR SOLVENTS FOR SOUR GAS PRODUCTION Lean Solvent Sulfur Uptake by TEX/10% Styrene/0.18. Traditionally. the kinetics of sulfur uptake for mixtures of styrene have been conducted at various temperatures in order to ascertain the chemical rate limitations of the reaction. This deposition can cause flow assurance issues in the near wellbore region. gathering lines and conditioning facilities.1% TEA Sampled at T = 40C 5 4 S8 Regeneration wt. solid sulfur deposition provides for very aggressive sulfur contact corrosion. The University of Calgary 19 .

S8 (vap) H2. The University of Calgary 20 . Thus.CO + CH4 • OR • Does benzene produce carsul ? 20. As depicted in the figure. Is fouling of Co-Mo catalysts in Claus tail gas units a myth? Specific Objective (a) To determine the effect of BTX on an alumina Co-Mo catalyst when used at conditions found in a reductive Claus tail gas unit.BTX is known to foul Claus catalysts (alumina or titania) as a result of oxidative processes which occur between the hydrocarbon and sulfur and/or oxidized sulfur species. water and hydrogen are the preferred products. T and X are the most destructive species in this case. N2. Short Contact Time Claus Process Commercial Objective: to develop a simplified sulfur recovery process A thermodynamic analysis of the Claus process suggests that the preferred H2S – O2 ratio is 4:1 as at this condition sulfur. T and X would be expected to form benzene and benzene should be hydrogenated to gas phase products. It is also claimed that BTX can foul Co-Mo catalysts in reductive Claus tail gas units but this observation would be contrary to what might be expected as the reduction processes that occur mimic those in a classic HDS unit. EFFECT OF BTX ON AL2O3 – CoS / MoS2 CATALYSTS B H2O. 4 H2S + O2 → 2 S2 + 2 H2 + 2 H2O Previous research in our laboratories has shown that short contact time catalysis (SCT) allows achievement of a product slate close to this ratio when the contact time is around 10 – 50 ms. pure O2 could be used in two or more stages so limiting the temperature of ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. H2S SO2. CO T X H2S MoS2 CoS Al2O3 • Are BTX converted to carsul ? CH3 CH3 CH3 Al2O3 – CoS / MoS2 H2 .

To date. (c) Confirmation of tail gas unit operation with species concentrations produced by SHORT CONTACT . In the world of sulfur.each stage to < 1000⁰C.TIME CATALYTIC CLAUS O2 Acid gas T1 T2 water O2 water (SO2 Liquid S8 Water quench Sour water H2S) Steam O2 Steam H2S. Excess H2 and any CO would be consumed in a final catalytic incineration stage. t(res) ≈ 10 – 50 ms. To support the hypothesis that sulfur dust is kinetically stable. CO2 (H2O) H2S recovery Catalytic incineration Atmosphere • • respectively. H2. like most aerosols or fogs. The key advantages of this type of process is that all of the “usual” catalytic stages are eliminated in favour of one tail gas stage that uses the standard hydrogenation of any SO2 and other sulfur species with return of H2S to the thermal stage. Reducing and catalytic conditions eliminate BTX and CS2 Conversion to sulfur: 80 – 85% per cycle 21. Specific Objectives (a) Determination of BTX and hydrocarbon conversion in SCT. we have not demonstrated destruction of hydrocarbon impurities or ammonia conversion by SCT so it proposed that these issues be examined in the core research program along with demonstration of the tail gas stage using the high H2 concentration produced by SCT. CO. thermodynamic changes ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. air borne dust may spontaneously ignite with explosive force. Sulfur Dust Properties Commercial Objectives: To determine selected properties of sulfur dust pertaining to handling and transportation of solid sulfur. (CO) O2 • T1 and T2 are approximately 800 and 600⁰C H2. sulfur dust poses a challenge in that air borne dust tends to remain suspended because of the development of surface charges which cause the particles to repel one another. The University of Calgary 21 . H2O (SO2). (b) Examination of ammonia destruction using SCT and typical sour water stripper gas concentration. Critically.

and use of materials designed specifically for SO2 capture will be conducted to complete this research. These studies. This involves showing that the melting temperature is not substantially different for small particles. H2Sx c. The University of Calgary 22 . surface adsorption reduces the charge potential of a surface. 22. These results. The objective is to heat the sulfur in a slow manner to obtain the physical melting point which is lower than the observed melting point. e. H2S. SO2 and H2S surface asorption isotherms for small particles will be measured for small sulfur particles. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. experiments have not been performed to validate capture of excess SO2 using the two-bed system.g. presented at the January 2011 Chalk Talks.can be investigated for small particle sizes. Water/other boundary effects on sulfur dust vs. Surface-adsorbed species. formed sulfur SULFUR DUST MELTING POINTS Sulfur dust (lab-generated) melting point experiments have been initiated. but. Low Tonnage Sulfur Recovery Commercial Objective: To develop improved technologies for small scale sulfur recovery Recent work has shown that a solid-phase Claus approach involving reaction of SO2 with H2S in high pressure natural gas results in effective H2S removal (see Figure). Melting point b. Finally. to date. Surface absorption capacity d. for small particles. Specific Objective (a) Characterize the physical properties of sulfur dust by making measurements in the following areas: a. SO2.. demonstrated that bed switching and regeneration would be required approximately every 60 hours when using basic Claus alumina. CO2.

when saturated with S8. The University of Calgary 23 . and bed C (regenerated) becomes SO2 scavenging bed. This potential technology has a distinct advantage in that the sulfur recovery step is decoupled from the gas treatment step so there is no possibility that either SO2 or O2. H2S REMOVAL BY “SOLID PHASE” CLAUS: THE OVERALL CONCEPT Natural Gas CH4. SMALL SCALE SULFUR RECOVERY . In addition. (b) Examine the H2S adsorbent concept.An alternative approach is to remove H2S with a selective adsorbent/catalyst system followed by conversion of H2S to sulfur off-line from the main gas production.000 ppmv P : 250-1000 psi O2 (membrane unit) Filtration (Particle removal) SO2 Liq. it may be possible to transport the H2S adsorbent reactor either by rail or road to a Claus sulfur recovery plant. Specific Objectives (a) Complete Claus-based solid sulfur recovery research examining the 2-bed system for SO2 capture and examine a combined Claus catalyst/SO2 adsorbent material.H2S REMOVAL Shale gas UPTAKE CH4 – H2S (10-1000ppmv) REGENERATION HOT GAS H2Sadsorbent Air S8 recovery S8 CH4 (H2S < 4 ppmv) • If adsorbent bed vessels are on “rail”. S8 A Claus catalyst 2H2S + SO2 3/ 8 Regen gas (200⁰C) S8 + 2 H2O C B Claus catalyst (SO2 removal) S8 (liq) Dehydration Pipeline (<16 ppmv) • Bed A accumulates solid sullfur. is switched to bed B. can contaminate the methane product stream. vessels can be transferred to a Claus plant ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. (H2S) H2S: 50 – 5. bed B acts as polishing reactor and • SO2 scavenger Gas flows: bed A. if it was used in the H2S conversion process.

d. p = 0. Would elemental sulfur in a CO2 pipeline really pose a problem? Experimental sulfur solubility in liquid/supercritical CO2 1000 900 800 SFT-10 Supercritical / liquid CO2 pump (maintaining CO2(l) feed at at p = 7. streams containing sulfur or streams which may have sulfur produced by oxidation could be problematic.] T = 0°C [S8] / (mg Sm3) 700 600 500 400 300 200 100 0 0 5 10 [Calc.) First glass-wool trap after experiment CO2(l) 99. investigate if the same method can be modified to look at low pressure and low temperature sour gases (a noted region where no data exists and models are questionable).99%+ (PraxAir bone dry) [Calc. (c) Time permitting.67 MPa) Thermostated needle valve (T = 30°C) 0. While current ASRL sulfur solubility models are capable of estimating saturation conditions. ELEMENTAL SULFUR SOLUBILITY IN HIGH-PRESSURE CO2 FLUIDS Data requirement .67 MPa CO2(l). In these cases. Rate of Decomposition of Polymeric Sulfur Commercial Objective: To determine the rate of disappearance of polymeric sulfur in solid sulfur to ascertain the potential for loss of mechanical strength in blocked sulfur.there are no sulfur saturation data at low temperature and pressure (we interpolate) (0<T<60°C. The University of Calgary 24 . (b) Recalibrate ASRL’s sulfur solubility model to handle low temperature CO2 fluids. 1<p<1000 psi). With the advent of CO2 pipelines for enhanced oil recovery and sequestration. there have been no experimental data available for calibration below T = 60°C. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. The Sulfur Carrying Capacity of Liquid and Supercritical CO2 Commercial Objective: To examine the capacity of industrial CO2 pipeline fluids to carry dissolved elemental sulfur. Some recently purchased equipment can be used to measure sulfur solubility in liquid and supercritical CO2 at T = 25°C.2 m frit Dry gas meter (Singer 802. which is a more reasonable temperature for surface pipelines. (2010) T = 60°C [Calc.] pSat CO2 [Calc.23. 1¼˝ i. T = 28°C p / MPa 15 20 25 24. Specific Objectives (a) To measure the sulfur solubility in liquid CO2 (T = 0 and 25°C) and supercritical CO2 (T = 50°C) up to 2000 psi. a critical parameter is how much sulfur can a CO2 stream contain before the CO2 fluid releases the sulfur from solution (sulfur precipitation).] T = 60°C [Exp] This Study.09 MPa) Glass-wool traps 100 cm3 Sulfur prill column (7.] T = 25°C [Exp] Serin et al.

5 2 2. To overcome this issue. (b) Using these rates determine the rate of decomposition of polymeric sulfur at conditions relevant to block storage of sulfur. EFFECT OF POLYMERIC SULFUR ON THE STRENGTH OF THE SOLID 30 Crush Strength vs Polymeric Content 25 25 20.5 1 1. reservoir temperatures must be increased to > 200⁰C in order to mobilize the highly viscous bitumen. experiments will be performed at higher temperatures. Specific Objectives (a) To determine the rates of decomposition of polymeric sulfur at 70.65 20 25 Crush Strength (lb. crude oil be injected into the reservoir along with in situ heating of the reservoir by an indirect method. In addition.13 3.08 5 0 Start 4 mo 8 mo 10 5 need longer times 0 0 0. The University of Calgary Polymeric Content (wt %) 20 Crush Strength(lb force) (lb force) Crush Strength 25 .5 Polymeric Content (wt %) 25. Recovery of Bitumen from a Subterranean Reservoir Commercial Objective: to increase the efficiency of bitumen extraction Steam assisted gravity drainage is used for bitumen recovery from deeply buried oil sands deposits but suffers the disadvantage of producing large volumes of water with the bitumen along with some H2S-containing gases. 80 and 90oC.The polymeric content of solid sulfur has been linked to the mechanical strength of the solid and this correlation has been strengthened by recent testing using a load cell method.03 3.5 3 3. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. It is suggested that instead of injecting steam. Preliminary measurements at 20oC over an extended time period (approaching 1 year) have shown that the loss of polymeric sulfur is too slow at this temperature to be accurately determined by direct means. where the rate of decomposition is faster. Since polymeric sulfur is meta-stable with respect to the S8 form it would be expected that the decomposition of polymeric sulfur in the solid could affect the mechanical strength and hence long-term viability of blocked sulfur. as a way of obtaining these data. force) 15 longer time 15 20 10 10 5 15 0 3. This study would aim to determine the rate of decomposition of polymeric sulfur under conditions relevant to the block storage of sulfur.

some upgrading of the bitumen could be anticipated if the reservoir temperature was raised above 250⁰C. The University of Calgary 26 . hence. Specific Objectives (a) Determine the amount of crude oil and temperature needed to reduce the bitumen viscosity to values required for reservoir recovery (b) Determine the potential for in situ upgrading at elevated temperatures (> 250⁰C) RECOVERY OF BITUMEN FROM A SUBTERRANEAN RESERVOIR P.The role of the crude oil would be to “dissolve” the bitumen at a temperature (ca. D. perhaps lower) to produce a mobile phase that could be pumped to the surface. and be suitable for pipeline transport without further addition of diluent. Since crude oil contains some “donor” hydrogen within its organic structures. some upgrading can be anticipated (H – donor reactions) moderately” Electric heating ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. surface handling costs. the reservoir T needs to raised only • If higher (>200⁰C) reservoir T is used. The advantage of this approach would be lower overall energy input in comparison to steam injection techniques and reduced gas formation and. Clark Solar Cell Light crude oil e e e Oil sands zone • Heating of reservoir by solar generated electricity • Crude oil “dissolves” bitumen creating a “medium. 100⁰C or. low viscosity” crude oil • If viscosity reduction is the key objective.

Z. high efficiency technologies for production of ethylene and propylene. Premji) Previous research in our laboratories has identified new. Aromatics (e. Production of C3 – C6 Olefins. The University of Calgary 27 . High Octane Alkylate and Valuable Petrochemicals (ongoing.FUNDAMENTAL RESEARCH PROGRAMS These projects include ongoing research (Graduate student and PDF) which has partial external funding (University of Calgary and Natural Sciences Engineering Research Council of Canada) A. program studies of Zahra Premji. FIGURE FRP A. a strategy that promotes very selective oxidation and very high yields of the olefins (Figure FRP A).D.D. (b) Use the mixed olefins to synthesize high octane alkane mixture so providing a direct route from refinery alkane off-gases to gasoline pool mixtures. This work will be expanded as part of the Ph. Alkylation OR 2. Specific Objectives (a) Determine the feasibility of producing a mixed olefin product from a C3 – C6 feed. studies.g. Assessments of this work by ASRL members suggest that sulfur assisted olefin manufacture would be more efficient than current technology and. The chemical principle behind these technologies is partial oxidation of a hydrocarbon feed using sulfur as an oxygen transfer agent. Ph. SYNTHESIS OF MIXED OLEFINS AND UTILIZATION IN ALKYLATE AND ALKYL BENZENE MANUFACTURE C3 – C6 Alkanes H2S / Air CH3 CH = CH2 CH3 CH2 CH = CH2 Pentenes 1. represents the highest yield (60%) yet reported. iso-propyl and butylbenzenes. (c) Use of the olefin mixture to alkylate benzene so providing a direct synthesis of ethyl. benzene) R’ R = CH3 CH2. C3 High octane alkylate ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. in the case of propylene.

Zeigler and colleagues in the Chemistry Department of the University of Calgary. John Lo) Commercial Objectives: Use of computational techniques to develop enhanced understanding of catalytic processes for sulfur recovery. Much of the theoretical development has been conducted by Dr. Recently.B. density functional theory (DFT) has allowed calculation of more precise models for surface catalyzed reactions. (c) Investigation of the mechanism of H2S assisted oxidation of alkanes to olefins. defining the most suitable materials for SO2 adsorption. FIGURE FRP B. This research will also aid the development of the research in projects # 1 and FRP A (Figure FRP B). SO2/H2S CO-ADSORPTION ON HYDRATED (110) C SURFACE (PATH 2) ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. Specific Objectives (a) Determine the mechanism of SO2 and H2S adsorption at catalytic surfaces. Computational Modeling of Catalytic Systems (Dr. (b) Examination of the Claus catalytic mechanism. The University of Calgary 28 . Recently. T. extra funding was obtained though the ASRL-University connection to fund a 2 year position to examine Claus catalysis at the mechanistic level using DFT.

During the last two years. In one case. There is currently one such project within the ASRL research portfolio.SPECIAL PROJECTS Special projects are research efforts which aim to take ASRL core research work to the commercial demonstration phase. 1. The test blocks have been poured at the Shell Burnt Timber gas plant and instrumentation is being put in place. laboratory work has been conducted to examine the viability of spray-on coatings based on construction stucco. ASRL is registered as a not-for-profit Company in the Province of Alberta and is located within the Department of Chemistry. new sour gas fields in the Middle East and Central Asia. Potentially. “Post recession” pricing is showing some recovery. new production in China and oil sands-derived sulfur could over-whelm the market requiring long term (50+ years) block storage. Three types of protective coating were applied in the Spring of 2010. Above Ground Sulfur Storage Commercial objective: To develop techniques for long-term. The University of Calgary 29 . The most recent cycle produced prices of up to $850/ton but “business as usual” was resumed with prices dropping to < $50/ton during the 2009 recession. This work was reported at the January 2008 and 2009 Chalk Talks. environmentally benign solid sulfur storage Sulfur supply/demand cycles over the last 50 years have resulted in the need for temporary block storage of many millions of tons worldwide. ASRL has been working with its members to identify strategies for long term storage and to design field pilot projects. This project was established in the Fall of 2009. fully founded by four industrial sponsors.

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