FINAL REPORT

Test of TDA's Direct Oxidation Process for Sulfur
Recovery


by

Girish Srinivas, Ph.D. (P.I.)
Steven C. Gebhard, Ph.D., P.E.
Eugene Peeples

TDA Research, Inc.
12345 W. 52nd Avenue
Wheat Ridge, CO 80033
(303) 422-7819


Sandra Huzyk

Huzyk Energy Management


Randy Welch

Whiting Petroleum Company



for

Jesse Garcia

U.S. Department of Energy
Contract No. DE-AC26-01BC15333

Period of Performance: March 13, 2001 – February 29, 2004

January 2005
2
Disclaimer

“This report was prepared as an account of work sponsored by an agency of the United States
Government. Neither the United States Government nor any agency thereof, nor any of their
employees, makes any warranty, express or implied, or assumes any legal liability or
responsibility for the accuracy, completeness, or usefulness of any information, apparatus,
product, or process disclosed, or represents that its use would not infringe privately owned
rights. Reference herein to any specific commercial product, process, or service by trade name,
trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any agency thereof. The
views and opinions of authors expressed herein do not necessarily state or reflect those of the
United States Government or any agency thereof.”
3
Abstract

This project was a Phase III pilot plant test of TDA’s gas sweetening process done under
realistic conditions. TDA Research Inc successfully completed the test at Whiting Petroleum’s
Sable San Andreas Gas Plant. The feed was approximately 228,000 standard cubic feet per
day (SCFD) of gas that contained approximately 60 vol% CO
2
, 20 vol% CH
4
and 10 vol% C
3
+
and higher hydrocarbons. The feed was associated gas from CO
2
flooding operations carried
out on Whiting’s oil wells. The gas is collected and piped to the Sable gas plant where it is
normally flared. We sited our pilot plant in line with the flare so that we could remove the
hydrogen sulfide (H
2
S) prior to flaring. The average H
2
S concentration in the gas during the
field test was 7341 ppm. The selectivity of our process for converting H
2
S into elemental sulfur
was essentially 100% and the catalyst converted 90% of the H
2
S into sulfur and water (the
remaining 10% of the H
2
S passed through unconverted). Importantly, no catalyst deactivation
was observed for over the course of the 1000+ hour test. Minimal (ca. 10-15 ppm) of SO
2
was
formed during the test. Approximately 3.6 tons of elemental sulfur was recovered from a total
inlet of 3.9 tons of sulfur (as H
2
S). The total amount of SO
2
released from the plant (taking into
account flaring of the unconverted 10% H
2
S) was 0.86 tons. This amount of SO
2
is much lower
than the normal 8 tons that would have been emitted if all of the H
2
S were flared over the time
of the pilot plant test. The pilot plant was simple to operate and required much less operator
intervention than is typical for a new unit being commissioned. Our operator (Mr. Eugene
Peeples) has more than 30 years of experience operating commercial scale liquid redox sulfur
recovery processes and in his opinion, TDA’s Direct Oxidation pilot plant is easier to operate
than liquid systems. The ease of use and low capital and operating costs of TDA’s Direct
Oxidation process makes it an attractive technology to be used where traditional sulfur recovery
technologies are too expensive (e.g. small to medium sized plants). Currently, TDA’s direct
oxidation process has been exclusively licensed to SulfaTreat, and is being offered
commercially under the trade name SulfaTreat-DO
®
. We anticipate that the first plant will be
installed in 2005.
4
Table of Contents

1. Executive Summary 5
2. Objectives 5
3. Project Description and Background 6
4. Description of the Pilot Plant 7
4.1. Overview 7
4.2. Catalytic Reactor 11
4.3. Sulfur Condenser 12
4.4. Sulfur Bins (“Pots”) 14
4.5. Modification of Flare Tie-In to Prevent Sulfur Vapor Plugging 14
5. Field Test Results 18
5.1. Feed Gas 18
5.2. Catalytic H
2
S Oxidation Test Results 19
5.3. Laboratory Testing of Fresh and Used Catalyst 22
6. Technology Transfer 23
6.1. Technology/Information Transfer 23
6.2. Public Relations and Marketing 23
7. Conclusions 24
8. References 25
9. LOCATION: NPTO 26

5

1. Executive Summary

This project was a Phase III pilot plant test of TDA’s gas sweetening process done under
realistic conditions. TDA Research Inc successfully completed the test at Whiting Petroleum’s
Sable San Andreas Gas Plant. The feed was approximately 228,000 standard cubic feet per
day (SCFD) of gas that contained approximately 60 vol% CO
2
, 20 vol% CH
4
and 10 vol% C
3
+
and higher hydrocarbons. The feed was associated gas from CO
2
flooding operations carried
out on Whiting’s oil wells. The gas is collected and piped to the Sable gas plant where it is
normally flared. We sited our pilot plant in line with the flare so that we could remove the
hydrogen sulfide (H
2
S) prior to flaring. The average H
2
S concentration in the gas during the
field test was 7341 ppm.

The selectivity of our process for converting H
2
S into elemental sulfur was essentially 100% and
the catalyst converted 90% of the H
2
S into sulfur and water (the remaining 10% of the H
2
S
passed through unconverted). Importantly, no catalyst deactivation was observed for over the
course of the 1000+ hour test. Minimal (ca. 10-15 ppm) of SO
2
was formed during the test.

Approximately 3.6 tons of elemental sulfur was recovered from a total inlet of 3.9 tons of sulfur
(as H
2
S). The total amount of SO
2
released from the plant (taking into account flaring of the
unconverted 10% H
2
S) was 0.86 tons. This amount of SO
2
is much lower than the normal 8
tons that would have been emitted if all of the H
2
S were flared over the time of the pilot plant
test.

The pilot plant was simple to operate and required much less operator intervention than is
typical for a new unit being commissioned. Our operator (Mr. Eugene Peeples) has more than
30 years of experience operating commercial scale liquid redox sulfur recovery processes and
in his opinion, TDA’s Direct Oxidation pilot plant is easier to operate than liquid systems. The
ease of use and low capital and operating costs of TDA’s Direct Oxidation process makes it an
attractive technology to be used where traditional sulfur recovery technologies are too
expensive (e.g. small to medium sized plants). Currently, TDA’s direct oxidation process has
been exclusively licensed to SulfaTreat, and is being offered commercially under the trade
name SulfaTreat-DO
®
. We anticipate that the first plant will be installed in 2005.

2. Objectives

The objective of the project was to perform a field test of TDA’s gas sweetening process under
realistic conditions. In TDA’s process, hydrogen sulfide gas (H
2
S) is catalytically oxidized (using
air) to form elemental sulfur and water. The elemental sulfur is formed in the vapor phase and
is subsequently condensed downstream of the catalytic reactor. The small amount of water
vapor produced by the process remains in the sweet gas exiting the sulfur condenser. Prior to
the field test, all testing had been done at the laboratory scale where synthetic mixtures of feed
gas were tested. While laboratory scale testing is sufficient for catalyst development and initial
studies, field-testing at the pilot plant scale is necessary to determine how the catalyst will
perform when exposed to the wide variety of hydrocarbons, mercaptans and other impurities
commonly found in natural gas and associated gas streams. Also, by testing at the pilot scale,
temperature gradients within the catalyst bed, non-uniformities in gas flow, and engineering
scale issues are addressed that cannot be investigated at the much smaller laboratory scale.
This report describes the results from a successful field test of TDA’s process to remove H
2
S
from an associated gas stream that contained approximately 8000 ppm of H
2
S, 60% CO
2
, 20%
CH
4,
and 20% ethane, propane, butane and traces of higher hydrocarbons. We also report an
6
economic analysis based on the field test data that shows that TDA’s process (which we refer to
as Direct Oxidation or DO) is much less complex and lower in cost than competing commercial
technologies.

3. Project Description and Background

Direct Oxidation (DO) uses a proprietary
patented catalyst that was developed by
TDA. The catalyst oxidizes hydrogen
sulfide (H
2
S) to elemental sulfur and
water, with minimal if any SO
2
formation.
DO catalyst development and
demonstration at the bench scale was
done with funding from the U.S.
Department of Energy under Phase I and
Phase II SBIR grants. After the
laboratory scale demonstration of DO,
the Gas Technology Institute (GTI) and
Unocal funded the design and fabrication
of a $1,300,000 pilot plant to test the
process at close to commercial scale.
The pilot plant was originally scheduled
to be field tested on a Unocal offshore
platform in Mobile Bay, located off the coasts of Mississippi and Alabama. Unocal anticipated
that the offshore platform would be subjected to more stringent SO
2
emissions regulations and
saw the Direct Oxidation process as a way to achieve increased gas production while reducing
SO
2
emissions. The environmental regulations on the platform however, were not increased
and Unocal decided not to spend the additional money needed to install and operate the plant.

After extensive negotiations and exploring possible sites for the field test, TDA completed
construction of the pilot plant and installed it at a new site in Texas (Figure 1) with funding from
the Department of Energy (this project). The plant was installed at Whiting Petroleum
Company’s Sable San Andreas gas plant outside Plains, TX and the field test was completed in
2003. The Whiting gas plant is located about 5 miles northwest of Plains, TX, which is about
equidistant between Midland, TX, Lubbock, TX and Hobbs, NM (Figure 1). The gas that was
used as the feed for the pilot plant contained about 8000 ppm of H
2
S, 20% methane and about
60% CO
2
with the balance being ethane, propane and butanes. This gas is associated gas
obtained after CO
2
flooding of Whiting oil wells.

The pilot plant test was completely successful and the data have enabled us to evaluate the
economics of the process and compare our process to currently available small-sulfur recovery
technologies such as various liquid redox processes. Having successfully demonstrated the
TDA DO process, potential customers will be much more confident about the reliability of the
technology. As a result of the field test and favorable economics (discussed later), TDA has
licensed the process to SulfaTreat, a business unit of M-I. The process is currently being
offered commercially under the trade name SulfaTreat-DO
®
. Westfield Engineering is the
primary contractor for detailed engineering design and for subcontracting the construction of
commercial SulfaTreat
®
-DO units. Westfield is a well-established company with a long and
successful history in designing and building sulfur recovery units, including Claus and SulFerox
units. The first commercial SulfaTreat-DO
®
plant is expected to be installed some time in 2005.


Figure 1. Location of Plains, TX.
7
4. Description of the Pilot Plant

4.1. Overview

The pilot plant tests were conducted at the Whiting Petroleum Sable San Andreas Gas Plant
located near Plains, TX. Startup and shakedown of the plant was done during the first week of
October in 2002. This included installation of the main electric gas heater, tuning controllers
and establishing the flow of process gas. Figure 2 is a photograph of the site where the pilot
plant was eventually located, and Figure 3 is a photograph of the plant during its initial
installation (before being heat traced and insulated).


The pilot plant has five main “subsystems:” 1) the feed gas system which includes the gas
manifold, a liquid knockout (KO) drum and a reactor bypass; 2) the catalytic reactor where H
2
S
oxidation into sulfur vapor and water takes place; 3) a sulfur condenser; 4) a sulfur u-trap and
heat traced liquid sulfur handling piping; and 5) sulfur storage bins.

The liquid knockout (KO) drum is located upstream of the catalytic reactors and its function is to
remove and hydrocarbon liquids that may be present in the gas stream. This minimizes the
amount of hydrocarbon vapors to which the catalyst can be exposed. The KO drum is equipped
with level controls, automatic drainage, a flare bypass etc. The P&ID for the inlet piping and KO
are shown in Figure 4.
Shed
Pad area for pilot plant
Pipe rack with flare
and feed gas lines
Shed
Pad area for pilot plant
Pipe rack with flare
and feed gas lines

Figure 2. Photograph of Whiting Sable San Andreas gas plant before
installation of the TDA sulfur pilot plant.
8


Sulfur condenser
Reactor
Electric
heater
attaches
here
Flare line
Gas inlet not attached in this photo
Sulfur
storage
pots
Sulfur condenser
Reactor
Electric
heater
attaches
here
Flare line
Gas inlet not attached in this photo
Sulfur
storage
pots

Figure 3. Photograph of pilot plant during installation at the Whiting site.

Figure 4. P&ID of the knockout drum section upstream of the catalytic reactors.
9

Figure 5 is the process and instrumentation diagram for the reactor and condenser sections of
the plant. Radian International did the detailed engineering (and made the drawings) early in
the history of the project under subcontract to TDA. Two fixed bed reactor vessels are shown in
Figure 5 because in the original plan was to place the plant on a Unocal offshore platform in
Mobile Bay. In this application, Unocal wanted the option of drying the gas over a desiccant
prior to desulfurization by catalytic oxidation. The second “reactor” was to be used to contain
the desiccant bed. In the field test at Plains, this vessel was empty and was valved off.


One of the reactor was used and was filled with catalyst. The reactor is made of carbon steel
and is lined with refractory (described in detail in Section 4.2). The sulfur condenser (described
bed in Section 4.3) is a heat exchanger with a half-height tube sheet that is half filled with
boiling water. The process gas exiting the catalytic reactor (that contains the elemental sulfur
vapor) flows tubeside. The temperature of the sulfur condenser tubes is maintained by
controlling the steam pressure on the shell side (boiling water) of the condenser. Because the
saturation pressure of the shellside steam determines the saturation steam temperature,
controlling the steam pressure controls the temperature of the sulfur condenser. The condenser
is mounted slightly off horizontal so that liquid sulfur exiting the condenser will flow downhill and
into a U-tube type trap and into sulfur bins (Figure 6).

The gas exiting the sulfur condenser was at the sulfur condensation temperature, which was
250-260°F in the field test. Liquid sulfur exits the bottom of the bonnet of the condenser and
sweet gas exits at the top. Because this gas is at 250-260°F and is in equilibrium with the liquid
sulfur leaving the condenser, the sweet gas contains about 75 ppm of sulfur vapor. Unless this
vapor is removed, it will plug downstream piping. To prevent plugging of Whiting’s flare header,

Figure 5. P&ID for reactor and sulfur condenser section of the pilot plant.
10
we installed about 75 ft of 6 inch SCH40 carbon steel pipe between the pilot plant and Whiting’s
flare header. This pipe was unheated so the 75 ppm sulfur vapor would condense in it leaving
only clean sulfur free gas to pass into the flare header. This is discussed in detail in Section
4.5. Commercially available technologies exist for condensing sulfur vapor, and because the
focus of the pilot plant test was proving the catalytic oxidation of H
2
S to sulfur with a real gas
stream, we installed the long pipe because this option was quick and inexpensive. In a
commercial application, we will use a heated coalescing filter (as recommended by Westfield
Engineering).


The sulfur condenser and sulfur storage vessels are located on the bottom level of the unit (the
unit has two levels to save space as per the original off-shore requirement). Liquid sulfur exiting
the sulfur condenser passed through a U-trap that acts as a sulfur seal and into collection bins.
The bins are purged with air to degas the sulfur (Figure 6). Unfortunately, during the field test,
we found that the bins badly leaked gas and were therefore not used. In addition, the heat
tracing on the P-trap was not sufficient to maintain the proper liquid level. Therefore, we
removed sulfur directly from the heat exchanger bonnet, storing the sulfur in 55 gal drums.

Several contractors were involved in the installation and start up of the unit. The primary
contractors were Huzyk Energy Management, Denver, CO; Wilbanks Engineering, Houston, TX;
and Ref-Chem, Odessa, TX. Sandra Huzyk of Huzyk Energy Management was the project
manager for installing the plant and found the test site.

Figure 6. P&ID for sulfur collection “pots.”
11

Ref-Chem is a heavy industrial construction,
maintenance and engineering company. They
provide roots facilities, plant expansions, revamps &
retrofits, and in-plant contract maintenance services
for the petrochemical, chemical, oil & gas, refining, air
separation, minerals processing, power, cement and
manufacturing industries. Ref-Chem did the physical
installation of the pilot plant at the Whiting site (Figure
7). Wilbanks installed the process control system and
the heat tracing.

4.2. Catalytic Reactor

The catalytic reactor is made from carbon steel, lined with refractory, and designed to operated
at 25 psig. Figure 8 is a detailed drawing of the reactor and how it was loaded with inerts and
catalyst prior to the field test. The reactor was operated adiabatically and contained about
1700 lb of catalyst in the form of 1/8 in x ¼ in pellets.

Solids are retained in the reactor by means of a
cylindrical screen that is located at the bottom of
the reactor. The cylindrical screen also has a
cap. The first layer was a 6-inch deep layer of
1-inch diameter ceramic balls (NorPro
Denstone®). A 6-inch layer of ½ inch ceramic
balls and then a 6-inch thick layer of ¼ in ceramic
balls followed this. A 10 x 10 mesh stainless
steel screen as placed over the Denstone® balls
and the catalyst (1700 lb of 1/8 inch x ¼ inch
cylindrical pellets) was placed on top of the
screen. A sheet of 10 x 10 mesh stainless steel
screen was then placed on top of the catalyst and
a final single 6-inch thick layer of ½ inch ceramic
balls was place on top. The balls act as a flow
distributor for the feed and product gases as a
support for the catalyst pellets.

Figure 7. Pilot plant installation (photo
courtesy of Huzyk Energy Mgmt.).

Figure 8. Detailed drawing of the pilot plant
catalytic reactor.
12

4.3. Sulfur Condenser

The sulfur condenser is essentially a
thermosiphon “reboiler” type of heat
exchanger that operates at about 265°F.
At this temperature the saturation
pressure of steam is about 38 psia (26
psig at the altitude of Plains, TX). By
controlling the steam pressure (back
pressure on the steam line from the
condenser to the air fin cooler (see P&ID
in Figure 5), the temperature of the boiling
water inside the condenser can be
controlled. Figure 9 is a schematic of how
the condenser functions and Figure 10 is
a close up photograph of the sulfur
condenser (the gas outlet is difficult to see
in the photograph – it is located on top of the bonnet at the end of the condenser just left of the
water level gauge).



It is important to keep the sulfur condenser temperature between about 240°F (the melting point
of sulfur) and 320°F (where the viscosity rises dramatically) because of the peculiar viscosity
versus temperature behavior of liquid sulfur. Our typical operating temperature range is 250°F
to 280°F. At these temperatures, liquid sulfur has its minimum viscosity (Figure 11). The
viscosity data shown in Figure 11 below 240°F (left side) are for the supercooled liquid, which
we never have in our application. Above 320°F, the viscosity of sulfur rapidly increases,
eventually reaching enormous values (right side of Figure 11) when the so-called plastic or
µ−sulfur exists (Tuller 1954). For example, Figure 11 shows that the viscosity of sulfur at 375°F
is about 60 lb/ft-sec, which is equal to 89,000 centipoise. For comparison, the viscosity of water
at room temperature is about 1 centipoise. The huge increase in viscosity of liquid sulfur with
Hot gas from reactor
Liquid sulfur out
Sweetened product gas
Water level
Steam to air-fin cooler
Water returns from air-fin cooler
Hot gas from reactor
Liquid sulfur out
Sweetened product gas
Water level
Steam to air-fin cooler
Water returns from air-fin cooler

Figure 9. Schematic of sulfur condenser.
Hot gas inlet
Gas outlet
Flare line
Liquid sulfur outlet
Water level
gauge
Water return
Hot gas inlet
Gas outlet
Flare line
Liquid sulfur outlet
Water level
gauge
Water return

Figure 10. Photograph of sulfur condenser.
13
increasing temperature above 320°F is due to the rupture of the normal eight-atom sulfur rings
(Figure 12) followed by polymerization of the now linear S
8
chains. The resulting material,
(called µ-sulfur) is extremely viscous. The phase change is irreversible, and therefore once
µ-sulfur is formed, the equipment will plug and will require shutdown for cleaning.


The narrow temperature window (ca.
60°F) for operating the sulfur condenser
requires that there be a minimal
temperature gradient along the length of
the condenser tubes (which are about 15
ft long). In a conventional cold-fluid-in,
hot-fluid-out, counter-current type of heat
exchanger, it is difficult to guarantee enough a uniform enough temperature along the length of
the tubes so that overheating (making µ-sulfur) or too much cooling (sulfur solidification) can be
prevented. Either situation would plug the condenser. To avoid this, the constant
temperature/boiling water design was used. Figure 10 is a close-up of the condenser with the
various lines labeled.

The sulfur condenser is a standard design and it functions essentially as a boiler with a
thermosiphon. Steam generated on the shell side of the condenser (by heat transfer from the
hot product gas in the tubes) flows up to an air-fin cooler where it is condensed and returned
through a standpipe (see Figure 10). The height of the standpipe determines the hydraulic
head that drives the water back into the shellside of the condenser. In our case this was about
15 ft of water (approx 2 psi). One problem we observed with this design during operation was
that the volume of water in the standpipe was too small. This was because the return pipe was
2 inch SCH40 and there was no water reservoir. As a result, establishing natural circulation
was very sensitive to the operation of the steam control valve. Too much steam pressure would
blow the standpipe dry and with too little steam pressure, the steam in the condenser would
drive water backwards up the standpipe into the air-fin cooler. We were able to control the loop
and operate with continuous circulation, but in commercial models we will use a larger diameter
standpipe so that the standpipe volume is greater.


Figure 11. Sulfur viscosity at low temperatures (left) and high temperatures
(right); data from the Sulfur Data Book (Tuller 1954).
S
8
µ-S

T > 320°F
S
8
µ-S

T > 320°F

Figure 12. S
8
ring breaking and polymerization.
14
4.4. Sulfur Bins (“Pots”)

The sulfur bins were not used in the field test because of an operational difficulty in the lines
that transport liquid sulfur from the outlet of the sulfur condenser to the bins. During the test, we
found several cold spots between the exit of the sulfur condenser and the bins that would plug
with solid sulfur. Worse, the bins were not gas tight, which would have made using them
dangerous.

Rather than shut down the plant and re-heat-trace the entire downstream liquid piping, we
modified the system so that we could withdraw the liquid sulfur directly from the sulfur
condenser. While not a permanent solution, this enabled us to continue the field test and was
acceptable because the test was focused on the performance of the Direct Oxidation catalyst,
and not how to handle liquid sulfur (which is existing technology that can be easily engineered
by Westfield Engineering for commercial units).

4.5. Modification of Flare Tie-In to Prevent Sulfur Vapor Plugging

The sulfur condenser was operated at
about 260°F. While the vapor pressure
of sulfur at this temperature is relatively
low (P
vapor
= 0.063 Torr = 1.22x10
-3
psia;
see Figure 13) the volume of gas
passing over the liquid sulfur is large
enough that considerable sulfur will exit
the condenser as vapor. The average
sour gas flow rate was about 200
SCFM. Assuming that this gas is in
equilibrium with the liquid sulfur in the
condenser when it exits the condenser,
then the sulfur vapor concentration in
the gas would be approximately 75 ppm.
At this concentration and 200 SCFM,
about 100 lb of sulfur would deposit in
the piping downstream of the condenser during the test. If not removed, this sulfur would plug
Whiting’s flare lines, which was unacceptable. The goal of the pilot plant test was to
demonstrate that the catalytic technology; methods and equipment for handling liquid and vapor
phase sulfur is commercially available. Thus, we needed a quick and importantly, inexpensive
way to prevent sulfur vapor from condensing and depositing in Whiting’s flare line while
permitting us to finish the field test on budget.

We investigated several options to remove the sulfur vapor before the gas reached Whiting’s
flare header. Among the options considered were: 1) treating the gas with a cold water spray;
2) scrubbing the gas with a solvent; 3) plumbing the gas through a packed tower scrubber
(using water) – there was an unused tower located on-site, and 4) adding a long section of
unheated, large diameter, pipe section upstream of the flare heater to allow the sulfur to deposit
in that line before reaching the flare header.

0.0
0.1
0.2
0.3
0.4
0.5
0.6
200 250 300 350 400 450 500 550
Temperature (F)
V
a
p
o
r

P
r
e
s
s
u
r
e

(
p
s
i
a
)

Figure 13. Sulfur vapor pressure (Daubert et al.
1997).
15
We chose to protect Whiting’s flare line by
installing 75 ft of 6 inch SCH40 pipe
between the vapor outlet of the sulfur
condenser and Whiting’s flare header.
With this length of pipe, the gas exiting
the sulfur condenser was cooled to below
200°F before it entered the flare header.
In addition, the pipe was not a straight
run; several tees were installed (instead of
elbows) to permit both cleaning (if
necessary) and to create turbulence
where sulfur would preferentially deposit.
Several thermocouples were installed
along the length of pipe so that we could
check the gas temperature. In a
commercial application, we would install a
commercially available heated sulfur
coalescing filter, but time and cost constraints prevented us from using such a device during the
field test.

The sulfur vapor recovery line was sized by assuming that free convection around the pipe was
the only mechanism that would cool the gas. Most sections of the pipe would be cooled by
radiation (especially at night when the air was cool); however during the day, solar radiation
would slightly heat the pipe. Ignoring radiation heat transfer simplified the analysis and more
importantly, gave a pipe length that was longer than actually needed because natural
convection is less efficient at cooling in this situation; ”too much cooling” is not a problem.

To make the calculations even more conservative, the temperature of the air was assumed to
be rather warm (80°F). The properties of air at this temperature were used in the free
convection calculations. The gas inlet temperature was assumed to be 266°F and the outlet
was assumed to be 230°F (10°F below the sulfur melting point). The temperature of the surface
of pipe was assumed to be the average of these temperatures (248°F). For free convection
from a horizontal pipe in air, the Rayleigh number (Ra) is given by Equation 1. This
dimensionless number expresses the balance between thermal expansion, temperature,
thermal diffusivity, viscosity, and the thickness of the convection layer of the gas in which the
body being cooled is immersed (in this case air). Natural convection begins near Ra = 2000
and becomes turbulent for Ra ≥ 10
6
.


The definitions of the terms in Equation 1 are as follows: α
air
is the thermal diffusivity of air
[k/(ρ∗Cp)], β is the coefficient of thermal expansion of air (2.725x10
-3
K
-1
), g is the gravity
constant (32.2 ft/s
2
), and ν
air
is the kinematic viscosity of air (taken at the average pipe wall
temperature, ν
air
= 1.74x10
-4
ft
2
/sec). The value of Ra calculated from Equation 1 was found to
be Ra = 5.8x10
7
which is in the turbulent flow regime.

0 50 100 150 200 250
0.000
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008

File: C:\STEVE GEBHARD\SG_ PROJECTS\SULFUR proje
C
kmol
Temper
S
S8(g)
S6(g) S2(g)
S7(g)
S5(g)

Figure 14. Composition and dew point of for 8000
ppm of sulfur vapor.
air air
3
pipe air surface
d ) T T ( g
Ra
α ν
− β
=
Equation 1. Rayleigh number for free convection
(Incropera and Dewitt 1996).
16
The Nusselt number is used to calculate a heat transfer coefficient from which the required heat
transfer area can be calculated. The Nusselt number is given by Equation 2 when 10
-5
≤ Ra ≤
10
12
and in this case was Nu = 47.9 (using a Prandtl number for air of Pr = 0.707). The heat
transfer coefficient under these conditions was calculated from Nu using Equation 3 and was h
fc

= 0.97 Btu/(ft
2
hr °F). This low value of heat transfer coefficient is typical for free convection
situations where values are typically 1-2 Btu/(ft
2
hr °F).





Because the inlet and outlet temperatures are different, a log-mean temperature difference
(LMTD) was used to calculate the heat transfer area required for cooling. The LMTD is given by
Equation 4 and the calculated value was LMTD = 168°F.


The amount of heat to be removed is the heat needed to cool the gas from 266°F to 230°F and
was q = m
*
Cp
gas*
(T
hotIN
-T
hotOUT
) = 12,190 Btu/hr. There is so little sulfur in the vapor (75 ppm)
that its contribution to the total heat duty (via the heat of fusion) is miniscule and essentially all
of cooling duty is used in removing sensible heat from the gas.

The heat transfer surface area required to remove 12,190 Btu/hr of heat from the gas given a
LMTD = 168°F and h
fc
= 0.97 Btu/(ft
2
hr °F) is A = q/(h*LMTD) = 75 ft
2
. This corresponds to 43
feet of 6 inch SCH40 pipe (the schedule number is relevant because it determines the outside
diameter of the pipe for a standard pipe size). To be conservative we installed 75 ft of pipe, an
overdesign factor of 1.7.

The flow of gas inside the pipe is turbulent (Reynolds number = Re = 1.1x10
5
) which improves
the collection efficiency of sulfur depositing on the walls of the pipe rather than being carried
along as tiny solid particles in the streamlines of cool gas (as would occur if the flow were
2
27
8
16
9
6
1
Pr
559 . 0
1
Ra 387 . 0
6 . 0 Nu
(
(
(
(
(
(
(
(
(
¸
(

¸

(
(
(
¸
(

¸

|
.
|

\
|
+
+ =
Equation 2. Nusselt number for horizontal pipe in free convection
(Incropera and Dewitt 1996).
Nu
d
k
h
pipe
air
fc
=
Equation 3. Heat transfer coefficient
( ) ( )
( )
( )
(
¸
(

¸



− − −
=
cold hotOUT
cold hotIN
cold hotOUT cold hotIN
T T
T T
ln
T T T T
LMTD
Equation 4. LMTD calculation
17
laminar). The calculated pressure drop (assuming incompressible at these low pressures) was
less than 1 psi and in practice, we observed a pressure drop of about 0.6 psi.

Figure 15 is a photograph of the pilot unit with an overlay of how the new line was attached (the
actual configuration was somewhat different when installed, but the basic concept was
unchanged). In the original configuration, the pilot plant was attached to Whiting’s flare header
(on the left side of the photograph) using 6 inch SCH40 uninsulated pipe that served as both the
inlet gas bypass as well as the exit from the sulfur condenser (red line in Figure 15). If this line
were to plug with condensed sulfur vapor, then there would be no way to bypass the sour gas
feed at the pilot plant. In addition, this line was much shorter than 75 ft cooling line making it
more likely that sulfur would reach Whiting’s flare system. More alarming, sulfur powder was
observed in the original line at a small sampling port located about 15 ft upstream of the header
entrance, so sulfur was making it to the flare piping in the original layout.

In the new configuration, the original tie-in to the flare header remained connected but was only
used for bypassing and flaring the feed gas. The tee that connected the original flare line to the
exit of the sulfur condenser was disconnected and blinded, and the independent, 75 ft x 6 inch
SCH40 line was attached between the exit of the sulfur condenser and the flare header (yellow
line in Figure 15). Blocking valves were placed at both ends so that the line so that it could be
taken out of service and cleaned if necessary. Flanged tees were used rather than elbows to
facilitate cleaning and to increase turbulence in the piping to help with sulfur collection.





Use minimum number of tees
w/blinds that will still allow for easy
cleaning
New flare line has its
own tie into the flare
header (manual block
valve just before
header)
Sulfur Condenser
Old flare connection blanked
off
Existing flare
line
Point where
inlet gas can
be bypassed to
flare remains
unchanged
Block valve
Slope line down hill to a
tee so that line can drain
after cleaning
Skid
New vapor line to flare
heater
75 ft of 8 inch SCH40 pipe
tied into vapor outlet of
sulfur condenser
Use minimum number of tees
w/blinds that will still allow for easy
cleaning
New flare line has its
own tie into the flare
header (manual block
valve just before
header)
Sulfur Condenser
Old flare connection blanked
off
Existing flare
line
Point where
inlet gas can
be bypassed to
flare remains
unchanged
Block valve
Slope line down hill to a
tee so that line can drain
after cleaning
Skid
New vapor line to flare
heater
75 ft of 8 inch SCH40 pipe
tied into vapor outlet of
sulfur condenser

Figure 15. Photograph of pilot plant showing original flare line
(highlighted in red) and planned location of new flare line (yellow).
18
We found that the long cooling pipe was necessary and functioned as designed. At the end of
the run after the pilot plant had been shut down, about 100 lb of sulfur was removed from the
flare extension when it was opened for inspection (we predicted that about 102 lb should have
been deposited). Most of the sulfur was deposited close to the first tee where the concentration
of sulfur vapor was highest and where the flow first impinges on a pipe tee at a right angle.
Importantly, smaller amounts of sulfur were found farther downstream, as close as 20 ft
upstream of the flare header; but fortunately, no sulfur made it to the flare header. Therefore,
our solution for removing entrained and vapor phase sulfur from the product gas exiting the
sulfur condenser worked quite well and was inexpensive to implement. For a commercial
application of course, a more permanent solution such as a heated sulfur coalescing filter would
be used.

5. Field Test Results

As mentioned previously, the field test was very successful. In this section we describe the
results in detail in Section 5.1 we discuss the composition of the feed stream; in Section 5.2 we
discuss the catalytic oxidation results and finally in Section 5.3 we compare the results of
laboratory testing the catalyst used in the field test with fresh catalyst.

Whiting’s Sable San Andreas Gas Plant is used to collect and flare associated gas from CO
2
oil
well flooding operations. The total gas flow varied somewhat but averaged about 300,000
ft
3
/day (ca. 200 SCFM) and contained about 6000 to 8000 ppm of H
2
S. The H
2
S concentration
varied from day to day, as did the total feed flow rate when different oil wells went on and off
line. The main components of the gas were methane (ca. 20%), CO
2
(ca. 60%), ethane (9-
10%), propane (6-7%) and butanes (ca. 3%). The gas also contained about 3000 ppm of
hydrocarbon liquids as vapor in equilibrium with the liquid in the knockout drum located
upstream of the feed preheater.

5.1. Feed Gas

A detailed analysis of the feed and product gases was performed on grab samples by an
outside laboratory. The results of those analyses are given in Table 1.

Most of the C
5
+ hydrocarbons in the gas are removed when then enter the Whiting plant using a
knockout drum. In addition there is a second liquid knockout located on the pilot plant skid
(Figure 4). Still the inlet gas analysis in Table 1 shows that the gas contained almost 2.8 vol%
of C
5
+ hydrocarbons. Under these conditions, the catalyst was continuously exposed to these
hydrocarbons at the reaction temperature of 360°F (182°C) for the entire 1000+ hours of
operation. After 1000 hours at sour gas flow rate of 200 SCFM, more than 13 million standard
cubic feet of gas were processed and assuming that the total concentration of hydrocarbons
with molecular weights higher than butane (i.e. C
5
and up) was a constant 2.8 vol%, the catalyst
(1700 lb) was exposed to over 35 short tons of C
5
+ hydrocarbons over the course of the test.
This represents over 40 times the weight of the catalyst in higher molecular weight
hydrocarbons. If these hydrocarbons had been deleterious to catalyst performance, we would
have observed severe catalyst deactivation and we did not; no catalyst deactivation was
observed over the 1000+ hour course of the test.


19


5.2. Catalytic H
2
S Oxidation Test Results

Figure 16 shows the sour gas flow rate and the inlet H
2
S concentration during the 1000+ hour
test. During the first 150 hours of the test (6 days), the flow rate was about 280 SCFM but the
H
2
S concentration was low (6000 ppm). There was a significant change in the sour gas flow
rate during the pilot plant test as different wells were brought on and off line. The H
2
S
concentration gradually increased over the first 300 hrs (12.5 days), but after that the
concentration was essentially constant at about 8000 ppm. The inlet and outlet H
2
S, SO
2
and
O
2
concentrations were measured using GasTech stain tubes. The stain tubes provided a
simple and reliable method to determine the H
2
S, SO
2
and O
2
concentrations without the
problems we encountered with gas chromatography (GC). The hydrocarbon vapors present in
the gas (few thousand ppm) contaminated the GC column making the GC gas analysis results
erratic. We also analyzed for O
2
to determine if there was any oxygen slipping through the
catalyst bed; none was detected. The oxygen concentration was also measured using an
electrochemical analyzer. Because H
2
S will damage the electrochemical cell, this instrument
was protected from H
2
S and hydrocarbons by a series of molecular sieve, and Purafil (KMnO
4

impregnated alumina) beds. The molecular sieve traps hydrocarbons and the potassium
permanganate (KMnO
4
) oxidized H
2
S to sulfate (which remains adsorbed on the Purafil beads).

Figure 17 shows the H
2
S conversion as a function of time on stream during the pilot plant direct
oxidation test. The H
2
S conversion was approximately 90% for the duration of the test and did
not decrease with time. Because we kept the catalyst temperature constant during this time, the
constant H
2
S conversion indicates that no catalyst deactivation had occurred in 1000+ hours of
the test (this was confirmed by testing the spent catalyst from the pilot reactor in the laboratory
with fresh catalyst as discussed in Section 5.3). The reason that the conversion remains
constant even through the flowrate of feed gas is changing, is because the reaction is mass
transfer limited. The lack of deactivation is especially significant considering that the catalyst
was exposed to over 40 tons of C
5
+ hydrocarbon vapors and even larger quantities of methane,
Table 1. Gas analysis from Laboratory Services, Hobbs, New Mexico (only compounds that
were detected are listed).
Component Mol% (inlet) Mol% (outlet) Component Mol% (inlet) Mol% (outlet)
H
2
S 0.8000 0.095 cyclohexane 0.1698 0.1387
N
2
1.5972 2.8794 n-heptane 0.0976 0.0703
CH
4
17.6750 17.7853 methylcyclohexane 0.0517 0.0378
CO
2
58.6264 58.6625 toluene 0.0218 0.0136
Ethane 8.7006 8.5607 n-octane 0.0053 0.0032
Propane 6.4640 6.2643 ethyl benzene 0.0029 0.0024
isobutane 0.9798 0.9228 p and m xylene 0.0029 0.0027
n-butane 2.3841 2.3154 o-xylene 0.0007 0.0004
isopentane 0.7385 0.7115 n-nonane 0.0022
n-pentane 0.7715 0.7453
cyclopentane 0.0105 0.012 Mercaptans (ppm) 101.00 20
2-methylpentane 0.1512 0.1354
3-methylpentane 0.1345 0.1203 Specific gravity
(air =1 )
0.45
n-hexane 0.2658 0.2353 Gross BTU/CF dry 731.00
methylcyclopentane 0.1375 0.1144 Gross BTU/CF wet 718.00
benzene 0.2107 0.1692
20
ethane and butanes during the test without any adverse affects. The resistance of the catalyst
to deactivation when exposed to hydrocarbon vapors is consistent with our earlier laboratory
investigations where we contaminated our synthetic gas with toluene, xylene and hexane. No
deactivation was observed in the laboratory studies and the hydrocarbons simply passed over
the catalyst bed unreacted without coking or fouling the catalyst.



Figure 17 also shows the airflow as a function of time during the pilot plant test. The airflow is
included in Figure 17 to show how the fluctuations observed in the H
2
S conversion (although
small) were due to our intentionally varying the airflow (and consequently the O
2
/H
2
S ratio).
This was done to determine the affect of changing O
2
/H
2
S ratio on H
2
S conversion and the
catalyst’s selectivity to sulfur and SO
2
. When the airflow was held constant, the H
2
S conversion
was constant (see for example the data between 400 and 500 hours in Figure 17).

5000
6000
7000
8000
9000
0 200 400 600 800 1000 1200
Time on stream (hours)
H
2
S

i
n
l
e
t

c
o
n
c
e
n
t
r
a
t
i
o
n

(
p
p
m
)
0
50
100
150
200
250
300
S
o
u
r

g
a
s

f
l
o
w

r
a
t
e

(
C
F
M
)
H2S inlet (ppm) Sour gas flow CFM
Figure 16. Sour gas flow rate and inlet H
2
S concentration during field test.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 200 400 600 800 1000 1200
Time on stream (hours)
H
2
S

c
o
n
v
e
r
s
i
o
n
0
2.5
5
7.5
10
A
i
r

f
l
o
w

(
c
f
m
)
H2S conversion AIR FLOW (cfm)

Figure 17. H
2
S conversion and air flow rate during field test
21

Figure 18 shows the concentration of SO
2
in the outlet (product gas) during the test. The airflow
is shown again to illustrate that by varying the airflow, we can control the concentration of SO
2

in the outlet gas. Note that the SO
2
concentration tracks with the airflow quite well. In any case,
the SO
2
concentration never exceeded 75 ppm and was typically about 12 ppm when operating
under conditions that produced a high selectivity for elemental sulfur (e.g. the time between 200
and 700 hours in Figure 18.

Table 2 compares the sour gas flow rates, sulfur production and SO
2
emissions when the pilot
plant is removing an average of 89% of the sulfur in the gas. Because the pilot plant processes
all of the gas that would normally be flared by Whiting, and the selectivity to elemental sulfur is
practically 100%, the reduction on SO
2
emissions from the Whiting flare is equal to the mass of
sulfur (as H
2
S) converted. For example, operation for over 1000 hours with an average H
2
S
concentration of 7341 ppm, a total of 3.9 tons of sulfur enters the plant. The DO process
converts 89% of that into elemental sulfur. The unconverted (11%) H
2
S is burned in the flare in
the usual manner producing SO
2
. Over the course of 1000 hours, our process discharged
about 0.8 tons of SO
2
including the amount of unconverted H
2
S that is flared. For comparison, if
0
25
50
75
100
0 200 400 600 800 1000 1200
Time on stream (hours)
S
O
2

o
u
t
l
e
t

(
p
p
m
)
0.0
1.0
2.0
3.0
4.0
5.0
6.0
A
i
r

F
l
o
w

(
C
F
M
)
SO2 outlet (ppm) AIR FLOW (cfm)

Figure 18. SO
2
outlet concentration and air flow during field test.
Table 2. Production summary for field test at time = 1000 hours.
Field Test Case No Sulfur Recovery Case
Average sour gas flow rate
(SCFM)
228 228
Average air inlet flow rate
(SCFM)
3.5 0
Average H
2
S inlet (ppm) 7341 7341
Average H
2
S outlet (ppm) 790 0
Selectivity to elemental sulfur 100% N/A
Average sulfur yield 89% 0
Total sulfur inlet (lbs) 7953 7953
Total sulfur inlet (tons) 3.9 3.9
Total sulfur recovered (lbs) 7097 0
Total sulfur recovered (tons) 3.6 0
Total sulfur flared as SO
2
(tons) 0.86 7.95
22
the feed gas were directly flared, then almost 8 tons of SO
2
would have been emitted. This
comparison illustrates one advantage of TDA’s direct oxidation process, that even at modest
low sulfur recovery efficiencies (ca 90%), very large reductions in SO
2
emissions are possible.

The Direct Oxidation process also can be used if higher sulfur recovery efficiencies are
required. In that case, a tail gas treatment unit (TGTU) such as liquid redox, amine with recycle
or scavengers (e.g. SulfaTreat
®
) is placed downstream of the DO unit to remove the
unconverted H
2
S.

5.3. Laboratory Testing of Fresh and Used Catalyst

On concern we had was that because the H
2
S conversion remained constant at about 90%, but
that over time the flow rate of feed gas slowly decreased (Figure 16), was that this effect might
have masked catalyst deactivation. To test this possibility, we tested used catalyst taken from
the pilot plant reactor after the end of the pilot run, with fresh catalyst. The tests were done in
the laboratory under carefully controlled conditions of temperature, gas composition and gas
flow rate.

Figure 19 shows the results from the laboratory testing of fresh (blue bars) and used (red bars)
catalyst. The used catalyst was removed from the pilot plant reactor after the 1000+ hour test.
The samples were taken from three radial locations at three depths in the catalyst bed. The
used catalyst tested in the laboratory was an average sample made by grinding and sieving a
portion of each sample from the reactor and then mixing equal amounts of these samples
together.

The reaction conditions for the laboratory test were essentially identical to those used during the
field test. The temperature was 356°F (180°C), the space velocity was approximately 600
ft
3
gas
/ft
3
catalyst
/hr, and the gas contained 8000 ppm of H
2
S. The oxygen concentration was varied
between 3200 ppm and 4400 ppm and data were obtained at O
2
/H
2
S ratios that corresponded
to 80%, 90% and 100 % of the stoichiometric amount of O
2
need for the reaction H
2
S + ½ O
2
Æ
S + H
2
O (i.e. O
2
/H
2
S = 0.40, 0.45 and 0.5 respectively). Fresh catalyst (from the same batch
that was used when filling the reactor on the pilot plant) was tested under identical conditions.
Both the fresh and the used catalysts exhibited essentially identical performance indicating that
65
70
75
80
85
90
95
0.8 0.9 1.0
O
2
Concentration (Fraction of Stoichiometric)
P
e
r
c
e
n
t

C
o
n
v
e
r
s
i
o
n
Used Catalyst Fresh Catalyst
T = 356
o
F
P = 1 atm
8000 ppm H
2
S
3200 - 4400ppm O
2
Balance = N
2
No SO
2
Detected

Figure 19. Laboratory testing of fresh (dark bars) and used (light bars)
catalyst.
23
there was no deactivation of the catalyst while it was in service in the pilot plant test. The
reason that the conversion remained at 90% while the gas flow dropped was that, at least at the
lower flow rates, the H
2
S oxidation reaction was mass transfer limited.

6. Technology Transfer

6.1. Technology/Information Transfer

TDA has successfully completed the Phase III pilot plant testing project and has shown that the
TDA catalyst developed for the direct oxidation of H
2
S into sulfur and water is active, selective
and long-lived. The test lasted for more than 1000 hours (42 days) desulfurizing 100,000–
300,000 SCFD of CO
2
-rich, associated gas that contained 8000 ppm of H
2
S. The overall H
2
S
conversion was approximately 90% during the course of the test, and minimal SO
2
was formed.
Currently, TDA’s direct oxidation process has been exclusively licensed to SulfaTreat, a
business unit of MI and is being offered commercially under the brand name SulfaTreat
®
-DO.
The original pilot plant (now in Plains, TX) will be disassembled and shipped back to GTI in
Chicago, IL by June 2005.

6.2. Public Relations and Marketing

TDA’s H
2
S oxidation process has been licensed to SulfaTreat as the SulfaTreat-DO
®
process

(SulfaTreat
®
-“Direct Oxidation”). SulfaTreat is a business unit of M-I, LLC. M-I is a Smith-
International/Schlumberger Company. SulfaTreat is actively marketing the technology, and the
first commercial unit will be installed in 2005. SulfaTreat is in final negotiations with the
customer. That unit will process approximately 1 million SCFD of natural gas containing about
1% H
2
S.

The SulfaTreat-DO
®
process is being advertised in appropriate trade magazines and has
generated many inquires. Figure 20 is a copy of the advertisement published in Oil, Gas and

Figure 20. Advertisement in Oil, Gas and Petrochemical Equipment for the SulfaTreat-
DO
®
process.
24
Petrochemical Equipment and Figure 21 is a copy of the advertisement for the process that
appeared in the March 2004 issue of Hydrocarbon Processing (Gulf Publishing Co).




7. Conclusions

The objective of the project was to perform a field test of TDA’s gas sweetening process under
realistic conditions. TDA Research Inc has successfully completed this Phase III pilot plant test
at Whiting Petroleum’s Sable San Andreas Gas Plant. The average gas flow during the test
was 228,000 SCFD. The gas contained significant quantities of CO
2
(ca 60%), CH
4
(ca 20%)
and C
3
+ hydrocarbons (ca 10%). The average H
2
S concentration was 7341 ppm. No catalyst

Figure 21. Ad for direct oxidation in March 2004 issue of
Hydrocarbon Processing (scanning and slight rotation of the
image caused blurring of the text – the original is crisp and clear).
25
deactivation was observed for over the course of the 1000+ hour test. Minimal (ca 10-15 ppm)
of SO
2
was formed during the test.

The selectivity to sulfur was essentially 100% and the catalyst converted 90% of the H
2
S into
sulfur and water. Approximately 3.6 tons of sulfur (in the elemental form) were recovered from a
total inlet of 3.9 tons of sulfur (as H
2
S). The total SO
2
emissions from the plant (taking into
account flaring of the unconverted H
2
S) were 0.86 tons. This much lower than the normal 8
tons of SO
2
that would have been generated with straight flaring of the feed gas over the same
period of time. The pilot plant was simple to operate and required much less operator
intervention than is typical for a new unit coming on line. It was also considerably easier to
operate than a typical liquid redox system. The chief plant operator during the test was Mr.
Eugene Peeples. Mr. Peeples has more than 30 years of experience operating commercial
scale liquid redox processes, and thus he is highly qualified to judge the ease of operation of
the Direct Oxidation process compared to existing commercial liquid redox sulfur recovery
processes. Mr. Peeples indicated that the Direct Oxidation process was considerably easier to
run from an operator’s standpoint. The ease of use and low capital and operating costs of the
TDA Direct Oxidation process makes this an attractive technology to be used where traditional
sulfur recovery technologies are too expensive. As a result, the Direct Oxidation process is well
suited for sulfur recovery in small to medium sized plants. Currently, TDA’s Direct Oxidation
process has been exclusively licensed to SulfaTreat, and is being offered commercially under
the trade name SulfaTreat-DO
®
.

SulfaTreat is a division of M-I, which is a joint venture between Schlumberger and Smith
International. SulfaTreat’s flagship H
2
S scavenging technology is the market leader and is
currently used to treat nearly 3 trillion cubic feet of gas annually from more than 1,000
applications in more than 20 countries worldwide. The SulfaTreat Company has become a
widely recognized and trusted leader in the industry serving international markets of Energy,
Environmental and Water Treatment. A new SulfaTreat system is installed somewhere in the
world nearly every business day.

With SulfaTreat’s background and expertise, they are ideally suited for marketing the Direct
Oxidation process. In SulfaTreat-DO
®
, the Direct Oxidation process can be operated as a stand
alone unit, or used upstream of a gas polishing step such as the SulfaTreat
®
scavenger, a liquid
redox process or other sulfur recovery technologies. In addition to stand-alone units, the
SulfaTreat-DO
®
process can be used to “unload” existing sulfur recovery systems, thus
providing customers with a low cost simple alternative to increasing the sulfur handling capacity
of their equipment.

8. References

Daubert, T.E.; Danner, R.P.; Sibul, H.M. and Stebbins, C.C. (1997) Physical and
Thermodynamic Properties of Pure Chemicals, Design Institute for Physical Property
Data (DIPPR), American Institute of Chemical Engineers, Taylor and Francis.
Incropera, F.P. and DeWitt, D.P.(1996), Fundamentals of Heat and Mass Transfer, 4th ed.,
John Wiley & Sons, New York (1996).
Tuller, W.N. (1954) Sulfur Data Book, Freeport Sulfur Company.

Updated By: Date:

Girish Srinivas January 2005

Disclaimer
“This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.”

2

Minimal (ca.86 tons. small to medium sized plants). The pilot plant was simple to operate and required much less operator intervention than is typical for a new unit being commissioned. The feed was associated gas from CO2 flooding operations carried out on Whiting’s oil wells.6 tons of elemental sulfur was recovered from a total inlet of 3.000 standard cubic feet per day (SCFD) of gas that contained approximately 60 vol% CO2. 10-15 ppm) of SO2 was formed during the test. We anticipate that the first plant will be installed in 2005. 20 vol% CH4 and 10 vol% C3+ and higher hydrocarbons. The ease of use and low capital and operating costs of TDA’s Direct Oxidation process makes it an attractive technology to be used where traditional sulfur recovery technologies are too expensive (e. Currently.Abstract This project was a Phase III pilot plant test of TDA’s gas sweetening process done under realistic conditions. TDA Research Inc successfully completed the test at Whiting Petroleum’s Sable San Andreas Gas Plant. and is being offered commercially under the trade name SulfaTreat-DO®. 3 . TDA’s Direct Oxidation pilot plant is easier to operate than liquid systems. This amount of SO2 is much lower than the normal 8 tons that would have been emitted if all of the H2S were flared over the time of the pilot plant test. Approximately 3. We sited our pilot plant in line with the flare so that we could remove the hydrogen sulfide (H2S) prior to flaring. The feed was approximately 228. Our operator (Mr. The gas is collected and piped to the Sable gas plant where it is normally flared. TDA’s direct oxidation process has been exclusively licensed to SulfaTreat.9 tons of sulfur (as H2S). The selectivity of our process for converting H2S into elemental sulfur was essentially 100% and the catalyst converted 90% of the H2S into sulfur and water (the remaining 10% of the H2S passed through unconverted). The total amount of SO2 released from the plant (taking into account flaring of the unconverted 10% H2S) was 0. Importantly. no catalyst deactivation was observed for over the course of the 1000+ hour test.g. The average H2S concentration in the gas during the field test was 7341 ppm. Eugene Peeples) has more than 30 years of experience operating commercial scale liquid redox sulfur recovery processes and in his opinion.

2.3. Sulfur Bins (“Pots”) 4. Overview 4.1. 4. LOCATION: NPTO 5 5 6 7 7 11 12 14 14 18 18 19 22 23 23 23 24 25 26 4 .5. Modification of Flare Tie-In to Prevent Sulfur Vapor Plugging 5. 3. Catalytic Reactor 4.1. Laboratory Testing of Fresh and Used Catalyst 6. Conclusions 8. 2.Table of Contents 1.3.1. Sulfur Condenser 4. Catalytic H2S Oxidation Test Results 5. Executive Summary Objectives Project Description and Background Description of the Pilot Plant 4. References 9. Field Test Results 5.2. Technology Transfer 6. Feed Gas 5.2.4. Public Relations and Marketing 7. Technology/Information Transfer 6.

Our operator (Mr.g. 10-15 ppm) of SO2 was formed during the test. Executive Summary This project was a Phase III pilot plant test of TDA’s gas sweetening process done under realistic conditions. The small amount of water vapor produced by the process remains in the sweet gas exiting the sulfur condenser. The average H2S concentration in the gas during the field test was 7341 ppm. The feed was approximately 228. Eugene Peeples) has more than 30 years of experience operating commercial scale liquid redox sulfur recovery processes and in his opinion. Minimal (ca. propane. We sited our pilot plant in line with the flare so that we could remove the hydrogen sulfide (H2S) prior to flaring. mercaptans and other impurities commonly found in natural gas and associated gas streams. In TDA’s process. TDA’s Direct Oxidation pilot plant is easier to operate than liquid systems. no catalyst deactivation was observed for over the course of the 1000+ hour test. temperature gradients within the catalyst bed.6 tons of elemental sulfur was recovered from a total inlet of 3. Prior to the field test. field-testing at the pilot plant scale is necessary to determine how the catalyst will perform when exposed to the wide variety of hydrocarbons. hydrogen sulfide gas (H2S) is catalytically oxidized (using air) to form elemental sulfur and water. and is being offered commercially under the trade name SulfaTreat-DO®. small to medium sized plants). The gas is collected and piped to the Sable gas plant where it is normally flared. 2. and 20% ethane. by testing at the pilot scale. We anticipate that the first plant will be installed in 2005. TDA Research Inc successfully completed the test at Whiting Petroleum’s Sable San Andreas Gas Plant. all testing had been done at the laboratory scale where synthetic mixtures of feed gas were tested. Also. The pilot plant was simple to operate and required much less operator intervention than is typical for a new unit being commissioned. and engineering scale issues are addressed that cannot be investigated at the much smaller laboratory scale. non-uniformities in gas flow. 20% CH4. The feed was associated gas from CO2 flooding operations carried out on Whiting’s oil wells. 60% CO2.000 standard cubic feet per day (SCFD) of gas that contained approximately 60 vol% CO2. The ease of use and low capital and operating costs of TDA’s Direct Oxidation process makes it an attractive technology to be used where traditional sulfur recovery technologies are too expensive (e. Objectives The objective of the project was to perform a field test of TDA’s gas sweetening process under realistic conditions. butane and traces of higher hydrocarbons. This report describes the results from a successful field test of TDA’s process to remove H2S from an associated gas stream that contained approximately 8000 ppm of H2S. The elemental sulfur is formed in the vapor phase and is subsequently condensed downstream of the catalytic reactor.1. While laboratory scale testing is sufficient for catalyst development and initial studies.9 tons of sulfur (as H2S).86 tons. Importantly. Approximately 3. Currently. We also report an 5 . The total amount of SO2 released from the plant (taking into account flaring of the unconverted 10% H2S) was 0. The selectivity of our process for converting H2S into elemental sulfur was essentially 100% and the catalyst converted 90% of the H2S into sulfur and water (the remaining 10% of the H2S passed through unconverted). TDA’s direct oxidation process has been exclusively licensed to SulfaTreat. 20 vol% CH4 and 10 vol% C3+ and higher hydrocarbons. This amount of SO2 is much lower than the normal 8 tons that would have been emitted if all of the H2S were flared over the time of the pilot plant test.

300. The catalyst oxidizes hydrogen sulfide (H2S) to elemental sulfur and water. 20% methane and about 60% CO2 with the balance being ethane. The first commercial SulfaTreat-DO® plant is expected to be installed some time in 2005. Project Description and Background Direct Oxidation (DO) uses a proprietary patented catalyst that was developed by TDA. were not increased and Unocal decided not to spend the additional money needed to install and operate the plant. Unocal anticipated that the offshore platform would be subjected to more stringent SO2 emissions regulations and saw the Direct Oxidation process as a way to achieve increased gas production while reducing SO2 emissions. The pilot plant test was completely successful and the data have enabled us to evaluate the economics of the process and compare our process to currently available small-sulfur recovery technologies such as various liquid redox processes. with minimal if any SO2 formation. 3. to be field tested on a Unocal offshore platform in Mobile Bay. Having successfully demonstrated the TDA DO process. TDA has licensed the process to SulfaTreat. TX. TX. propane and butanes. The plant was installed at Whiting Petroleum Company’s Sable San Andreas gas plant outside Plains.economic analysis based on the field test data that shows that TDA’s process (which we refer to as Direct Oxidation or DO) is much less complex and lower in cost than competing commercial technologies. including Claus and SulFerox units. a business unit of M-I. The pilot plant was originally scheduled Figure 1. the Gas Technology Institute (GTI) and Unocal funded the design and fabrication of a $1. The process is currently being offered commercially under the trade name SulfaTreat-DO®.S. NM (Figure 1). 6 . which is about equidistant between Midland. Location of Plains. Lubbock. Department of Energy under Phase I and Phase II SBIR grants. potential customers will be much more confident about the reliability of the technology. DO catalyst development and demonstration at the bench scale was done with funding from the U. After extensive negotiations and exploring possible sites for the field test.000 pilot plant to test the process at close to commercial scale. After the laboratory scale demonstration of DO. Westfield is a well-established company with a long and successful history in designing and building sulfur recovery units. located off the coasts of Mississippi and Alabama. The environmental regulations on the platform however. The Whiting gas plant is located about 5 miles northwest of Plains. The gas that was used as the feed for the pilot plant contained about 8000 ppm of H2S. As a result of the field test and favorable economics (discussed later). This gas is associated gas obtained after CO2 flooding of Whiting oil wells. TX. Westfield Engineering is the primary contractor for detailed engineering design and for subcontracting the construction of commercial SulfaTreat®-DO units. TDA completed construction of the pilot plant and installed it at a new site in Texas (Figure 1) with funding from the Department of Energy (this project). TX and Hobbs. TX and the field test was completed in 2003.

The KO drum is equipped with level controls. a liquid knockout (KO) drum and a reactor bypass. a flare bypass etc. The pilot plant has five main “subsystems:” 1) the feed gas system which includes the gas manifold. Overview The pilot plant tests were conducted at the Whiting Petroleum Sable San Andreas Gas Plant located near Plains. 4) a sulfur u-trap and heat traced liquid sulfur handling piping. This included installation of the main electric gas heater. Figure 2 is a photograph of the site where the pilot plant was eventually located. tuning controllers and establishing the flow of process gas.4. Description of the Pilot Plant 4. 3) a sulfur condenser. The P&ID for the inlet piping and KO are shown in Figure 4. Photograph of Whiting Sable San Andreas gas plant before installation of the TDA sulfur pilot plant. automatic drainage. TX. Startup and shakedown of the plant was done during the first week of October in 2002. and 5) sulfur storage bins. and Figure 3 is a photograph of the plant during its initial installation (before being heat traced and insulated). This minimizes the amount of hydrocarbon vapors to which the catalyst can be exposed. 2) the catalytic reactor where H2S oxidation into sulfur vapor and water takes place. 7 . The liquid knockout (KO) drum is located upstream of the catalytic reactors and its function is to remove and hydrocarbon liquids that may be present in the gas stream.1. Shed Pipe rack with flare and feed gas lines Pad area for pilot plant Figure 2.

Photograph of pilot plant during installation at the Whiting site.Electric heater attaches here Reactor Sulfur storage pots Sulfur condenser Flare line Gas inlet not attached in this photo Figure 3. P&ID of the knockout drum section upstream of the catalytic reactors. Figure 4. 8 .

which was 250-260°F in the field test. Figure 5. Liquid sulfur exits the bottom of the bonnet of the condenser and sweet gas exits at the top. this vessel was empty and was valved off. The temperature of the sulfur condenser tubes is maintained by controlling the steam pressure on the shell side (boiling water) of the condenser. Unless this vapor is removed. In this application. Two fixed bed reactor vessels are shown in Figure 5 because in the original plan was to place the plant on a Unocal offshore platform in Mobile Bay. The process gas exiting the catalytic reactor (that contains the elemental sulfur vapor) flows tubeside. One of the reactor was used and was filled with catalyst. The gas exiting the sulfur condenser was at the sulfur condensation temperature. controlling the steam pressure controls the temperature of the sulfur condenser. The second “reactor” was to be used to contain the desiccant bed. The condenser is mounted slightly off horizontal so that liquid sulfur exiting the condenser will flow downhill and into a U-tube type trap and into sulfur bins (Figure 6). The reactor is made of carbon steel and is lined with refractory (described in detail in Section 4. Radian International did the detailed engineering (and made the drawings) early in the history of the project under subcontract to TDA. 9 . Because the saturation pressure of the shellside steam determines the saturation steam temperature. P&ID for reactor and sulfur condenser section of the pilot plant. In the field test at Plains. To prevent plugging of Whiting’s flare header. Because this gas is at 250-260°F and is in equilibrium with the liquid sulfur leaving the condenser.3) is a heat exchanger with a half-height tube sheet that is half filled with boiling water. the sweet gas contains about 75 ppm of sulfur vapor.2).Figure 5 is the process and instrumentation diagram for the reactor and condenser sections of the plant. The sulfur condenser (described bed in Section 4. Unocal wanted the option of drying the gas over a desiccant prior to desulfurization by catalytic oxidation. it will plug downstream piping.

10 . and because the focus of the pilot plant test was proving the catalytic oxidation of H2S to sulfur with a real gas stream. Wilbanks Engineering. we removed sulfur directly from the heat exchanger bonnet. Liquid sulfur exiting the sulfur condenser passed through a U-trap that acts as a sulfur seal and into collection bins. we will use a heated coalescing filter (as recommended by Westfield Engineering). and Ref-Chem. CO. Commercially available technologies exist for condensing sulfur vapor. TX. Sandra Huzyk of Huzyk Energy Management was the project manager for installing the plant and found the test site. Several contractors were involved in the installation and start up of the unit. we installed the long pipe because this option was quick and inexpensive. Figure 6.5. The bins are purged with air to degas the sulfur (Figure 6).we installed about 75 ft of 6 inch SCH40 carbon steel pipe between the pilot plant and Whiting’s flare header. Unfortunately.” The sulfur condenser and sulfur storage vessels are located on the bottom level of the unit (the unit has two levels to save space as per the original off-shore requirement). during the field test. This is discussed in detail in Section 4. we found that the bins badly leaked gas and were therefore not used. storing the sulfur in 55 gal drums. Houston. the heat tracing on the P-trap was not sufficient to maintain the proper liquid level. Therefore. P&ID for sulfur collection “pots. In addition. Denver. The primary contractors were Huzyk Energy Management. Odessa. TX. This pipe was unheated so the 75 ppm sulfur vapor would condense in it leaving only clean sulfur free gas to pass into the flare header. In a commercial application.

A 10 x 10 mesh stainless steel screen as placed over the Denstone balls and the catalyst (1700 lb of 1/8 inch x ¼ inch cylindrical pellets) was placed on top of the screen. They provide roots facilities. minerals processing. power.2. The catalytic reactor is made from carbon steel. A sheet of 10 x 10 mesh stainless steel screen was then placed on top of the catalyst and a final single 6-inch thick layer of ½ inch ceramic balls was place on top. Figure 8. and designed to operated at 25 psig. revamps & retrofits. refining.). Catalytic Reactor Solids are retained in the reactor by means of a cylindrical screen that is located at the bottom of the reactor. and in-plant contract maintenance services for the petrochemical. The first layer was a 6-inch deep layer of 1-inch diameter ceramic balls (NorPro Denstone). chemical. cement and manufacturing industries.Ref-Chem is a heavy industrial construction. A 6-inch layer of ½ inch ceramic balls and then a 6-inch thick layer of ¼ in ceramic balls followed this. The cylindrical screen also has a cap. Pilot plant installation (photo courtesy of Huzyk Energy Mgmt. Figure 8 is a detailed drawing of the reactor and how it was loaded with inerts and catalyst prior to the field test. 11 . Wilbanks installed the process control system and the heat tracing. oil & gas. Ref-Chem did the physical installation of the pilot plant at the Whiting site (Figure 7). The reactor was operated adiabatically and contained about 1700 lb of catalyst in the form of 1/8 in x ¼ in pellets. Figure 7. Detailed drawing of the pilot plant catalytic reactor. maintenance and engineering company. 4. plant expansions. air separation. The balls act as a flow distributor for the feed and product gases as a support for the catalyst pellets. lined with refractory.

which we never have in our application. For comparison. TX). Our typical operating temperature range is 250°F to 280°F. Schematic of sulfur condenser.000 centipoise. Figure 11 shows that the viscosity of sulfur at 375°F is about 60 lb/ft-sec.4. in the photograph – it is located on top of the bonnet at the end of the condenser just left of the water level gauge). At these temperatures. the viscosity of water at room temperature is about 1 centipoise. the viscosity of sulfur rapidly increases. Above 320°F. For example. Figure 9 is a schematic of how the condenser functions and Figure 10 is Liquid sulfur out Water returns from air-fin cooler a close up photograph of the sulfur condenser (the gas outlet is difficult to see Figure 9. By controlling the steam pressure (back pressure on the steam line from the condenser to the air fin cooler (see P&ID in Figure 5). Water level gauge Gas outlet Hot gas inlet Liquid sulfur outlet Flare line Water return Figure 10. eventually reaching enormous values (right side of Figure 11) when the so-called plastic or µ−sulfur exists (Tuller 1954). Photograph of sulfur condenser. It is important to keep the sulfur condenser temperature between about 240°F (the melting point of sulfur) and 320°F (where the viscosity rises dramatically) because of the peculiar viscosity versus temperature behavior of liquid sulfur. The huge increase in viscosity of liquid sulfur with 12 .3. the temperature of the boiling water inside the condenser can be controlled. Sulfur Condenser The sulfur condenser is essentially a Steam to air-fin cooler thermosiphon “reboiler” type of heat exchanger that operates at about 265°F. Hot gas from reactor At this temperature the saturation Sweetened product gas pressure of steam is about 38 psia (26 Water level psig at the altitude of Plains. The viscosity data shown in Figure 11 below 240°F (left side) are for the supercooled liquid. which is equal to 89. liquid sulfur has its minimum viscosity (Figure 11).

Steam generated on the shell side of the condenser (by heat transfer from the hot product gas in the tubes) flows up to an air-fin cooler where it is condensed and returned through a standpipe (see Figure 10). it is difficult to guarantee enough a uniform enough temperature along the length of the tubes so that overheating (making µ-sulfur) or too much cooling (sulfur solidification) can be prevented. hot-fluid-out. 60°F) for operating the sulfur condenser ∆ requires that there be a minimal T > 320°F temperature gradient along the length of the condenser tubes (which are about 15 S8 µ-S ft long). Either situation would plug the condenser. and therefore once µ-sulfur is formed. data from the Sulfur Data Book (Tuller 1954). As a result. but in commercial models we will use a larger diameter standpipe so that the standpipe volume is greater. The narrow temperature window (ca. S8 ring breaking and polymerization. We were able to control the loop and operate with continuous circulation. the constant temperature/boiling water design was used. The resulting material. This was because the return pipe was 2 inch SCH40 and there was no water reservoir.increasing temperature above 320°F is due to the rupture of the normal eight-atom sulfur rings (Figure 12) followed by polymerization of the now linear S8 chains. The phase change is irreversible. Too much steam pressure would blow the standpipe dry and with too little steam pressure. In a conventional cold-fluid-in. establishing natural circulation was very sensitive to the operation of the steam control valve. 13 . Figure 11. Figure 10 is a close-up of the condenser with the various lines labeled. In our case this was about 15 ft of water (approx 2 psi). Sulfur viscosity at low temperatures (left) and high temperatures (right). To avoid this. the steam in the condenser would drive water backwards up the standpipe into the air-fin cooler. (called µ-sulfur) is extremely viscous. Figure 12. counter-current type of heat exchanger. The sulfur condenser is a standard design and it functions essentially as a boiler with a thermosiphon. One problem we observed with this design during operation was that the volume of water in the standpipe was too small. The height of the standpipe determines the hydraulic head that drives the water back into the shellside of the condenser. the equipment will plug and will require shutdown for cleaning.

and 4) adding a long section of unheated. about 100 lb of sulfur would deposit in the piping downstream of the condenser during the test. Sulfur vapor pressure (Daubert et al. Rather than shut down the plant and re-heat-trace the entire downstream liquid piping. The goal of the pilot plant test was to demonstrate that the catalytic technology. pipe section upstream of the flare heater to allow the sulfur to deposit in that line before reaching the flare header. we modified the system so that we could withdraw the liquid sulfur directly from the sulfur condenser. methods and equipment for handling liquid and vapor phase sulfur is commercially available. The average sour gas flow rate was about 200 0. During the test. Tem perature (F) then the sulfur vapor concentration in the gas would be approximately 75 ppm.4. the bins were not gas tight.0 equilibrium with the liquid sulfur in the 200 250 300 350 400 450 500 550 condenser when it exits the condenser. Vapor Pressure (psia) 14 . we needed a quick and importantly. Among the options considered were: 1) treating the gas with a cold water spray. 0. Sulfur Bins (“Pots”) The sulfur bins were not used in the field test because of an operational difficulty in the lines that transport liquid sulfur from the outlet of the sulfur condenser to the bins. 3) plumbing the gas through a packed tower scrubber (using water) – there was an unused tower located on-site.1 SCFM. we found several cold spots between the exit of the sulfur condenser and the bins that would plug with solid sulfur.063 Torr = 1.3 passing over the liquid sulfur is large enough that considerable sulfur will exit 0. At this concentration and 200 SCFM. While the vapor pressure 0. Thus.4. this enabled us to continue the field test and was acceptable because the test was focused on the performance of the Direct Oxidation catalyst. 2) scrubbing the gas with a solvent.22x10 psia.5 of sulfur at this temperature is relatively -3 low (Pvapor = 0.4 see Figure 13) the volume of gas 0. Figure 13. We investigated several options to remove the sulfur vapor before the gas reached Whiting’s flare header. and not how to handle liquid sulfur (which is existing technology that can be easily engineered by Westfield Engineering for commercial units).6 about 260°F. Worse. which was unacceptable. Assuming that this gas is in 0. Modification of Flare Tie-In to Prevent Sulfur Vapor Plugging The sulfur condenser was operated at 0. 1997). While not a permanent solution.5. large diameter. If not removed. 4. inexpensive way to prevent sulfur vapor from condensing and depositing in Whiting’s flare line while permitting us to finish the field test on budget. this sulfur would plug Whiting’s flare lines.2 the condenser as vapor. which would have made using them dangerous.

the temperature of the air was assumed to be rather warm (80°F). The sulfur vapor recovery line was sized by assuming that free convection around the pipe was the only mechanism that would cool the gas. but time and cost constraints prevented us from using such a device during the field test. β is the coefficient of thermal expansion of air (2. solar radiation would slightly heat the pipe. thermal diffusivity. we would install a ppm of sulfur vapor. gave a pipe length that was longer than actually needed because natural convection is less efficient at cooling in this situation. The definitions of the terms in Equation 1 are as follows: αair is the thermal diffusivity of air [k/(ρ∗Cp)].002 necessary) and to create turbulence 0. Rayleigh number for free convection (Incropera and Dewitt 1996). several tees were installed (instead of elbows) to permit both cleaning (if 0. This dimensionless number expresses the balance between thermal expansion. The temperature of the surface of pipe was assumed to be the average of these temperatures (248°F). Ignoring radiation heat transfer simplified the analysis and more importantly. and νair is the kinematic viscosity of air (taken at the average pipe wall temperature. The gas inlet temperature was assumed to be 266°F and the outlet was assumed to be 230°F (10°F below the sulfur melting point). and the thickness of the convection layer of the gas in which the body being cooled is immersed (in this case air).8x107 which is in the turbulent flow regime.007 condenser and Whiting’s flare header.008 kmol S installing 75 ft of 6 inch SCH40 pipe between the vapor outlet of the sulfur 0.2 ft/s2). Most sections of the pipe would be cooled by radiation (especially at night when the air was cool). In a Figure 14. Ra = 3 gβ(Tsurface − Tair )d pipe 15 . S7(g) S5(g) Temper 0. The value of Ra calculated from Equation 1 was found to be Ra = 5. the Rayleigh number (Ra) is given by Equation 1. For free convection from a horizontal pipe in air. The properties of air at this temperature were used in the free convection calculations. Composition and dew point of for 8000 commercial application.000 Several thermocouples were installed C 0 50 100 150 200 250 along the length of pipe so that we could check the gas temperature. commercially available heated sulfur coalescing filter. ”too much cooling” is not a problem. To make the calculations even more conservative.001 S8(g) S6(g) S2(g) where sulfur would preferentially deposit. however during the day.005 200°F before it entered the flare header.006 With this length of pipe.File: C:\STEVE GEBHARD\SG_ PROJECTS\SULFUR proje We chose to protect Whiting’s flare line by 0. νair = 1. temperature. the gas exiting the sulfur condenser was cooled to below 0. the pipe was not a straight 0. Natural convection begins near Ra = 2000 and becomes turbulent for Ra ≥ 106. viscosity. 0.004 In addition.74x10-4 ft2/sec). ν air α air Equation 1.725x10-3 K-1). g is the gravity constant (32.003 run. 0.

Nusselt number for horizontal pipe in free convection (Incropera and Dewitt 1996).97 Btu/(ft2 hr °F) is A = q/(h*LMTD) = 75 ft2.1x105) which improves the collection efficiency of sulfur depositing on the walls of the pipe rather than being carried along as tiny solid particles in the streamlines of cool gas (as would occur if the flow were 16 . The heat transfer coefficient under these conditions was calculated from Nu using Equation 3 and was hfc = 0. The Nusselt number is given by Equation 2 when 10-5 ≤ Ra ≤ 1012 and in this case was Nu = 47.97 Btu/(ft2 hr °F).190 Btu/hr. k air Nu dpipe h fc = Equation 3.387Ra 6  0 . LMTD calculation (ThotIN − Tcold ) − (ThotOUT − Tcold ) The amount of heat to be removed is the heat needed to cool the gas from 266°F to 230°F and was q = m*Cpgas*(ThotIN-ThotOUT) = 12.9 (using a Prandtl number for air of Pr = 0. To be conservative we installed 75 ft of pipe. There is so little sulfur in the vapor (75 ppm) that its contribution to the total heat duty (via the heat of fusion) is miniscule and essentially all of cooling duty is used in removing sensible heat from the gas. The heat transfer surface area required to remove 12.6 +  Nu = 8   9   27    1 +  0. This corresponds to 43 feet of 6 inch SCH40 pipe (the schedule number is relevant because it determines the outside diameter of the pipe for a standard pipe size). an overdesign factor of 1.The Nusselt number is used to calculate a heat transfer coefficient from which the required heat transfer area can be calculated.559  16        Pr            Equation 2. Heat transfer coefficient Because the inlet and outlet temperatures are different. The LMTD is given by Equation 4 and the calculated value was LMTD = 168°F. 2       1   0. LMTD =  (T − Tcold )  ln hotIN   (ThotOUT − Tcold )  Equation 4.7. The flow of gas inside the pipe is turbulent (Reynolds number = Re = 1.707).190 Btu/hr of heat from the gas given a LMTD = 168°F and hfc = 0. This low value of heat transfer coefficient is typical for free convection situations where values are typically 1-2 Btu/(ft2 hr °F). a log-mean temperature difference (LMTD) was used to calculate the heat transfer area required for cooling.

so sulfur was making it to the flare piping in the original layout. sulfur powder was observed in the original line at a small sampling port located about 15 ft upstream of the header entrance. the pilot plant was attached to Whiting’s flare header (on the left side of the photograph) using 6 inch SCH40 uninsulated pipe that served as both the inlet gas bypass as well as the exit from the sulfur condenser (red line in Figure 15). If this line were to plug with condensed sulfur vapor. Photograph of pilot plant showing original flare line (highlighted in red) and planned location of new flare line (yellow). The calculated pressure drop (assuming incompressible at these low pressures) was less than 1 psi and in practice. In the new configuration. In addition. Figure 15 is a photograph of the pilot unit with an overlay of how the new line was attached (the actual configuration was somewhat different when installed. Blocking valves were placed at both ends so that the line so that it could be taken out of service and cleaned if necessary. then there would be no way to bypass the sour gas feed at the pilot plant.6 psi. The tee that connected the original flare line to the exit of the sulfur condenser was disconnected and blinded. Use minimum number of tees w/blinds that will still allow for easy cleaning Point where inlet gas can be bypassed to flare remains unchanged Old flare connection blanked off New vapor line to flare heater 75 ft of 8 inch SCH40 pipe tied into vapor outlet of sulfur condenser New flare line has its own tie into the flare header (manual block valve just before header) Existing flare line Sulfur Condenser Skid Slope line down hill to a tee so that line can drain after cleaning Block valve Figure 15. we observed a pressure drop of about 0. this line was much shorter than 75 ft cooling line making it more likely that sulfur would reach Whiting’s flare system. and the independent. More alarming. 17 . the original tie-in to the flare header remained connected but was only used for bypassing and flaring the feed gas. 75 ft x 6 inch SCH40 line was attached between the exit of the sulfur condenser and the flare header (yellow line in Figure 15). but the basic concept was unchanged). In the original configuration.laminar). Flanged tees were used rather than elbows to facilitate cleaning and to increase turbulence in the piping to help with sulfur collection.

000 ft3/day (ca. our solution for removing entrained and vapor phase sulfur from the product gas exiting the sulfur condenser worked quite well and was inexpensive to implement. CO2 (ca. In addition there is a second liquid knockout located on the pilot plant skid (Figure 4). 18 . The H2S concentration varied from day to day. For a commercial application of course. Most of the sulfur was deposited close to the first tee where the concentration of sulfur vapor was highest and where the flow first impinges on a pipe tee at a right angle. 3%). Importantly. 5. smaller amounts of sulfur were found farther downstream.8 vol% of C5+ hydrocarbons.1. The gas also contained about 3000 ppm of hydrocarbon liquids as vapor in equilibrium with the liquid in the knockout drum located upstream of the feed preheater. a more permanent solution such as a heated sulfur coalescing filter would be used. Under these conditions.1 we discuss the composition of the feed stream. Feed Gas A detailed analysis of the feed and product gases was performed on grab samples by an outside laboratory. the catalyst was continuously exposed to these hydrocarbons at the reaction temperature of 360°F (182°C) for the entire 1000+ hours of operation. If these hydrocarbons had been deleterious to catalyst performance. At the end of the run after the pilot plant had been shut down. Whiting’s Sable San Andreas Gas Plant is used to collect and flare associated gas from CO2 oil well flooding operations. more than 13 million standard cubic feet of gas were processed and assuming that the total concentration of hydrocarbons with molecular weights higher than butane (i. no sulfur made it to the flare header.8 vol%. about 100 lb of sulfur was removed from the flare extension when it was opened for inspection (we predicted that about 102 lb should have been deposited). the field test was very successful. C5 and up) was a constant 2.3 we compare the results of laboratory testing the catalyst used in the field test with fresh catalyst. Most of the C5+ hydrocarbons in the gas are removed when then enter the Whiting plant using a knockout drum. Still the inlet gas analysis in Table 1 shows that the gas contained almost 2. 200 SCFM) and contained about 6000 to 8000 ppm of H2S.2 we discuss the catalytic oxidation results and finally in Section 5. The results of those analyses are given in Table 1. we would have observed severe catalyst deactivation and we did not.e. In this section we describe the results in detail in Section 5. After 1000 hours at sour gas flow rate of 200 SCFM. ethane (910%).We found that the long cooling pipe was necessary and functioned as designed. propane (6-7%) and butanes (ca. 5. Therefore. 20%). The total gas flow varied somewhat but averaged about 300. as close as 20 ft upstream of the flare header. The main components of the gas were methane (ca. in Section 5. but fortunately. Field Test Results As mentioned previously. 60%). no catalyst deactivation was observed over the 1000+ hour course of the test. as did the total feed flow rate when different oil wells went on and off line. the catalyst (1700 lb) was exposed to over 35 short tons of C5+ hydrocarbons over the course of the test. This represents over 40 times the weight of the catalyst in higher molecular weight hydrocarbons.

9228 2. SO2 and O2 concentrations without the problems we encountered with gas chromatography (GC). the flow rate was about 280 SCFM but the H2S concentration was low (6000 ppm).00 718. We also analyzed for O2 to determine if there was any oxygen slipping through the catalyst bed. The molecular sieve traps hydrocarbons and the potassium permanganate (KMnO4) oxidized H2S to sulfate (which remains adsorbed on the Purafil beads). The stain tubes provided a simple and reliable method to determine the H2S. The lack of deactivation is especially significant considering that the catalyst was exposed to over 40 tons of C5+ hydrocarbon vapors and even larger quantities of methane. The H2S conversion was approximately 90% for the duration of the test and did not decrease with time.0004 0.6750 58.2.1144 0.0027 0.1387 0.1375 0.1692 cyclohexane n-heptane methylcyclohexane toluene n-octane ethyl benzene p and m xylene o-xylene n-nonane Mercaptans (ppm) Specific gravity (air =1 ) Gross BTU/CF dry Gross BTU/CF wet 0. Figure 17 shows the H2S conversion as a function of time on stream during the pilot plant direct oxidation test.5 days).9798 2.1354 0. Mol% (inlet) Mol% (outlet) Component Mol% (inlet) Mol% (outlet) Component H2S N2 CH4 CO2 Ethane Propane isobutane n-butane isopentane n-pentane cyclopentane 2-methylpentane 3-methylpentane n-hexane methylcyclopentane benzene 0.5607 6.0517 0.0105 0. is because the reaction is mass transfer limited. Gas analysis from Laboratory Services. The oxygen concentration was also measured using an electrochemical analyzer. and Purafil (KMnO4 impregnated alumina) beds.095 2.8000 1. New Mexico (only compounds that were detected are listed).7006 6.1698 0.1203 0. The H2S concentration gradually increased over the first 300 hrs (12. The reason that the conversion remains constant even through the flowrate of feed gas is changing.2658 0. SO2 and O2 concentrations were measured using GasTech stain tubes. this instrument was protected from H2S and hydrocarbons by a series of molecular sieve.1345 0.0024 0.0703 0.7385 0.012 0.Table 1.0378 0.00 0.7715 0.0007 0.0029 0. Catalytic H2S Oxidation Test Results Figure 16 shows the sour gas flow rate and the inlet H2S concentration during the 1000+ hour test.2643 0.0029 0.1512 0.2107 0.7453 0.3841 0. but after that the concentration was essentially constant at about 8000 ppm.4640 0. none was detected. The hydrocarbon vapors present in the gas (few thousand ppm) contaminated the GC column making the GC gas analysis results erratic.0976 0. There was a significant change in the sour gas flow rate during the pilot plant test as different wells were brought on and off line.0053 0.0032 0.5972 17. Because H2S will damage the electrochemical cell.45 731. Because we kept the catalyst temperature constant during this time.7853 58.8794 17.6625 8. 19 .3154 0.2353 0.7115 0.6264 8. the constant H2S conversion indicates that no catalyst deactivation had occurred in 1000+ hours of the test (this was confirmed by testing the spent catalyst from the pilot reactor in the laboratory with fresh catalyst as discussed in Section 5.3).00 5. The inlet and outlet H2S.0022 20 101. Hobbs.0218 0.0136 0. During the first 150 hours of the test (6 days).

100% 90% 80% 70% H2S conversion 60% 50% 40% 30% 20% 10% 0% 0 200 400 600 Time on stream (hours) H2S conversion AIR FLOW (cfm) 800 1000 10 7. The airflow is included in Figure 17 to show how the fluctuations observed in the H2S conversion (although small) were due to our intentionally varying the airflow (and consequently the O2/H2S ratio). This was done to determine the affect of changing O2/H2S ratio on H2S conversion and the catalyst’s selectivity to sulfur and SO2.5 0 1200 Figure 17. The resistance of the catalyst to deactivation when exposed to hydrocarbon vapors is consistent with our earlier laboratory investigations where we contaminated our synthetic gas with toluene.5 Air flow (cfm) 5 2. 9000 300 H2S inlet concentration (ppm) 250 Sour gas flow rate (CFM) 8000 200 7000 150 100 6000 50 5000 0 200 400 600 Time on stream (hours) 800 1000 0 1200 H2S inlet (ppm) Sour gas flow CFM Figure 16.ethane and butanes during the test without any adverse affects. When the airflow was held constant. Sour gas flow rate and inlet H2S concentration during field test. xylene and hexane. the H2S conversion was constant (see for example the data between 400 and 500 hours in Figure 17). 20 . H2S conversion and air flow rate during field test Figure 17 also shows the airflow as a function of time during the pilot plant test. No deactivation was observed in the laboratory studies and the hydrocarbons simply passed over the catalyst bed unreacted without coking or fouling the catalyst.

and the selectivity to elemental sulfur is practically 100%. the SO2 concentration never exceeded 75 ppm and was typically about 12 ppm when operating under conditions that produced a high selectivity for elemental sulfur (e.9 tons of sulfur enters the plant.g. The airflow is shown again to illustrate that by varying the airflow. the reduction on SO2 emissions from the Whiting flare is equal to the mass of sulfur (as H2S) converted.95 all of the gas that would normally be flared by Whiting.100 6.0 75 SO2 outlet (ppm) Air Flow (CFM) 4.0 2. Field Test Case No Sulfur Recovery Case Average sour gas flow rate 228 228 (SCFM) Average air inlet flow rate 3.9 Total sulfur recovered (lbs) 7097 0 Total sulfur recovered (tons) 3.6 0 Total sulfur flared as SO2 (tons) 0.5 0 (SCFM) Average H2S inlet (ppm) 7341 7341 Average H2S outlet (ppm) 790 0 Selectivity to elemental sulfur 100% N/A Average sulfur yield 89% 0 Total sulfur inlet (lbs) 7953 7953 Total sulfur inlet (tons) 3. Because the pilot plant processes Table 2.0 25 1.0 0 0 200 400 600 Time on stream (hours) SO2 outlet (ppm) AIR FLOW (cfm) 800 1000 0.0 5. SO2 outlet concentration and air flow during field test. we can control the concentration of SO2 in the outlet gas. In any case. Over the course of 1000 hours. Production summary for field test at time = 1000 hours. The DO process converts 89% of that into elemental sulfur.0 1200 Figure 18. Note that the SO2 concentration tracks with the airflow quite well. sulfur production and SO2 emissions when the pilot plant is removing an average of 89% of the sulfur in the gas.86 7. operation for over 1000 hours with an average H2S concentration of 7341 ppm. a total of 3. the time between 200 and 700 hours in Figure 18.9 3. Table 2 compares the sour gas flow rates.8 tons of SO2 including the amount of unconverted H2S that is flared. For comparison. our process discharged about 0. The unconverted (11%) H2S is burned in the flare in the usual manner producing SO2. if 21 . For example. Figure 18 shows the concentration of SO2 in the outlet (product gas) during the test.0 50 3.

The oxygen concentration was varied between 3200 ppm and 4400 ppm and data were obtained at O2/H2S ratios that corresponded to 80%.0 T = 356oF P = 1 atm 8000 ppm H2S 3200 . The used catalyst was removed from the pilot plant reactor after the 1000+ hour test. SulfaTreat®) is placed downstream of the DO unit to remove the unconverted H2S. a tail gas treatment unit (TGTU) such as liquid redox. amine with recycle or scavengers (e. but that over time the flow rate of feed gas slowly decreased (Figure 16). very large reductions in SO2 emissions are possible. O2/H2S = 0. The temperature was 356°F (180°C). Figure 19 shows the results from the laboratory testing of fresh (blue bars) and used (red bars) catalyst. then almost 8 tons of SO2 would have been emitted.8 0. The used catalyst tested in the laboratory was an average sample made by grinding and sieving a portion of each sample from the reactor and then mixing equal amounts of these samples together. The tests were done in the laboratory under carefully controlled conditions of temperature. was that this effect might have masked catalyst deactivation. The samples were taken from three radial locations at three depths in the catalyst bed. 95 90 Percent Conversion 85 80 75 70 65 0.4400ppm O2 Balance = N2 No SO2 Detected Figure 19. Laboratory Testing of Fresh and Used Catalyst On concern we had was that because the H2S conversion remained constant at about 90%.the feed gas were directly flared. Both the fresh and the used catalysts exhibited essentially identical performance indicating that 22 . In that case.40.9 O2 Concentration (Fraction of Stoichiometric) Used Catalyst Fresh Catalyst 1.3. Laboratory testing of fresh (dark bars) and used (light bars) catalyst.45 and 0. The Direct Oxidation process also can be used if higher sulfur recovery efficiencies are required. and the gas contained 8000 ppm of H2S. Fresh catalyst (from the same batch that was used when filling the reactor on the pilot plant) was tested under identical conditions. 5.5 respectively). gas composition and gas flow rate. 90% and 100 % of the stoichiometric amount of O2 need for the reaction H2S + ½ O2 S + H2O (i. To test this possibility.g. we tested used catalyst taken from the pilot plant reactor after the end of the pilot run. that even at modest low sulfur recovery efficiencies (ca 90%). The reaction conditions for the laboratory test were essentially identical to those used during the field test. the space velocity was approximately 600 ft3gas/ft3catalyst/hr. 0. with fresh catalyst.e. This comparison illustrates one advantage of TDA’s direct oxidation process.

Technology Transfer 6. TDA’s direct oxidation process has been exclusively licensed to SulfaTreat. selective and long-lived. 23 . The original pilot plant (now in Plains. TX) will be disassembled and shipped back to GTI in Chicago. Technology/Information Transfer TDA has successfully completed the Phase III pilot plant testing project and has shown that the TDA catalyst developed for the direct oxidation of H2S into sulfur and water is active. The test lasted for more than 1000 hours (42 days) desulfurizing 100.1.there was no deactivation of the catalyst while it was in service in the pilot plant test. The reason that the conversion remained at 90% while the gas flow dropped was that. 6. 6. a business unit of MI and is being offered commercially under the brand name SulfaTreat®-DO. LLC. The overall H2S conversion was approximately 90% during the course of the test. The SulfaTreat-DO® process is being advertised in appropriate trade magazines and has generated many inquires. Advertisement in Oil.000 SCFD of CO2-rich. Gas and Petrochemical Equipment for the SulfaTreatDO® process. Public Relations and Marketing TDA’s H2S oxidation process has been licensed to SulfaTreat as the SulfaTreat-DO® process (SulfaTreat®-“Direct Oxidation”). SulfaTreat is actively marketing the technology.2. and the first commercial unit will be installed in 2005. Gas and Figure 20. Figure 20 is a copy of the advertisement published in Oil. and minimal SO2 was formed. M-I is a SmithInternational/Schlumberger Company. SulfaTreat is in final negotiations with the customer. That unit will process approximately 1 million SCFD of natural gas containing about 1% H2S. the H2S oxidation reaction was mass transfer limited. IL by June 2005.000– 300. at least at the lower flow rates. Currently. associated gas that contained 8000 ppm of H2S. SulfaTreat is a business unit of M-I.

The average H2S concentration was 7341 ppm. 7. The gas contained significant quantities of CO2 (ca 60%). No catalyst 24 . CH4 (ca 20%) and C3+ hydrocarbons (ca 10%). Conclusions The objective of the project was to perform a field test of TDA’s gas sweetening process under realistic conditions. Figure 21.Petrochemical Equipment and Figure 21 is a copy of the advertisement for the process that appeared in the March 2004 issue of Hydrocarbon Processing (Gulf Publishing Co).000 SCFD. TDA Research Inc has successfully completed this Phase III pilot plant test at Whiting Petroleum’s Sable San Andreas Gas Plant. The average gas flow during the test was 228. Ad for direct oxidation in March 2004 issue of Hydrocarbon Processing (scanning and slight rotation of the image caused blurring of the text – the original is crisp and clear).

(1996). The SulfaTreat Company has become a widely recognized and trusted leader in the industry serving international markets of Energy. 8. Freeport Sulfur Company. and thus he is highly qualified to judge the ease of operation of the Direct Oxidation process compared to existing commercial liquid redox sulfur recovery processes. C.000 applications in more than 20 countries worldwide. thus providing customers with a low cost simple alternative to increasing the sulfur handling capacity of their equipment. the SulfaTreat-DO® process can be used to “unload” existing sulfur recovery systems. W.N. It was also considerably easier to operate than a typical liquid redox system. a liquid redox process or other sulfur recovery technologies. References Daubert. Design Institute for Physical Property Data (DIPPR). In addition to stand-alone units. which is a joint venture between Schlumberger and Smith International.C.6 tons of sulfur (in the elemental form) were recovered from a total inlet of 3. The selectivity to sulfur was essentially 100% and the catalyst converted 90% of the H2S into sulfur and water. 4th ed. As a result. R. Fundamentals of Heat and Mass Transfer. and Stebbins. The total SO2 emissions from the plant (taking into account flaring of the unconverted H2S) were 0. the Direct Oxidation process can be operated as a stand alone unit. Peeples has more than 30 years of experience operating commercial scale liquid redox processes.86 tons.9 tons of sulfur (as H2S). and DeWitt. SulfaTreat is a division of M-I.. American Institute of Chemical Engineers. TDA’s Direct Oxidation process has been exclusively licensed to SulfaTreat. (1954) Sulfur Data Book. T. Approximately 3. or used upstream of a gas polishing step such as the SulfaTreat® scavenger. and is being offered commercially under the trade name SulfaTreat-DO®. John Wiley & Sons. The pilot plant was simple to operate and required much less operator intervention than is typical for a new unit coming on line.deactivation was observed for over the course of the 1000+ hour test. Updated By: Girish Srinivas Date: January 2005 25 . New York (1996). F.. SulfaTreat’s flagship H2S scavenging technology is the market leader and is currently used to treat nearly 3 trillion cubic feet of gas annually from more than 1. H. The chief plant operator during the test was Mr. D. Currently. they are ideally suited for marketing the Direct Oxidation process. Peeples indicated that the Direct Oxidation process was considerably easier to run from an operator’s standpoint. Sibul. Mr. Taylor and Francis. Environmental and Water Treatment. Danner. With SulfaTreat’s background and expertise.P. The ease of use and low capital and operating costs of the TDA Direct Oxidation process makes this an attractive technology to be used where traditional sulfur recovery technologies are too expensive.P. the Direct Oxidation process is well suited for sulfur recovery in small to medium sized plants. Minimal (ca 10-15 ppm) of SO2 was formed during the test. (1997) Physical and Thermodynamic Properties of Pure Chemicals. Incropera. In SulfaTreat-DO. A new SulfaTreat system is installed somewhere in the world nearly every business day.M. Mr. Eugene Peeples.E. Tuller. This much lower than the normal 8 tons of SO2 that would have been generated with straight flaring of the feed gas over the same period of time.P..

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