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SOUR GAS TREATMENT

Process Engineering for By Kevin S. Fisher,


CrystaTech, Inc.; and
Dennis Leppin, Raj Palla
Natural Gas Treatment and Dr. Aqil Jamal, GTI E&P
and Gas Processing Group.
using Direct-Injection
H2S Scavengers
Design, troubleshooting and optimization of direct-injection H2S scavenging systems pose many challenges.
GTI and others from the oil and gas industry are working together to develop engineering test data and
modeling software needed to effectively address these tasks.
atural gas producers, domes- costs and/or the severe restrictions on ling the direct-injection scavenging

N tically and abroad, have


increasingly targeted lower-
quality gas resources for development.
space and weight encountered with off-
shore applications. While the direct-
injection method offers these advan-
process. The potential benefit of such
an effort is substantial, considering the
estimated $50 million/year spent on
This trend continues to drive the tages over batch application of liquid or H2S scavenging chemicals in the United
industry to search for better, more solid scavenging agents in large tower States alone.
cost-effective and environmentally contactors, the ability to predict the H2S scavenging research has been
acceptable methods for treating sour performance of the direct-injection sys- conducted primarily by independent
gas. For economic reasons, hydrogen tem or achieve treatment specifications research organizations such as GTI,
sulfide (H2S) scavenging has emerged without excessive chemical usage is fre- product development groups within H2S
as the technology of choice for gas quently a challenge. For these reasons, scavenging agent manufacturing compa-
with low H 2S concentrations, for Gas Technology Institute (GTI) and nies or companies that use the products
example, less than 200 ppmv. others in the industry have directed to treat their gas. For example, a group
Operators frequently select the research during the past decade to of several companies involved in North
direct-injection method of applying H2S develop an improved understanding of Sea gas production sponsored a project
scavengers because of the lower capital the fundamental mechanisms control- to develop a better understanding of

Figure 1: The basic direct-injection scavenging installation consists of a chemical injection pump, a means of introducing the scavenging agent into
the natural gas pipeline, a length of pipe to allow for gas/liquid contact, and a downstream device for separating spent or excess scavenging agent
from the gas .

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how scavenging applications might be However, for situations where contact higher capital costs because there are
made more efficient. As a follow-up to time is relatively short, some benefit may fewer standard cubic feet of natural gas
this proprietary work, GTI, on behalf of result from advanced contacting devices. to amortize the capital, and therefore
three gas producer companies, began a Scavenging liquids may be partially costs per standard cubic feet are higher.
joint-industry project (JIP) in 2001 to removed downstream using gravity sepa- As a result, direct-injection scavenging
gather specific engineering test data to rators and/or coalescing filter/separators. becomes more favorable for these oper-
develop a software package to improve For facilities with existing sparged- ations because of the lower capital
techniques for designing, troubleshoot- tower contactors, some operators may costs. For example, direct-injection scav-
ing and optimizing H2S scavenging sys- prefer to fill the towers with water and enging has been used to successfully
tems. This package expands on the use them to remove spent scavenging treat slightly sour gas (10 ppmv to 20
capabilities of an existing GTI software agent from the treated gas, effectively ppmv H2S) from underground natural
product, Scavenger CalcBase (GRI- polishing the gas and increasing the effi- gas storage systems that operate for
96/0482), developed to allow rapid ciency of the system. only 4 months during the year.
screening of H2S scavengers for particu- EconomicsThe economics of treat- When gas must be treated offshore,
lar applications. The first phase of the ing natural gas with nonregenerable equipment size and weight greatly affect
JIP project will be completed in 2003. scavengers strongly depends on the con- treatment costs. The large size and
This article provides an overview of the centration of H2S in the gas stream. For weight of tower contactors largely
issues faced when designing or optimizing relatively low concentrations, capital cost makes them prohibitive for offshore
direct-injection scavenging systems and becomes the dominant factor, favoring operations, leaving only the direct-injec-
describes GTIs collaboration with the continuous direct-injection applications tion option. In addition to the size and
industry to develop test data and model- over the more expensive tower-based weight limitations, the handling of spent
ing software to support these activities. method of application. As H2S concentra- scavenger becomes more difficult off-
tion increases, the scavenging agent cost shore. All these factors tend to favor the
How is Natural Gas Treated becomes dominant, favoring solid-based use of liquid scavenging agents in a
using Direct-Injection H2S agents that, in many cases, have lower direct-injection configuration for off-
Scavenging? costs per pound of sulfur removed. shore application. In some cases, spent
Method of ApplicationContinuous For preliminary analyses, scavenger- liquid scavenger can be blended with
direct-injection of scavenging agents treating costs can be estimated using produced water and disposed of via
into a natural gas pipeline is usually published data. GTIs Scavenger CalcBase injection wells or discharged to the sea
applied near the wellhead (after separa- program provides a method for quickly after treatment.
tion from produced water and hydrocar- estimating capital and operating costs The cost for disposal of spent scav-
bons) or at centralized treating facilities for several H2S scavenging processes. enging agent varies widely depending
prior to dehydration. The basic direct- The program is intended primarily for on how these wastes are regulated by
injection scavenging installation consists initial screening of processes using the governing authorities. In some cases,
of a chemical injection pump, a means algorithms based on design equations the spent scavenging agents must be
of introducing the scavenging agent into provided by scavenger vendors. handled and disposed of as a hazardous
the natural gas pipeline, a length of pipe Other important factors include proj- waste, greatly increasing disposal costs.
to allow for gas/liquid contact and a ect life, seasonal operations, installation A careful study of applicable regulations
downstream device for separating spent location (offshore vs. onshore) and for a particular site location is an impor-
or excess scavenging agent from the gas spent scavenger disposal costs. A short tant part of the scavenger-selection
(Figure 1). Piping tees, quills or atomiza- economic project life or seasonal opera- process. It should also be noted that
tion nozzles are used to introduce the tions tend to penalize technologies with while scavenging agents themselves
scavenging agent into the pipeline.
Atomization nozzles enhance mixing
when gas velocities are low. While static
mixers have been used to enhance
A careful study of applicable regulations
gas/liquid contact, test data from GTIs for a particular site location is an important
test loop in South Texas have raised
questions about the benefit of using part of the scavenger-selection process.
static mixers for this application.

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may not be hazardous, the spent scav- pipes and contactor vessels are gen- the use of iron-sponge has declined
enging agent could become hazardous erally larger in size. during the years, in part because of the
because of the concentration of contam- Variations in flow rateDirect-injection pyrophoric nature of the spent scav-
inants such as benzene or mercury systems are vulnerable to changes in enging agent.
removed from the gas. flow rate. The H2S removal perform- For direct-injection scavenging sys-
Gas Stream CharacteristicsMost ance drops off severely as flow rate tems, the potential for exposure to toxic
H2S scavenging agents are designed to (and thus gas velocity) is reduced. materials is highest during maintenance
treat gas over a wide range of pressure, Tower-based contractors allow for operations or when handling spent
temperature, composition and flow con- better turndown of gas flow rates. scavenger material. Pump repairs, change-
ditions. However, several gas stream GTI patented a contactor in 2000 for out of atomization nozzles, or repair
characteristics should be evaluated care- direct-injection applications whereby and maintenance of spent-scavenger
fully during the process design phase. the turndown ability is improved to handling equipment are operations that
Water saturationNatural gas is allow operation over a large range have the potential for exposure. During
usually treated before being dehy- (e.g., a factor of ten or better) of gas these times, high levels of volatile organic
drated; however, it is sometimes flow rates. compounds may be present, and operators
necessary to treat a dry gas using Onshore vs. OffshoreFor onshore have more potential of coming into direct
scavenging agents, for example, at a applications, providing adequate contact with a scavenging agent or the
terminal handling offshore produc- length of pipe to promote good spent scavenger material.
tion being brought ashore through conversion of the scavenger and to Process design considerationsMany
a sour gas line to avoid platform reach H2S outlet specifications is factors, including some site-specific,
processing. Water-based scavenging usually not difficult. For offshore require careful consideration during the
agents, such as solutions of triazine operations, adequate pipe length is process design for a particular direct-
and iron oxide-based scavenging usually not available, and it may be injection H2S scavenging system. The
agents, generally require the gas to necessary to treat high temperature following discussion provides a check-
be saturated with water to prevent gas after a compressor. list of several items that need to be
formation of unwanted solid by- Environmental and Safety Considera- addressed during the process design.
products and to achieve the tionsNumerous federal, state and local Inlet and Outlet Knockout
required H2S level. regulations in the United States and sim- SeparatorsVendors of H2S scavenging
Oxygen contentOxygen is usually ilar governing authorities in many other agents frequently recommend the use of
not present in natural gas unless countries regulate the disposal of spent an inlet knockout separator to remove
gas is collected from wells under a scavenger material. In addition to vary- water and/or free hydrocarbon liquids
partial vacuum. In these systems, ing by jurisdiction, the regulatory from the gas before treatment. The pres-
oxygen sometimes leaks into the requirements depend on the scavenging ence of excess free liquids has the poten-
gas and may cause the formation of agent selected and the levels of other tial to increase scavenger usage and
elemental sulfur in beds of iron potentially hazardous components pres- treatment costs because of the addi-
oxide-based scavenging agents, ent in the natural gas stream. tional scavenger required to react with
resulting in a higher than normal All sour natural gas treating processes the H2S present in these liquids. Outlet
pressure drop across the bed. Oxygen share the common hazards (fire, explo- knockouts usually are recommended to
may also cause the formation of cor- sion and worker exposure to H2S) asso- prevent entrained liquid droplets from
rosive nitrogen dioxide when a ciated with handling high-pressure com- reaching downstream glycol dehydra-
nitrite-based scavenger is used. bustible gases containing toxic levels of tors or other process equipment that
TemperatureLow-temperature gas H2S. In addition to these areas of con- could be adversely affected.
can cause scavenger reaction kinetics cern, other potential hazards associated Length of Pipe for ContactThe
to slow down and affect system with the use of H2S scavenging agents length of pipe available for gas/liquid
performance. High temperature can include eye and respiratory irritation; contacting in direct-injection applica-
cause the scavenger to break down benzene, formaldehyde and toxic metals tions is an important design parameter.
and form corrosive products. exposure; and height and confined In general, longer pipe lengths result in
PressureH2S scavenging is more space entry hazards. improved H2S removal and reduced
difficult at low pressures because Formaldehyde and caustic are not chemical consumption.
the partial pressure of H2S is lower used much because of the related AtomizationThe importance of
for a given concentration and because health and safety problems. Similarly, atomizing the scavenging agent as it is

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injected varies by application. When gas


velocities are low, pipe lengths are short,
or when large pipe diameters are used,
atomization can significantly improve
performance. In other situations where
long pipe lengths are available and gas
velocities are high, atomization has little
or no effect.
Water SaturationWater addition
is sometimes required if the gas is not
saturated with water at the temperature
and pressure where scavenging treat-
ment is applied. This situation some-
times occurs when gas is heated before
treatment or when previously dehy-
drated gas is present in the feed sour
gas. In the case of triazine-based liquid
scavengers, the reaction products are
intended to stay dissolved in the spent
scavenger, where they are ultimately
separated from the gas stream for dis-
posal. However, if the gas is subsatu-
rated with water, enough water may
evaporate from the scavenger solution Figure 2: The GTI software modeling package reports the H2S profile over the length of pipe along
to cause unwanted precipitation of with other quantities of interest such as the chemical usage, e.g. liters of scavenging agent
solid reaction products in the pipeline. per kg sulfur removed.
Some operators operate a small water
injection pump upstream to add the
required amount of water to saturate GTI and Industry Sponsors Theoretical models of the direct-
the gas. Develop New Process injection process require knowledge of
Scale InhibitionThe formation of Modeling Software the following:
scale is a consideration when hard water GTI, acting on behalf of JIP partici- reaction stoichiometry and kinetics
may contact highly alkaline scavenging pants, is developing a new software- between H2S, CO2 and the scaveng-
agent formulations. This may occur if modeling package to make process cal- ing agent
the scavenging agent is diluted with culations for direct-injection H2S scav- physical solubility of H2S in the
water before use or if hard water is enging systems. In 1998, GTI pub- scavenger solution
injected to maintain water saturation. In lished a set of equations largely based liquid- and gas-film mass transfer
other cases, the spent scavenger may be on empirical correlation of field data coefficients
commingled with other sources of hard that could be used for direct-injection interfacial surface area available for
water in downstream separators and systems. The new model being devel- mass transfer.
produced water facilities. oped is more mechanistic in nature and Once the above quantities are known,
CO2 InterferenceCarbon dioxide is based on rigorous modeling of the the H2S absorption can be calculated based
(CO2) does not normally present a major two-phase flow hydraulics, mass trans- on the following mass balance equation,
problem because the most commonly used fer and chemical kinetics. Further, the which is at the core of the new model:
H2S scavengers react selectively with H2S. new model will be incorporated into a
However, CO2 is known to react at least user-friendly program with a graphical
partially with triazine-based scavengers and user interface. The program will not be
does compete for the scavenging chemical. made available to the general public where
In these cases, chemical consumption but will be available to the JIP partici-  H S = Mole fraction H2S in the gas
2

may be increased as a result of high pants and potentially to other parties phase
levels of CO2. expressing interest in it. G = Molar gas velocity, lbmol/hr/ft2

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Figure 3: This diagram shows the design of the laboratory direct injection test rig commissioned in June.

z = Pipe length, ft coefficients, and enhancement factors GTI Constructs


K G = Overall mass transfer coeffi- used to describe the enhancement of High-Pressure Test Flow
cient, lbmol/hr/ft2/atm mass transfer in the liquid phase Loop in Des Plaines
a = Interfacial area for mass transfer, because of rapid chemical reactions Laboratory Facility
ft2/ft3 taking place in the diffusion film near GTI is in the process of constructing a
P = Pressure, atm the gas-liquid interface. laboratory direct-injection test rig to
The model solves these equations and study H2S scavenging of natural gas
This equation is a first-order linear reports the H2S profile over the length of under controlled conditions. A schematic
ordinary differential equation and can pipe (Figure 2) along with other quantities diagram of the laboratory test rig is
be solved using standard numerical of interest such as the chemical usage, for shown in Figure 3. This setup is made of
techniques (for example, a fourth- example, liters of scavenging agent per schedule 80 carbon steel pipe with total
order Runge-Kutta method) as long as kilogram of sulfur removed. A full report of contact length of 240ft. The entire struc-
the function (z) can be evaluated at all intermediate quantities such as mean ture is housed inside a 20-ft x 12-ft fume
each point in the pipe. Evaluation of droplet size, interfacial areas, gas and liquid hood equipped with a carbon adsorp-
(z) requires an estimation of the inter- film coefficients, kinetic rate coefficients, tion bed. The unit has a maximum gas
facial area, gas and liquid mass transfer etc., also is available. flow of 0.6 MMscf/d under once-through

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is experienced in field operations and


certified regarding H2S safety.
Through the course of the various
scavenger projects GTI has been
involved in during the past decade,
the organization has amassed a large
database on direct-injection scaveng-
ing that has proved useful for design
and troubleshooting of applications.
In late 2003, GTI will be offering par-
ticipation opportunities in a follow-
up JIP to the current program that
has focused on developing a model
for direct injection scavenging.
Testing new scavengers and contac-
tor devices in the new testing system
at Des Plaines, Ill., as well as in the
field system in McAllen, Texas, and
improving the computer model are
all on the table for the program work
scope, which the participants will
finalize. GTI also is interested in car-
rying out projects directly for clients.
Recent work has included design of
direct-injection scavenging installa-
tions based on the GTI patent at
Figure 4: Construction of the negative pressure chamber is already complete. storage field installations, and field-
testing of proprietary scavengers is
and recycled flow conditions at temper- disposal, recycled and/or sampled as being discussed with several clients. GTI
atures up to 319F and pressures up to necessary. This unit will allow GTI to continues to offer and support the GTI
1,100 psig. collect significantly more data under a Scavenger CalcBase program for tower
During a typical test, pure methane wider variety of conditions and more applications of scavengers and will devel-
or nitrogen gas will be mixed with precisely control the test conditions. op a commercial version of the direct injec-
appropriate amounts of pure H2S gas The purchase of various equipment tion model in the future.
and the mixture will be continuously items such as compressor, gas-liquid For more information on GTI gas process-
fed to the system and metered. The separator, heater, cooler, carbon beds ing products and services, or to join the JIP
scavenger will be fed from a pressur- and storage vessel is complete. The con- described in this article, please contact
ized tank in lieu of pumps and metered struction of the negative pressure cham- Dennis Leppin at GTI. Portions of this arti-
using a rotameter. The scavenger will ber (Figure 4) and compressor room are cle were reproduced from an earlier GasTips
be injected into the pipe loop using a completed and the work on building the article from the Fall of 2000. For a complete
small nipple, quill or atomization nozzle pipe loop is underway. The setup is listing of published test data, literature refer-
from a pressurized storage tank. Gas- scheduled to be commissioned by the ences and related information, the reader
sampling taps are provided at conven- end of June 2003. is referred to Fundamentals of H 2 S
ient intervals. The gas and liquid exits Scavenging for Treatment of Natural
the system and enters a separator. The GTI Offers Services for Gas, by Fisher et. al., published in the pro-
gas then proceeds to a booster com- Testing of New Scavenging ceedings of the Ninth GRI Sulfur Recovery
pressor, which compresses the gas back Agents and/or New Mass Conference, 1999. Additional detailed
up to inlet pressure. Any additional Transfer Devices information on scavenging has been com-
components to achieve the desired GTI is set up to carry out research projects piled in the collected proceedings of the GRI
composition are added back to the gas. related to H2S scavenging for interested Small-Scale Sulfur Recovery Conferences,
The spent liquid will be sent to parties. The staff involved in these projects GRI-00/0085.

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