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AMMONIA

REMOVAL
PROCESS
ANIMAL WASTE
RECOVERY
PROCESS
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METAL RECOVERY
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PLATING
PRE-TREATMENT
SOUR WATER
WHAT IS SOUR WATER?
TRADITIONAL SOUR WATER TREATMENT PROCESS
STRIPPING SULFIDE AND AMMONIA
CASTION'S TREATMENT SOLUTIONS
EXAMPLE OF BENEFITS
What is Sour Water?
Sour water is any water from a refinery that contains hydrogen sulfide.
In addition, sour water may contain ammonia, phenol and cyanide.
Historically, sour water from refinery process units is treated to remove
hydrogen sulfide prior to disposal. Today, the removal of
ammonia from sour water is more important due to recent
regulation reducing nitrogen into estuaries. Selenium is also important
as regulators seek to reduce selenium because of the mutagenic effects
found in wildlife with high selenium concentrations. While ammonia,
selenium, phenol, salts and other constituents are removed while
during hydrogen sulfide treatment, removal efficiencies of these
chemicals are lower due to the physics and chemistry of hydrogen
sulfide treatment systems.
Traditional Sour Water Treatment Process
Traditionally, sour water is sent to a stripping unit where steam is used
to heat the sour water to above 1800 F. Hydrogen sulfide and ammonia
are released at the top of the stripping tower and sent to the Claus unit
where they are converted into sulfur and nitrogen. The stripped sour
water is treated in a biological wastewater treatment plant where the
remaining ammonia is nitrified and then denitrified.
Stripping Sulfide and Ammonia
Interestingly, the physical conditions for the efficient removal of both
hydrogen sulfide and ammonia from the sour water are not possible in
a traditional hydrogen sulfide treatment system. The ideal pH for
stripping hydrogen sulfide is below 5.5 and at a pH above 5.5 sulfide is
primarily found in the form of ions and cannot be as effectively
removed. Conversely, efficient ammonia stripping requires a pH above
10 to prevent the formation of ammonium ion that cannot be stripped.
Removal of Ammonia | Sour Water Filtration http://www.castion.com/IndustrialSolutions/SOUR-WATER.aspx
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SYSTEMS
PRIMARY
SEPARATION
SYSTEMS
RCAST SYSTEMS
SOUR WATER
SYSTEM
INTEGRATION
WASTEWATER
EVAPORATORS
ZERO LIQUID
DISCHARGE
SYSTEM
WINERY
WASTEWATER
TREATMENT
Most refineries target a pH of about 8 in the steam stripper which
allows removal of both ammonia and hydrogen sulfide but at lower
efficiencies. Selenium is not removed during the stripping process and
it finds its way into the stripped water.
After stripping the stripped sour water usually contains 50-100 million
ppm of ammonia plus the selenium. Some of the ammonia found in the
stripped water is resistant to removal. It has been hypothesized that
acidic materials such as thiosulfuric acid, thiocyanic acid and weak
organic acids may cause ammonia fixation. This issue may go away if
the pH of the stripped water increases to above10.
There have been proponents of using dual strippers to increase the
removal of ammonia from sour water. The first stripper
removes the hydrogen sulfides under acidic conditions and the second
stripper would remove the ammonia under caustic conditions. While
hydrogen sulfide and the removal of ammonia from sour water would
increase, and ammonia fixation avoided, the selenium would remain in
the stripped sour water.
CASTions Sour Water Treatment Solution
CASTions CAST and RCAST systems when combined with reverse
osmosis and other traditional filtration systems can be a very efficient
and cost effective sour water treatment for hydrogen sulfide,
ammonia, selenium and salts. Because of our flash vacuum distillation
platform our sour water system would be less costly to operate than a
stripper. Our sour water treatment system can be either single
or dual staged with the first stage removing hydrogen sulfide and
selenium and the second stage targeting the removal of ammonia from
sour water. In addition, we could retrofit our RCAST system after the
hydrogen sulfide stripper to remove just the ammonia
Example of Benefits
A CASTion CAST system was combined with a vibrating membrane to
treat the stripped sour water for selenium at a West Coast refinery.
CASTion was able to remove 93% of the selenium in the stripped sour
water.
2008 Castion Corporation, A ThermoEnergy Company
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Removal of Ammonia | Sour Water Filtration http://www.castion.com/IndustrialSolutions/SOUR-WATER.aspx
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PH-A-008
http://www.yokogawa.com/us
Sour Water
Industry: Refining, Oil and Gas
Product: PH450


Background Information
Sour Water is the wastewater that is produced from
atmospheric and vacuum crude columns at refineries.
Hydrogen sulfide and ammonia are typical components in
sour water that need to be removed before the water can be
reused elsewhere in the plant. Removal of these
components is done by sending the sour water from the
process to a stripping tower where heat, in the form of
steam, is applied. The ammonia and hydrogen sulfide
contained in the water is released by the heat and exits the
top of the tower.

Introduction
The ideal pH value for stripping H
2
S is below 5, since above
5, sulfide is primarily found in the form of ions (HS
-
or S
-2
).
Alternatively, efficient ammonia stripping requires a pH
above 10 to prevent the formation of ammonium (NH
4+
) ion
that cannot be stripped. Although the most favorable strategy
for sour water stripping is a three step process where two
separate stripper towers are used, one for removing
hydrogen sulfide and the other for removing ammonia,
economics usually dictates a compromise. Having only one
stripper tower and using a pH around 8 allows adequate
removal of both gases.

There are three distinct processing steps in the sour water
stripping process: degasification, hydrogen (acid-gas)
stripping and ammonia stripping. Figure 1 shows only one
stripper column.

During the degasification stage the sour water feed from the
plant is cooled and fed to a degasser where dissolved
hydrogen, methane and other light hydrocarbons are
removed. These removed gases are known as sour Gas and
are pumped off to the Sulfur Recovery Unit (SRU). This
degassed sour water is pumped into a storage tank that
serves to dampen the flow rate and facilitates removal of
entrained oil and solids.

The next step in the process is known as hydrogen sulfide
stripping. The degassed sour water is fed to the acid gas or
hydrogen sulfide stripper, which is a steam-reboiled
distillation column. The hydrogen sulfide, which is stripped
overhead, is of high purity an excellent feed for sulfur
recovery units or sulfuric acid plants.

Next, the hydrogen sulfide stripper stream, containing all the
ammonia in the feed water and some hydrogen sulfide, is fed
directly to the ammonia stripper, which is a refluxed
distillation column. In this column, essentially all ammonia
and hydrogen sulfide are removed from the water. After
exchanging heat with the hydrogen sulfide stripper feed, the
stripped water is cooled and sent off for either reuse or
treating.

Challenges
Measuring pH in sour water poses several challenges. The
abrasiveness of the wastewater affects the pH electrodes
over time; the reference electrode junction may plug and
require cleaning; and the reference element itself will be
poisoned over time due to the presence of hydrogen sulfide.
Process temperatures, which affect sensor life, can be quite
high in order to facilitate removal of the unwanted
components. Ammonia and cyanide can poison the
reference electrode by reacting with the silver element.

Product Recommendations
There are two recommended pH sensor combinations we
recommend for sour water monitoring. If you are looking for
a retractable installation assembly, the PH87 holder with the
PH97/DP sensor is the best chose. The sensors solid state
reference provides longer lifetime by lengthening the amount
of time it takes for the reference to become poisoned.

For either a flow thru or a direct insertion assembly we
recommend breaking the pH measuring system up into it
three parts: the measuring electrode, reference electrode,
and the temperature electrode. The Yokogawa FF20 is the
flow thru holder and the FS20 is the direction insertion
holder, each are available in different materials of
construction. For the temperature electrode we recommend
the SM60-T1, a Pt1000 thermometer. The measuring
electrode we recommend is the SM21-AL6, a heavy duty
glass electrode that is strengthened for chemical resistance
and higher temperatures. The Bellowmatic SR20-AC32
reference electrode is recommended for the reference



electrode because of its flowing junction and ability to
automatically compensates for process pressure variations.

When either pH assembly is matched with any Yokogawa pH
analyzer, the user is provided with diagnostics that warn for
sensor breakage or coating. Yokogawa analyzers reduce the
guesswork as to when maintenance is required in the pH
measuring loop. Compatible pH analyzers are either the
Model PH202 for Class I Div I areas, or the model PH450 for
Class I Div II areas. For Complete details on each piece of
equipment please refer to the appropriate product
specification pages.


Figure 1

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<HOME : TECHNOLOGIES &SERVICES : SOUR WATER STRIPPING
Sour Water Stripping

CB&I supplies sour water stripping units for the removal of hydrogen sulfide and ammonia fromrefinery wastewater. Around the world, we have
designed and built more than 30 sour water stripping units with capacities of 32 to 925 gallons per minute.
Our sour water strippers are designed to provide superior energy efficiency and enhanced performance. We incorporate proprietary features such as
low-pressure feed flash drums for maximumhydrocarbon separation and light hydrocarbon removal; optimized steam-to-feed ratios for cost-effective
compliance with effluent specifications; and innovative applications of corrosion-resistant materials.
Integrated process sol uti ons. We offer a full spectrumof sulfur control solutions to help refiners meet fuel quality standards and
environmental regulations. We can seamlessly integrate our sour water stripping units with our Claus sulfur recovery plants, tail gas treaters, thermal
incineration units and other processing units for maximumperformance and efficiency.
We execute most projects on a lump-sum, turnkey basis. Our comprehensive services for sulfur-control projects include feasibility studies, front-end
engineering design, detail engineering, HAZOP analyses, procurement, fabrication, construction, startup, commissioning and operator training. By
offering a complete EPC services package, we consistently deliver systems that provide superior long-termvalue-often at lower costs and on shorter
schedules.
Effecti ve proj ect executi on. We carefully plan and execute our projects to minimize disruption to plant operations. In many cases, we utilize
modular construction methods, prefabricating and assembling the units at our shops and shipping themto the installation site. By performing much of
the work at our own facilities, we minimize on-site requirements for lay-down space, enhance safety and quality control and can minimize delays due
to inclement weather. Contact: sulfur@CBI.com.
Copyright 2004-2010 Chicago Bridge &Iron CompanyN.V.
Legal Information (General Provisions)
All Rights Reserved.
CB&I : Sour Water Stripping Units http://www.cbi.com/services/sour-water-stripping-units.aspx
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Analyzing Hazards of Sour Water Spills
John L. Woodward, Baker Engineering and Risk Consultants, Inc., 3330 Oakwell Court, Suite 100, San
Antonio, TX 78218-3024
Sour water in petrochemical plants can contain a significant concentration of hydrogen sulfide and ammonia.
Design of sour water storage tanks should account for the hazards of a large leak. The dike area and location
are important, as is predicting the extent of toxic vapor plumes.
Analyzing the risk of a large spill of sour water from a sour water storage tank requires applying dispersion
analysis to predict the contours of both H2S and of NH3 plumes out to ppm concentrations. This requires first
estimating the vapor pressures of the toxic gases using Henry's law constants. Fortunately, the vapor pressure
of both H2S and of NH3 are reduced substantially by the ionization of the molecular species to the ionic form
(hydrosulfide and ammonium ions). The equilibrium concentrations of these ions is a strong function of pH since
a hydrogen ion is lost in forming the hydrosulfide ion and is gained in forming the ammonium ion. This suggests
that pH adjustment can be an effective mitigation measure for a spill event.
This paper makes use of chemical equilibrium constants and of rigorous thermodynamic formulas, coupled with
dispersion modeling to show how the plume contours of H2S and of NH3 vary with initial concentrations and pH.
Extended Abstract Status: File Uploaded
Assuring Safety in the Design and Construction of Process Systems
The Preliminary Program for 2007 Spring National Meeting
Analyzing Hazards of Sour Water Spills http://aiche.confex.com/aiche/s07/preliminaryprogram/abstract_80296.htm
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