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Application Note

pH Control
in Sour Water Stripping
In petroleum refining, so called sour water (process water that contains dissolved hydrogen sulfide H2S) is produced in various processes. Due
to environmental legislation and the fact that H2S
is extremely toxic, refineries nowadays adhere to
strict sulfur management which involves removing
the H2S from the sour water through steam stripping.
Background
Sulfur compounds such as mercaptans and hydrogen sulfide
occur naturally in crude oil or are formed in certain process
steps. Water and steam are extensively used in petroleum refining, and sour water is formed in the presence of hydrogen
sulfide. The increased use of sour crudes obviously leads to an
increase in sour water formation. Apart from H2S, sour water
contains ammonia, phenols, HCN, CO2, acids, salts and many
other water soluble waste compounds. After stripping, the water may be used as process water, for example in the desalter,
or be treated as waste water.
Process
After the removal of solids and hydrocarbons, the sour water
is fed to the top of the stripper column. A reboiler provides heat
or steam to the bottom of the stripper, or steam is injected
directly. In a counter current flow the steam liberates the dissolved gases from the sour water. Subsequently, the overhead
gas flow is directed to the Sulfur Recovery Unit where elemental sulfur is produced through catalytic oxidation of H2S.
Unfortunately things are slightly more complicated than this
and the use of steam alone is not enough to remove all the
dissolved (sour) gases. Gas concentrations vary and both hydrogen sulfide and ammonia occur in different forms. Fur-

Sour gas to SRU


Sour water

Stripper

Caustic

Process
ss water
w
reuse or
to treatment
atment
Reboiler

Application Note

ther, depending on the pH of the sour water the gases can be


found either in ionic or gas form. It is even possible that hydrogen
sulfide and ammonia are found bound as ammonium bisulfide,
a solid salt. The following chemical equilibria take place:
H2S <> H+ + HS
HS <> H+ + S2
NH3 + H2O <> NH4+ + OH
NH4+ + HS <> H2S + NH3
As long as these components are present in an ionic state they will
not be completely stripped from the water. So in order to increase
the efficiency of the sour water stripper it is important to force the
components into their gas form.
This is where the pH of the sour water plays an important role. A
common misconception is that sour water by definition is acidic.
This is not the case, as in this context sour refers to the presence of hydrogen sulfide. Sour water definitely can be alkaline in
nature. (In fact alkaline sour water is one of the most underestimated sources of corrosion in oil refining and natural gas production.) Being a weak acid in solution, hydrogen sulfide remains dissociated and dissolved under alkaline conditions and is
difficult to strip from the solution. At pH < 5.5 though, it returns
to its gas form and, thanks to its increased partial pressure, stripping becomes easy with less steam required. Ammonia would
behave similarly if it were not for the fact that ammonia is a weak
base when dissolved in water. Contrary to hydrogen sulfide it requires a pH > 10 to return it to its gas form. The process conditions for efficient and economic stripping of both gases are thus
rather contradictory.

The ideal solution would be to use two strippers: one working at


low pH for the removal of hydrogen sulfide, and the other working
at high pH for the removal of ammonia. Most refineries however
do not have the benefit of multiple sour water strippers, so alternative remedies have to be found.
Increasing the carbon dioxide content by adding flue gas helps
lower the pH of sour water and the release of hydrogen sulfide in
the upper part of the tower. For the same purpose, some refineries
still use sulfuric or acetic acid for preacidification of the sour
water. Although acidification improves the stripping of hydrogen
sulfide, some of these acids form ammonium salts which make
the stripping of ammonia more difficult. Injection of caustic at
the bottom of the tower to keep the pH above 8 will improve ammonia stripping.
Instrumentation
The foul conditions, the presence of ammonia and sulfides and
the elevated temperatures, are extremely tough on pH electrodes.
Diaphragms easily clog up and the reference electrode can quickly become poisoned. This leads rapidly to unstable measurements
and sensors may not last longer than two weeks.
The InPro 4260i pH sensor with its open reference junction and
Xerolyt solid electrolyte has a proven track record in sour water
stripper service. It resists fouling from hydrocarbon contaminants and the solid electrolyte provides an excellent barrier
against poisoning from sulfides, ammonia or cyanides, guaranteeing high accuracy and fast response throughout many months
of operation.
Featuring Intelligent Senor Management (ISM) technology, the
sensor provides full diagnostics that advise when maintenance is
due or when the sensor needs replaced.
The corresponding transmitter for the sensor is the M420, a twowire pH analyzer that is fully certified for hazardous area use,
and offers HART communication and ISM diagnostics functionality.

pH electrode InPro 4260i

Mettler-Toledo AG
Process Analytics
Im Hackacker 15
CH-8902 Urdorf
Switzerland

Transmitter M420

For more information:


www.mt.com/pro-petrochem

www.mt.com/pro
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