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311 Article PDF
311 Article PDF
stable salts
Mass transfer rate-based simulation models sour water stripping and assesses
the distribution of ammonia in conventional amine treating systems
I
n a recent article dealing with a live steam- almost exclusively NH3, H2S and possibly a trace
injected stripper (PTQ, Q3 2012), we discussed of CO2. It is generated by refinery hydrotreating
how steam usage affected the stripped water (hydrodesulphurisation, or HDS) units. When
residual ammonia and hydrogen sulphide levels, stripped of contaminants, non-phenolic water can
how ammonia distributed itself within the strip- typically be recycled for reuse in the HDS unit as
per in an unexpected way, and how Murphree wash water, or it can be used as make-up water to
(1925) vapour efficiencies varied with location the crude desalting process. Phenolic (or more
within the tower at various stripping steam broadly, non-HDS) water typically contains HSS,
rates.4 The discussion was limited to non- phenols and caustic.
phenolic sour water. In the present article, we Finally, it may be useful to point out that
examine the effect of heat stable salts (HSS) on ammonia and hydrogen sulphide have almost
sour water stripper (SWS) performance, how the unlimited solubility in water when they are
injection of caustic soda can spring ammonia present together. This is an interesting conse-
from the sour water, and how caustic injection quence of the fact that the reactive component
can worsen H2S stripping if it is injected at the of the solvent, ammonia, is volatile and, if
wrong place, or too much caustic is injected. The present in the gas phase, it will continue to
analysis uses a mass transfer rate-based simula- absorb as long as it becomes protonated as a
tion model for sour water stripping and for result of H2S co-absorption. Thus, it is conceiv-
assessing the distribution of ammonia in conven- able that a particular sour water stream may be
tional amine treating systems. a lot more concentrated than the solubility of
either ammonia or H2S by itself might suggest.
Sour water sources SWS uses either steam generated by a reboiler,
The sour water generated in refineries comes from directly injected steam, or even a hot hydrocar-
numerous sources. Most refinery sour water bon stripping vapour to shift chemical reaction
systems contain very little CO2, but H2S levels equilibria by applying heat. Stripping vapour is
can become very high. The capacity of ammonia the “gaseous solvent” used to remove and carry
solutions for H2S is a direct result of the weak the ammonia and H2S out of the system. It func-
acid-weak base reactivity between H2S and tions by:
ammonia. The potentially high H2S content can • Heating the sour water feed to the boiling
make sour water extremely foul, and H2S point
removal from the sour water to quite low levels • Reversing chemical reactions
is mandatory to avoid unacceptable pollution • Diluting the partial pressure of the gases
levels. Many sour water sources have been noted stripped by furnishing excess vapour.
in the excellent review article by Asquith and Figure 1 shows a typical SWS column with
Moore.1 heating by the injection of live steam and with
Sour water is generally classified as phenolic or the possibility of injecting caustic soda to one of
non-phenolic. Non-phenolic water contains the trays in the column. Typical energy usage in
0 HSS
no matter how much steam is
300 ppmwt
injected into the stripper there
is a residual ammonia level that 1000
simply cannot be removed when
there are HSS in the sour water.
100
HSS have a negative effect on
ammonia stripping. However,
they have a beneficial effect on 10
H2S removal because they are
generally stronger acids. A two
order-of-magnitude reduction in 1
residual H2S is possible with 0.75 1.00 1.25 1.50
only a modest amount of HSS Steam, lb / Sour water, gallons
present.
One way to improve ammonia 103
removal is to inject caustic soda, 0 HSS
H2S in stripped water, ppmwt
102
a stronger base than ammonia, 300 ppmwt
onto a tray somewhere in the 10
column. At the risk of oversim- 1
plification, if the right amount is 10 −1
NH3, ppmwt
the conditions presented in this
case study — they should not be 80
generalised; rather, the ProTreat
60
SWS model should be run for the
conditions pertinent to the exist- 40
ent installation.
20
Set point for pH control and optimal 0
stripping 0.0 0.5 1.0 1.5 2.0
When using caustic injection Neutralisation ratio, NaOH/HSS
with phenolic sour waters, it is
common practice to control the
caustic flow to a pH set point. 1 1.48 lb/gal
The question is, what should the 10 −1 1.2 lb/gal
set point value be? The answer
almost certainly depends on the 10−2
amounts and kinds of HSS 10−3
H2S, ppmwt