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A Recarbonation
Process
Produced
for Treatment
by MSF Plants
H.E. Al-Rqobah,
Ministry
295
of Distilled
H. and Al-Munayyis,
of Electricity
Water
in Kuwait
and Water,
A.
Kuwait.
Abstract
Distilled
water
produced
are therefore
In Kuwait,
18
months
at
being
adopted
a recarbonation
Shuwaikh
by different
process
Desalination
MSF plants.
has been
Plant
in operation
treating
18
distilled
water as the first step in a major scheme
treating water produced by all MSF plants in Kuwait.
The
major
steps
in the
adopted
recarbonation
for
MIGD
of
aimed
at
process
include
extraction
of carbon dioxide from the vent gas system of the MSF
plant, compression and purification of Cop -air gas stream, acidification
of a pre-calculated
distilled
water stream in a gas
absorption tower, limestone dissolution to augment the water with
Caz+ and HCO; necessary for water to be self-inhibiting,
degasiwith by-passed
distilled
fication
of the excess COz, blending
water
and finally
This
the
paper
different
well as an
the last'18
pH adjustment.
presents
steps
analysis
months.
some
encountered
of plant
engineering
in the
operation
design
aspects
of
recarbonation
process
as
experience
gained
during
296
Introduction
tion
tube
Kuwait, like most Gulf countries, depends on seawater desalinafor its fresh water supply.
In 1953, the first submerged
distillation
plant was commissioned
in Shuwaikh with a capa-
of 263 MIGD.
distilled
water
produced
has
very
low concentrations
of
dissolved
salts and gases and a total alkalinity of less than 1
The high purity renders the water to be chemically
mg CaC03/L.
very
aggressive
towards
nearly
all
components
in the water
distribution
system, resulting
of
One
of
the
by-products
hydroxide,
a red-brown
in very severe
this
chemical
rust, which
results
corrosion problems.
attack
is ferric
in what
is called
"red
water".
To improve
the palatability
of distilled
water,
it is usually
blended
with brackish
water
in
different
blending
ratios,
depending
on the quality of the available
brackish water.
In
Kuwait, the blending ratio is nearly 1O:l.
underground
fresh water
is also added.
Negligible
The potable
amount
of
water thus
produced
has a total alkalinity
of 20-24 mg CaC03/L, which
is
less than the minimum value of 50 mg CaC03/L necessary to depress
the corrosion
rate of the
water distribution
system.
total
alkalinity
If iron
different
Chemical
of the potable
is immersed
rust
is developed
Fe(OH)3 or hydrated
this electrochemical
in water
water
materials
treatment
involved
in
to increase
is therefore
saturated
inevitable.
with dissolved
the
the
oxygen,
ferric
hydroxide
The mechanism of
by the following
equations:
Fe
Fe*+ + 2 e-
(I)
2 e- t 2 H20
(2)
+ 2 OH-
297
2 e
H,O + 1/2
0, +
2 OH-
(3)
0,
2 Fe3' t 2 OH-
(4)
Fe3+ + 3 H,O
Fe(OH), + 3 H+
(5)
0, +
2 Fe(OH), t 4 H'
(6)
298
as
water
temperature
increases,
prevent
distribution
The
complete-
the
PR decreases correspondin!
therefore increase. It is therefore
pH and depress
iron dissolution
and
failure
main
objective
of
this
bonation
process
adopted
in
comprehensive
scheme to solve
from
the
of the pipes
in the potable
water
system.
first
year
of
work
is
to
describe
Kuwait
as the
the problem of
operation
of
this
the
recar-
first phase
"red water".
process
will
in a
Data
also
be
discussed.
Corrosion
Inhibition
There
are various
methods
which
sion inhibition
of the pipe
distribution
system.
During
sive
study
Centre
1.
was
(WRDC)
To
conducted
of MEW with
establish
under
prevailing
the
by
used
period
the
4 main
potable
water
a comprehen-
1979-1981,
Water
data
in the
Resources
objectives
corrosion
Development
base
for
pipe
materials
conditions.
2.
To evaluate
alternative
3.
To
available
assess
can be applied
network
materials
metal
of construction.,
pacification
methods,
with
To
perform
suitable
One
of the
main
has
Pacification
investigated,
technical
chemical
the recommendation
with cement-mortar
tion
system
construction.
in
and
treatment
results
economic
process
of the
first
of using ductile
and seal-coated.
recently
of water
the
been
by
second
for
the
most
for self-inhibition.
part
of this
study
was
upgraded
of
to
this
its total
increasing
part
study
the
study,
material
of
alkalinity
was
using
different
299
of
high
alkalinity
and
calcium
content
is a stable
water, and can produce a thin protective layer of calcium carbonate by careful increase in the pH.
This is the concept of
self-inhibition
and can be described by the following two
reactions:
HCO-
OH-
co2- +HO
3
CO:- + Ca2+
CaC03(S)
(7)
(8)
The hydroxyl ions necessary for the first reaction are produced
during the reduction of dissolved oxygen, according to equation
There are three conditions which are necessary for self(3).
inhibition of water:
(1) The water must be free of C02.
Carbonic acid, even at
low concentrations, will neutralize the hydroxyl ions proIt will also dissolve
duced according to equation (3).
any protective calcium carbonate layer, and finally it
Free CO2 can be degasified in a
will attack the metal.
stripping tower using air, or by treatment with sodium
hydroxide.
(2) The concentration of calcium and carbonate ions must
satisfy the solubility product of calcium carbonate, in
order to precipitate the inhibition film.
(3) The pH value of water must be carefully adjusted.
Langelier saturation index, LSI, is defined by
following equation:
The
the
300
where
the
pH
of
saturation,
(9)
pHs,
is defined
as the
A is a constant
another
is
which
constant
positive
conditions,
negative
therefore
thus
index
indicates
index indicates
associated with
on
the
alkalinity
is associated
a tendency
TDS
non-corrosive
deposit
CaC03.
a tendency
to dissolve
CaC03 and
corrosive conditions.
It can then
deduced
that maintaining
the pH value of water above its
value will result in deposition of the protective CaC03 layer
hence
corrosion
Based
inhibition
on the
and
content.
with
to
(IO)
temperature,
water
at
saturated
alkalinity)
on the water
depends
and total
saturation
and
depends
which
- log (total
pH value
is just
A
is
be
pHs
and
can be achieved.
recommendation
of maintaining
the
same
level
of
calcium
ion concentration
and total alkalinity,
the following
equation
can be applied for a recarbonation
process,
operating
at 4O"C, a total alkalinity
of 70 mg CaC03/L and calcium concentration
of 70 mg CaC03/L:
pHs = 11.46
( 11)
recarbonation
process
water
with
proc'ess consists
Fig.
was established
and Water
plant is
Desalination
18 MIGD and
a total
alkalinity
3 main
steps
of
as
mg
schematically
CaC03/L.
shown
in
1.
Distilled
plant
is
water
acidified
from
in
an
three
units
absorption
of
tower
the
MSF
using
desalination
CO2
$35..
The
Fig.
1.
Schenicltic
CO?+
flow
AIR
diagram
of
ttls recarbonation
process.
302
acidified
in
water
number
reaction
limestone
by bicarbonate
dissolution
+ H20 + CO2
excess
limestone
CO2
present
dissolution
Ca*'
.The
CaC03
following
in
the
filters
+ Z(HCOa)-
It can
be observed
natural
that
carbonation
(12)
recarbonated
is degassified
using air.
Finally, a 15 wt% caustic
the water stream for final adjustment
the
ions using
filters.
takes place.
CaCOs
The
is then augmented
of
this
water
recarbonation
process
leaving
in a stripping
taking
process
place
in
the
tower
into
resembles
the
aquatic
system.
The
carbon
dioxide
gas,
required
according
to equation
(12),
can be produced
conditions.
If
in many different
ways depending
on the local
the water feed to be treated is produced by any
then extraction
of CO2 from the
thermal
desalination
process,
non-condensable
gases, released as a result of heating seawater
would represent
the most technically
and
When seawater
is heated to
alternative.
to high temperatures,
economically
feasible
Ca
+Q
(HCOJ2
The
amount
perature
from
of
CO2
the main
CaCOs
librated
heater
decompose
will
+ Hz0 + CO2
depends
and the
according
on
the
pressure
brine
top
tem-
in the first
flash
chamber
of the heat recovery
section of the MSF plant.
also
be
released
will
Dissolved
oxygen
and
nitrogen
gases
For better heat transfer
in the
together
with carbon dioxide.
these noncondensable
gases are
condenser
of the flash chamber,
vented
and
withdrawn,
using
steam
ejectors,
to
a vent
from
the
vent
gas
condenser
using
A two-stage
gas
con-
stream of
gases are
a booster
vacuum
reciprocating
gas
303
compressor,
recarbonated
water
leaving
the
limestone
dissolution
filters contains some excess CO2 and very little dissolved oxy-
VEXT
GAS
CO2 + AIR
NSF
DESALINATION
PLANT
DISTILLED
WATER
CO, PURIFICATION
H20 + CO
LINESTONE DISSOLUTIOX
BACK MASHING
SLURRY
pH ADJUSTNENT
RECAREONATED MATER
Fig. 2.
305
gen,
and is therefore
fed to a stripping
tower.
By direct
counter-
of about
For
final
system is
stream.
As can
7.7 m.
pH adjustment
used
to
inject
be observed
from
of the
water
15 wt%
NaOH
Fig.
to about
solution
1 and Fig.
8.0,
into
2, the
a dosing
the
water
recarbonation
mode,
filters
the
water
limestone,
The
stream
entering
and increase
amount
the
the total
of CO2 which
filters
to
dissolve
more
alkalinity.
can be extracted
involved
Results
The
Heavy
The
of Plant
Shuwaikh
Industries
WRDC
of MEW
Operation
Recarbonation
by Sumitomo
started in October
1987.
designed
recarbonated
water
the households
supplied
the quality of drinking
distillate
and
the
carbonated
drinking
water,
respectively.
Figures 3-9 display some of the results obtained in this investi-
306
Tab le
1.
433.67
7.93
18.93
91.9
173.14
43.64
1.0
10
16.88
Time
TDS
PI'
T.Alk
Cl
SO4
CA
L.1.
R.I.
Cl.S04/T.Alk
Oct. 87
86.0
8.28
72.68
0.20
5.0
26.05
0.54
7.12
0.069
Nov. 87
77.5
8.21
70.54
0.20
5.0
26.73
0.45
7.30
0.069
Dec.
87
87.8
a.26
69.33
0.20
5.0
25.87
0.48
7.30
0.07
Jan.
88
95.6
7.93
74.84
0.20
5.0
28.60
0.22
7.50
0.065
Feb. 88
9.30
7.85
71.50
0.20
5.0
29.48 0.10
7.65
0.082
Mar. 88
90.6
7.88
74.91
0.20
5.0
28.91 0.18
7.50
0.072
Apr. 88
83.5
8.11
74.82
0.20
5.0
28.53 0.40
7.30
0.058
May 88
87.4
8.09
67.00
0.20
5.0
30.07 0.28
7.50
0.77
80.3
7.99
72.50
0.20
5.0
26.67
7.50
0.067
Jul. 88
74.0
7.98
74.33
0.20
5.0
28.80 0.26
7.50
0.066
Aug. 88
32.5
7.90
64.50
0.20
5.0
28.20 0.06
7.80
0.069
Sep.
68.0
7.85
65.00
0.20
5.0
24.15 0.02
7.80
0.075
Jun.
88
88
0.25
307
Table
I 1I,\
TDS
PH
330.7 7.95
T.Alk
Cl
54.72
of Kuwait
CA
SO1
95.1)j
i.1.
Drinking
R.I.
-0.034
Water
Cl.S04/T.Alk
8.00
3.57
7.80
2.236
219.4 7.94
8.00
1.908
277.8 7.87
53.1
8.20
3.8
246.2 7.55
8.50
2.296
254.9 7.60
8.30
2.064
252.1 7.73
52.90
8.30
1.699
256.9 7.99
7.80
2.02
260.7 7.97
7.70
1.840
257.87 7.99
7.70
1.809
271.13 7.99
7.80
1.883
264.00 7.82
7.90
1.82
49.20
37.,29
3il.i
350
0
r
I
7
OCT.87 NOV.87 DEC.87 JAN.88
I.I
FEB.88
I
MAR.88
TIME
CARBONATED
Fig. 3.
DISTILL.
Total
I
APR.88
+
I
MAY 88
I
JUN.88
CARBONATED
JUL.83
I
AUG.68
DRINKING
SEP.89
308
--
OCT.37
NOV.87
DEC.E7
JM.83
FEB.83
kAZ.83
APR.83
WY
88
JUN.83
JUL.83
AUG.33
SEP.83
TIME
f
CARBONATED DISTILL.
Fig.
CARBONATED DRINKING
4.
as a function of time.
76
74 -
c
72
63 66 -
64
62
60
58
56
54
521
OCT.87
,
NOV.87
DEC.87
I
JAN.88
1
FEB.88
I
MAR.88
I
APR.83
I
MAY 88
1
JUN.88
I
JUL.83
AUG.38
nh4E
CARBONATED DISTILL.
Fig. 5.
CARBONATED DRINKING
SEP.33
41
40
39
38
37
36
35
34
33
32
31
30
29
28
27
26
25
OCT.87
NOV.67
DEC.87
JAN.88
FEB.88
MAR.88
APR.88
MAY 88
1
JUN.88
I
JUL.88
1
AUG.88
SEP.88
nME
+
CARBONATED DISTILL
Fig.
6.
Calcium
ion
and drinking
concentration
of the
water
as a function
CARBONATED DRINKING
carbonated
of time.
distillate
OX .
0.4
0.3
OCT.87
NOV.67
DEC.87
JAR.88
FE9.88
M.88
APR.88
hAY 88
JUN.88
~uL.88
~uG.66
s~p.86
TIME
Cl
CARBONATED DISTILL.
Fig.
7.
CARBONATED DRINKING
of
the
carbonated
Langelier
saturation
index (LI)
and drinking
water as a function
Of time.
distillate
310
9
8.8
8.6 8.4 -
~ub4.88
~~p.88
JLJI_.&~ 4~~33
TIME
cl
CARBONATED DISTILL.
Fig. 8.
Ryzner
Index of the carbonated
as a function
of time.
CARBONATED DRINKING
distillate
and
drinking
water
1.5-j
/
1
0.5
g
r-l
0
OCT.87 NOV.87 DEC.87 JAN.88 FEB.88 MAR.88 APR.88 MAY 86 JUN.88 JUL.38AUG.83 SEP.88
TIME
CARBONATEDDISTILL.
Fil.
9.
CARBONATEDDRINKING
Chloride-sulphate
to alkalinity
ratio for the carbonated
distillate
and drinking water as a function of time.
311
gation.
The
results
shown
reflect
the
quality
of
the
recarbonated
before
(distillate)
and after
blending
with
brackish
water
water
(drinking),
as a function of time.
It can be generally
stated
MIGD to
shown are monthly average values and apart from a start-up period
of 12 days, the plant operation is quite stable.
Besides the pH,
total alkalinity
and calcium content
the Langelier
CaCOS saturation index
index (R.1) and the
important
parameters
stated
bition
chloride-sulphate
used to evaluate
a zero L.1
earlier,
is chemically
of the recarbonated
water,
(L.I), the Ryznar stability
stable
value
while
characteristics
indicates
a positive
or
to alkalinity
ratio
the water quality.
the
value
ability
of
indicates
water
to
are
As
water
scale
inhi-
form
CaC08
Ryznar
Stability
Index
to stabilize
(R.1)
towards
the
can be calculated
end of
using
the
equation
R.1
Values
sion while
of
2 pHs - pH
R.1
greater
than
7.0
indicate
shows R.I.
shows chemical
stability towards the end of the period
with the drinking water quality before carbonation.
The
meter
chloride-sulphate
used to evaluate
(cl- + SO,*)/Total
Ratios
around
dissolved
0.1
oxygen
to alkalinity
water
Alkalinity
indicate
and
quality,
at
pH
is the third
and is expressed
para-
as
(mea/l)
chemical
values
ratio
compared
of
stability
7.0-8.0.
in presence
However,
it
of
is
312
reported
Figure
water.
by
Rabald4
that
this
ratio
can
take
higher
values.
distilled
in Kuwait
ratio values of
corrositivity.
about
Conclusion
The
operating
data,
over
period
of
12 months,
indicated
experience
has decided
at Doha
with
gained
to build
a capacity
outcome
recarbonation
of 90 MGID
of this
plants.
process,
The first
one
one at Az-Zour
After implementing
this scheme, all
with a capacity of 40 MIGD.
distilled
water produced
in Kuwait will be recarbonated
in an
attempt
to overcome
the problem
of "red water
".
References
1.
Abdel-Jawad,
M.A.
and Al-Turaihi,
M.A.
of Electricity
Abdel-Jawad,
M.A.,
and Water,
Al-Saleh,
S.A.
Report
and corrosion.
WRDC/R/48,
and Al-Qaisi,
1981.
M.
3.
Ministry
of Electricity
Standard
Methods
and Water,
1975.
4.
Rabald,
Corrosion
E.
Guide,
Elsevier,
1968.
Report
WRDCJRI48,
of water
1981.
and seawater,