Page 1 of 3 Date: 30-Oct-2020

Ammonia, pH and Environment

pH is a logarithmic scale.

When we prescribe to increase pH in boiler feed water then the ammonia requirement is different at
different stage say if you are at pH 8 area then 100 ppb ammonia will increase pH 0.25 but for the
same amount of ammonia at pH 9 area only increase it to 0.1pH.

It’s obvious. Imagine when we are dosing that ammonia ultimately it will come to our effluent in any
form but as nitrogenous compound.

When oxygenated treatment (OT) came in India by holding hand with once through super critical
boiler in around 2011 the requirement was pH 8 to 8.5 but with time the recommendation changed
gradually by different OEMs and others say as 8.5 to 9.0 and some even try to say 9 is good and
better be go beyond that. But does anybody have any tangible documentation? or we are just going
on increasing the pH without questioning?

In the left Graphical

pH
representation of pH and
9.8 ammonia concentration
9.6 (mg/L).
9.56
9.49
9.4 9.38

9.2 9.18
9.11
9 9.02 Where it indicates the
8.89 increase of pH reduces
8.8 8.79 at higher pH bracket for
8.65 the same amount of
8.6
0 0.5 1 1.5 2 2.5 ammonia injection.

Ammonia Understanding Concentration

jump:
0.45 0.4
0.4 Indicates twice ammonia
0.35 concentration to increase pH
0.3 to 8.89 from 8.65 (diff of pH
0.25 0.2 0.24)
0.2
0.15 And to raise pH 9.11 from 8.89
0.1
0.1 (pH diff 0.22) again twice
0.05 ammonia requirement.
0 i.e. 4 times ammonia needed
8.65 8.89 9.11 to increase 0.5 pH.

Ref: ASTM D 5128

Ammonia-Environment amitavadatta
Page 2 of 3 Date: 30-Oct-2020

Now we have to think for Environment & Sustainability and social cost we have to evaluate for
using any resource. Nitrogen and phosphorus are nutrients and can leads to algal boom.

The thinking on pH also gone to a different direction, when water is hot pH decreases!
pH has come from pKw and for pure water at 25 deg C pKw = 10 -14 then pH is 7 & pOH is also 7 but
say at 90 deg C pKw = 10 -12 then pH is 6 & pOH also 6 keeping the neutrality.

Recent media news indicates India, Russia & China are major environmental pollutants and India has
given lot of pressure to curb SOx & NOx in Thermal power plant. Though implementation will
increase thermal power plant net heat rate but there is no other option. If we trac regarding NOx
control we are still in the option for older units to restrict it in burner control method without going
to use Chemical treatment. Those who are aware of this know that NOx control to a very low level
require lot of Ammonia or Urea. And court order came in July to keep 450 mg/Nm3 in place of 300
and on 22nd October 2020 it came as a Gazette notification.

But in power plant chemistry we are using ammonia and we are increasing this ammonia day by day
though original oxygenated treatment came with a nominal pH of 8 (say <50 ppb ammonia).

The classical thinking of oxygen increase, increase corrosion has changed for pure water. But for pH?

The left side graph is a conventional

corrosion graph which indicates that
with oxygen corrosion increase.

But that graph is with impure water and

with pure water the graph changes and
in place of increase it actually drops with
oxygen.

And on that logic OT implemented.

Similarly, we also know that with increase of pH iron corrosion decreases but is it the same
requirement for very pure water. We know that for drum type boiler when impurity increase in
drum say Cl- increase, there is a requirement of solid alkalizer not ammonia.

Now coming to established say of 660 or 830 MW supercritical units where all CPUs are maintained
and feed water cation conductivity maintained ≤ 0.1 µS/cm is it required to increase pH?

We have done lot of improvement in boiler water chemistry and eliminated hydrazine in all ferrous
system ever in drum type boiler, it’s a big step and helped so many ways like non-use of carcinogenic
chemical, reduction of one inventory etc.

Ammonia-Environment amitavadatta
Page 3 of 3 Date: 30-Oct-2020

Similarly, at this stage when we are sacrificing heat rate for environmental purposes by introduction
of FGD (Flue Gas De-Sulphurisation) and NOx abatement, we have to ask ourselves do we need to
double our ammonia consumption.

The requirement of ammonia to increase pH of de-mineralized water for 8 pH is <50 ppb and for 8.5
it is 70 ppb. (we are talking about for water cation conductivity <0.1 to max <0.15, CPU is in good
condition)

Reduction of ammonia can be done in 2 ways, one by proper measurement of pH wrto ammonia and
secondly actual reduction knowingly.

Conclusion:

Here this discussion is considered for those units which are new less than 10 years of run with high
capacity say 660-700 MW, 830 MW (Once through supercritical Thermal Power) and running from its
initial time on Oxygenated Treatment (OT) well maintained cation conductivity of < 0.1 or max <0.15
with well-maintained CPU.

This may be a reasonable point that why this discussion required for ammonia use curtailment when
this boiler water treatment ammonia is a meager amount wrto ammonia use in fertilizer. In India we
thought Sulphur content is very low in Indian coal in the tune of 0.3 % but now it become mandatory
to install FGD (Flue Gas De Sulphurisation) and even for the older units.
Regarding advocacy of high pH comes from some units which are not similar type and chemical
regime is not same and even compared with heat recovery boilers. Here the aim should be is it really
required.

Now social cost of use anything whether it is chemical or other need to be considered.

[ When I am talking about pH for pure water (reagent grade water) or pure water slightly
ammoniated this is to be understood by following ASTM D 1193 & ASTM D 5128 as normal concept
of pH measurement by using glass electrode even by online instrument does not reflect the same as
high conductivity electrolyte buffer is used etc. And that is why even to maintain pH 8.5 chemist
used to go 1.5 µS/cm or beyond whereas only 1 µS/cm suffice]

Ammonia-Environment amitavadatta