Troubleshooting Water Chemistry

i an Electrical
in
El t i l Boiler
B il
Folmer FOGH, Monika Nielsen DONGEnergy

Chemie im Kraftwerk 2016, Karlsruhe

October 26th 2016

NJV3+2

SSV3+4
HEV1

ESV3

ASV2+5
SKV3

FYV7 3
FYV7+3
STV2

ENV3

Slide 2 of 11

AVV1+2
AMV1+3

Consumption

6000 MWe (high)

3000 MWe (low)

District heat

+3000 MJ/s

Thermal power

3000 MWe
+2000 MWe mothballed

Fuels

Coal, oil,
Coal
oil gas,
gas straw,
straw
wood (pellets/chips)

Interconnectors

+5000 MWe

Renewables

5000 MWe wind

800 MWe solar

Slide 3 of 11

26/12-2013

Slide 4 of 11

27/12-2013

Property

Makeup
water

Boiler
water

Residual hardness - dH

< 0.05

Conductivity - S/cm

< 5.00

< 70

8.5 9.2

8.5 - 10

pH
O2 - g/L

Slide 5 of 11

< 20

Apparently a peace of cake installation!

However operations experienced rising conductivities exceeding the prescribed limit

resulting
g in excessive need for blow down and refilling
g
The only on-line instrument was a conductivity meter
Samples were taken and send for the initial (forensic) analysis
pH

< 70

8,5-10

20/08-2015

63

7,2

2,2

0,1

5,3

0,5

4,6

27/08 2015
27/08-2015

60

67
6,7

12
1,2

01
0,1

04
0,4

74
7,4

31/08-2015

61

7,3

1,2

0,1

0,5

7,6

Limits

Slide 6 of 11

NH3 Chloride Nitrate Sulfate Sodium

mg/L
mg/L
mg/L
mg/L
mg/L

Conductivity
S/cm

Boiler 10

Sparking

Hydrolysis

N2 + O2 2 NO

H2O H2 + O2

2 NO + O2 2 NO2

N2 + 1 H2 NH3

3 NO2 + H2O 2 HNO3 + NO

NH3 + 2O2 NO3 + H+ + H2O (pH drop)

HNO3 H+ + NO3- (pH drop)

That wasnt the only reason

The increased minimum load (secure submersion of the electrodes) didnt cure the low

pH although
p
g the nitrate formation rate decreased.

Hydrolysis
H2O H2 + O2
N2 + 1 H2 NH3
-

NH3 + 2O2 NO3 + H + H2O (pH drop)

The Cavalary (chemist) is called in.
Slide 7 of 11

Something is missing
Conductivity
S/cm

pH

Limits

< 70

8,5-10

06/03-2016

59

7,8

0,15

<0,1

0,1

<0,1

13

08/03-2016

59

7,7

0,15

<0,1

0,1

<0,1

13

Comment

OK

OK

OK

OK

OK

OK

Boiler 10

Slide 8 of 11

NH3 Chloride Nitrate Sulfate Sodium

mg/L
mg/L
mg/L
mg/L
mg/L

Carbon

Conductivity
S/cm

pH

Limits
14-03-16 14:50
14-03-16 15:20

< 70
60
57

8,5-10
8,4
7,9

14-03-16
14
03 16 16
16:20
20
14-03-16 19:25
15-03-16 03:25
15-03-16 03:40
Comment

57
59
58
57
OK

8,3
8
3
9,1
8,4
8,5
OK

Boiler 10

Slide 9 of 11

NH3
mg/L

Chloride
mg/L

Nitrate
mg/L

Sulfate
mg/L

Sodium
mg/L

Iron
g/L

p-value
[OH- + CO32-]
mmol/L

b-value
[HCO3-]
mmol/L

HCO3mg/L

0,19
0,15

< 0,1
< 0,1

0,12
0,1

< 0,1
< 0,1

13
12

570
310

0,07
0

0,65
0,66

35,4
40,3

0,18
0
18
0,3
0,53
0,43

< 0,1
01
< 0,1
< 0,1
< 0,1
OK

0,12
0
12
0,1
0,15
0,14
OK

< 0,1
01
< 0,1
< 0,1
< 0,1
OK

12
12
12
11
OK

190
150
440
470

0,08
0
08
0,13
0,07
0

0,65
0
65
0,54
0,61
0,66

34,8
34
8
25,0
32,9
40,3

Here is the culprit

The final clue:
TOC in make up water:

54 ppb

TOC in boiler:

2,4 ppm

GRP is not a suitable material for

temperatures above 80C
Electrodes and top of overflow pipe
Slide 10 of 11

Thank you for listening

Questing and comments welcome

Wind electricity sharre

(energ
gy)

Yearly
y hours with
+100%
% wind electricity share
12

2006

17%

2007

20%

2008

19%

2009

19%

2010

22%

2011

34

28%

2012

41

30%

2013

202

33%

2014

280

39%

2015

409

42%

2006-2013

2013

June 2013
December2013
13