Cycle Chemistry

Challenges in Power
Industry
Engineer Training for Hach
2016-DUBAI
Dipl. Ing László Hilt
GWC Water Consultant GmbH
 Chemically Influenced Tube Failures
Source: EPRI – Dooley, 2004

2016.01.25. Dipl. Ing. Laszlo Hilt 2

 SG Component Failures Responsible for Forced Outages
(based on incident-equivalent downtime hours: EPRI)

• Water walls/economizer  50%

• Superheater/reheater  25%
• Equipment of fire side and others  25%
• Possible root causes
• Misapplications, not appropriate chemistry, worst feeding locations
• Lack of reliable on line monitoring instruments
• Lack of simple & practical procedures for making corrective actions by
operators; Who is responsible for what & when?
• Lack of automated adjustment of dosage pumps and CBD valves by on
line (in situ) control of pH, ORP and or CC/DCC
• Cycling operation and lack of appropriate lay up during idle periods

2016.01.25. Dipl. Ing. Laszlo Hilt 3

 Typical Cost of Replacement (EPRI report)

2016.01.25. Dipl. Ing. Laszlo Hilt 4

 Metallurgical Picture

2016.01.25. Dipl. Ing. Laszlo Hilt 5

 Concentration mechanism under deposition

2016.01.25. Dipl. Ing. Laszlo Hilt 6

 Conversion from AVT(R) to AVT(O) and OT

70 kg/y less magnetite

deposition

2016.01.25. Dipl. Ing. Laszlo Hilt 7

 Magnetite (Fe3O4) and alfa hematite (α–Fe2O3)

AVT(O)  T = 150 oC
All Steel, DO = < 10
pH = 9.2 – 9.6 (9.8)
ORP = +/- 50 mV

2016.01.25. Dipl. Ing. Laszlo Hilt 8

 Cycle chemistry in TPP-s

• Oxygen scavenging (?) and metal passivation

• Decreasing the corrosion product transport from preboiler system into EVA
• Internal BW treatment
• Mainly corrosion control of heat transfer surfaces of boiler
• Condensate corrosion (pH) control
• Improving pH distribution in phase transient zones and in the first
condensation areas

2016.01.25. Dipl. Ing. Laszlo Hilt 9

 Reactions and/or Breakdown Products

Chemical Formula %C (wt) Reaction and/or By-Products

Hydrazine - N2H4 0 Nitrogen, water, ammonia

Carbohydrazide - (N2H3)2CO 13.3 Hydrazine, nitrogen, water, ammonia

carbon dioxide

Hydroquinone - C6H4(OH)2 65.5 Benzoquinone, light alcohol, ketones, low

molecular weight species, carbon
Dioxide

Diethylhydroxylamine 53.9 Acetaldehyde, acetic acid,

(CH3CH2)2 NOH dialkylamines, ammonia, nitrate, nitrite

Methylethylketoxime 55.2 Methylethylketone, hydroxylamine,

(CH3)(CH3CH2)C=NOH nitrogen, nitrous oxide, ammonia, carbon
dioxide

Erythorbic Acid - C6H8O6 40.9 Dehydroascorbic acid, salts of lactic and

glycolic acid, carbon dioxide

2016.01.25. Dipl. Ing. Laszlo Hilt 10

 Coordinated phosphate treatment of BW

How much ppm NaOH

generates pH = 10?

2016.01.25. Dipl. Ing. Laszlo Hilt 11

EPRI: Phosphate Continuum (Low or High level) Guidelines

2016.01.25. Dipl. Ing. Laszlo Hilt 12

 Phase Transient Zones
Partially Condensation
Partially Evaporation

Resourching:
How can we improve the pH in the early condensate?

This figure were produced by MEI – Moscow

on their pilote turbine system:

Ammonia (w. High V/L ratio) can produce low pH, while
Organic amine (like morpholine w. Low V/L ratio)
can produce high pH in LP part of the turbines

2016.01.25. Dipl. Ing. Laszlo Hilt 13

 Ammonia Treated Turbine Blades

31-October-2006 Dipl. Ing. László Hilt 14

 Riser Failure at HRSG-LP Drum

31-October-2006 Dipl. Ing. László Hilt 15

 PTZ&Early Condensate

31-October-2006 Dipl. Ing. László Hilt 16

First condensation pH = (%Water Condensed&V/L)
Target pH after neutralization: 8,5

The initial pH of bulk steam was 8,5;

and it will be the pH = 8,5 in bulk
condensate only after 100%
condensation

Ammonia will approach it from down,

and produces pH < 7 in turbine
moisture region (2 to 14 % cond.)

Organic amine based product will

approach it from up, and can produce
pH > 9 in turbine moisture region

31-October-2006 Dipl. Ing. László Hilt 17

EPRI–FW limits for all ferrous and mixed metallurgy systems

For conventional and

CCGT stations as well.

2016.01.25. Dipl. Ing. Laszlo Hilt 18

EPRI: Key parameter limits of continuum of treatments

(1)For Na/PO4 molar ratio = 3/1; (2)New AVT guideline; (3)New OT guideleiene to be published at 2004; (4)New PC/CT guideleine

2016.01.25. Dipl. Ing. Laszlo Hilt 19

 BWR – Ionexchange treatment circuits

2016.01.25. Dipl. Ing. Laszlo Hilt 20

Thank you for YOUR
attantion!
 Evolution of FW & BW Chemistry

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 EPRI: Continuum of treatments

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