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CARBOHYDRAZIDE vs HYDRAZINE:
A Comparative Study
Dr. Mohammed Mahmoodur Rahman
Co-Investigators
Mr. Saad A Al-Sulami
Engr. Fahd Al-Muali
Mr. Kither Mohammed
Mr. A.J. Shahrani (Jubail Plants)
Saline Water Desalination
Research Institute
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CONTENTS
1
Background
Introduction
Objectives
3O
4
Experimental
Conclusions
2
2
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BACKGROUND
Saline Water Conversion Corporation (SWCC) produces
electricity and drinking water through its dual-purpose
plants. The total power generated from all these plants
exceeds 5000 MW. This enormous power is being
generated from 55 high pressure boilers.
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Despite the fact that all SWCC power plants are taking
necessary safety measures while handling hydrazine, it
has become a serious desire of the top SWCC
management to search for a suitable alternative to
hydrazine for all SWCC boilers, that provides excellent
oxygen scavenging, non-toxic and safe while handling.
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EQUIPMENT RELIABILITY
Uninterrupted Production
Routine Maintenance
reduces crisis maintenance
allows planned preventive maintenance
ECONOMICS
Decrease Overall Maintenance Cost
Decrease Downtime Cost
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OXYGEN CORROSION
O2
Fe2+
OH-
O2
WATER
ELECTRON FLOW
ANODE
CATHODE
ANODE REACTION
Fe. = Fe++ 2e-
CATHODE REACTION
1/2 O2 + H2O + 2e- = 20H-
MECHANISM
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7
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H2
OXYGEN REDUCTION
(CATHODE) (2)
Fe2O3
RED OXIDE
BLACK OXIDE
O2
OH-
MAGNETITE
Fe3O4
Fe(OH)2+ + FeOH++
ELECTRON
FLOW
HYDROGEN
EVOLUTION
(CATHODE) (4)
ACID SOLUTION
WITH REDUCED
OXYGEN CONTENT
H+ + FeOH+
PIT
BLACK OXIDE
PRECIPITATION
(CATHODE) (7)
OXIDATION (5) AND
HYDROLYSIS (6)
Fe++
eFe
HYDROLYSIS OF
DISSOLVED IRON
LOWERS pH (3)
IRON DISSOLUTION
(ANODE) (1)
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MECHANICAL
Deaerators
CHEMICALS
(Oxygen Scavengers)
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ORGANIC (volatile )
SOLID
SODIUM BISULFITE
SODIUM SULFITE
NON-SOLIDS
HYDRAZINE
HYDROQUINONE
DEHA
CARBOHYDRAZIDE
ASCORBIC ACID
ISO-ASCORBIC ACID
10
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Sulphite
REACTION:
2Na2SO3 + O2
2Na2SO4
SCAVENGER DECOMPOSITION:
Na2SO3 + H2O
SO2 + 2 NaOH
4 Na2SO3
3 Na2SO4 + Na2S
Na2S + 2H2O
NaOH + H2S
11
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Sulphite
ADVANTAGES:
TRUE RESIDUAL TEST
VERY FAST REACTIVITY
WITH OXYGEN
AVAILABLE IN LIQUID AND
DRY FORMS
INEXPENSIVE
SULFITE : FDA Approved
DISADVANTAGES:
CONTRIBUTES TO TDS
BREAKS DOWN AT 42
Kg/cm DRUM PRESSURE
12
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Hydrazine
REACTION:
N2H4 + O2
N2 + 2H2O
DECOMPOSITION REACTION:
2N2H4 + HEAT + 2H2O
4NH3 + O2
CONTROL LIMITS:
RESIDUAL N2H4 AT ECONOMIZER INLET
13
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Hydrazine
ADVANTAGES:
DISADVANTAGES:
14
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Hydroquinone
O
OH
REACTION:
C6H6O2 + 1/2O2
+ 1/2 O2
OH
Hydroquinone
Benzoquinone
H2O + C6H4O2
CONTROL LIMITS:
DISSOLVED OXYGEN TEST
TYROSINE AND LEUCO CRYSTALS VIOLET
TEST
IRON REDUCTION TEST
15
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Hydroquinone
ADVANTAGES:
DISADVANTAGES:
MORE EXPENSIVE
THAN HYDRAZINE
CAN INCREASE
CATION CONDUCTIVITY
16
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Ascorbic acid
CH2OH
CH2OH
CHOH
CHOH
O
CH
O
O
CH
C + 1/2 O2
C
C + H2O
C
OH
OH
Ascorbic Acid
O
O
Dehydroascorbate
REACTION:
C6H8O6 + 1/2O2
C6H6O6 + H2O
CONTROL LIMITS:
DISSOLVED O2 TEST
IRON REDUCTION TEST
17
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Ascorbic acid
ADVANTAGES:
WORKS WELL IN pH
RANGE (7-11)
CONTRIBUTES NO
TDS
OXYGEN
SCAVENGING
DISADVANTAGES:
18
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CH3 CH2
N - OH + 9 O2
CH 3 CH 2
O
H
Acetic acid
Diethyl Hydroxylamine
2(C2H5)2NOH + O2
Oxygen
DEHA
Nitrone
2(C2H5)CH3CHN=O + 2H2O
2C2H5HNOH
+ O2
Ethylhydroxylamine
Acetaloxime
4NH2OH
2CH3CHO
Acetaldehyde
Water
+ O2
Oxygen
+ O2
Oxygen
Ethylhydroxylamine
Acetaldehyde
2CH3CH=NOH + 2H2O
Oxygen
CH3CH=NOH + H2O
Water
2C2H5HNOH + 2CH3CHO
Water
Nitrone
Acelaloxime
Water
CH3CHO + NH2OH
Acetaldehyde
2N2 + 6H2O
Nitrogen
Water
2CH3COOH
Acetic acid
19
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ADVANTAGES:
No solids contribution to the
boiler
Steam volatile magnetite
promoter
Simple to dose and control
Effective oxygen scavenger
DISADVANTAGES:
Cost per kg is high
Is not thermally stable
Non-volatile product (acidic)
Decomposition of acidic products
may end up in condensate circuit
20
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ADVANTAGES
DISADVANTAGES
21
Carbohydrazide
O
NH2 - NH - C - NH - NH2 + 2 O2
Indirect reaction
(N2H3)2CO + H2O
2 N2H4 + 2 O2
> 135C
Decomposition
(N2H3)2CO + H2O
l
> 200C
2 N2H4 + CO2
4 H2O + 2 N2
2 NH3 + N2 + H2 + CO2
23
23
Carbohydrazide
An oxygen scavenger that contributes no
inorganic solids to the feed water or boiler
water
An oxygen scavenger that DOES NOT
decomposes in organic acid species
Contributes to passivation
Controls oxygen corrosion
24
24
Carbohydrazide
Chemical/Formula
%C
(wt.)
Hydrazine
0
N2H4
Cabohydrazide
(N2H3)2CO
13.3
Erythrobic acid
C6H8O6
40.9
Diethylhydroxylamine
(CH3CH2)2NOH
53.9
Methylethylketoxime
(CH3)(CH3CH2)C=NOH
55.2
Hydroquinone
C6H4(OH)2
65.5
25
25
OBJECTIVES
To evaluate the suitability and efficiency of carbohydrazide
as an alternative oxygen scavenger to hydrazine in the
high-pressure boiler.
To determine the consequences of degradation byproducts on boiler system.
To evaluate the ability of the alternative oxygen scavenger
in forming and maintaining an oxide film in the boiler.
26
26
EXPERIMENTAL
Two boilers # 81 and # 82 of PhaseII at Al-Jubail
Plants, each generating 130 MW/h, were selected
for the trial tests in consultation with chemical
manufacturing company.
Boiler # 81 was run with carbohydrazide and
boiler # 82 with hydrazine. Both these boilers are
pressurized box type water tube boilers. The
maximum continuous rating (MCR) of steam is
710 tons/h.
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27
Test Conditions
Parameters/
Samples
pH
Sp. Conductivity (S/cm)
Cat. Conductivity (S/cm)
Copper (ppb)
Ammonia (ppm)
Iron (ppb)
Dissolved O2 (ppb)
Hydrazine (ppb)
Silica (ppb)
Sodium (ppb)
Chloride (ppm)
Phosphate (ppm)
P-Alkalinity(ppm)
M-Alkalinity(ppm)
Daerator
Condensate
out
8.5 9.2
<3
<0.5
<5
<0.3
<10
<20
-----<20
<10
<0.01
----------------
------------------------------------<10
-------------------------------------------
(Boiler chemistry)
Feed Water/
Economizer
inlet
8.7 9.2
<3
------<5
<0.3
<10
Nil or <7
10 - 20
<20
<10
<0.05
-------------------
Boiler Blow
Down (Drum)
9 9.8
<50
------<20
------<50
----------1000
-----<0.5
5 - 10
<5
<15
Saturated
Steam
8.7 9.2
<3
<0.5
---<0.3
---------------<20
<10
<0.05
----------------
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28
Test Conditions
S. No.
Equipment
1
2
3
4
5
6
7
8
9
Condensate
Deaerator
10
11
Capacity
---------86 M3
25 M3
Boiler feed Pump 900 M3
HP Heater 1
---HP Heater 2
----Economizer
----Boiler
12 1M3
Super heater
39 M3
Hydrazine tank
560 L
pump
Phosphate tank
560 L
pump
(Operations)
Water/Steam
Pres.
Temp.
0C
(Bar)
9.5-9.8
99-121
5
156
-----103
---103
160-195
103
195-233
102
230-295
104
310
95
515
Flow
M3/H
---700
---697
697
697
700
700
700
150
----
50L/H
150
--------
50L/H
29
29
30
30
Boiler water
(boiler drum)
Feed water
Make-up water
Brine heater
condensate
31
31
30
FW CHDZ (ppb)
20
150
15
100
10
50
FW Hydrazine (ppb)
25
200
5/17/05
5/31/05
6/14/05
6/28/05
7/12/05
7/26/05
8/9/05
8/23/05
9/6/05
9/20/05
10/4/05
Date
CHDZ
Limit CHDZ
Hydrazine
Limit Hydrazine
32
32
SS Ammonia (ppm)
1.2
1
0.8
0.6
0.4
0.2
0
5/17/05
5/31/05
CHDZ
6/14/05
6/28/05
Hydrazine
7/12/05
Limit
7/26/05
8/9/05
8/23/05
9/6/05
9/20/05
10/4/05
8/9/05
8/23/05
9/6/05
9/20/05
10/4/05
8/9/05
8/23/05
9/6/05
9/20/05 10/4/05
Date
1
0.8
0.6
0.4
0.2
0
5/17/05
5/31/05
6/14/05
6/28/05
7/12/05
7/26/05
Date
CHDZ
BHC Ammonia (ppm)
FW Ammonia (ppm)
Optimization of Carbohydrazide
Hydrazine
Limit
0.8
0.6
0.4
0.2
0
5/17/05 5/31/05 6/14/05 6/28/05 7/12/05 7/26/05
Date
CHDZ
Hydrazine
Limit
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33
Boiler Chemistry
9.2
8.7
8.2
5/17/05
5/31/05
6/14/05
Carbohydrazide
6/28/05
Hydrazine
7/12/05
Limit
7/26/05 Date8/9/05
8/23/05
9/6/05
9/20/05
10/4/05
7/26/05Date 8/9/05
8/23/05
9/6/05
9/20/05
7/26/05 Date
8/9/05
8/23/05
9/6/05
9/20/05
10/4/05
7/26/05Date 8/9/05
8/23/05
9/6/05
9/20/05
10/4/05
7/26/05
Date
8/23/05
9/6/05
9/20/05
10/4/05
BBD pH
10.2
8.2
5/17/05
5/31/05
6/14/05
5/31/05
6/14/05
BHC pH
Carbohydrazide
Carbohydrazide
SSpH
6/28/05
7/12/05
6/28/05
7/12/05
Hydrazine
Limit
10/4/05
9.4
9.2
9
8.8
8.6
8.4
8.2
5/17/05
Hydrazine
Limit
9.4
9.2
9
8.8
8.6
8.4
8.2
5/17/05
5/31/05
6/14/05
Carbohydrazide
DAO pH
pH Control
pH values for both
hydrazine
and
Carbohydrazide
were found to be
maintained in the
range of 8.6 and 9.0
for
Brine
heater
condensate (BHC),
Feed water (FW),
Saturated
steam
(SS) and Deaerator
outlet
(DAO)
whereas for Boiler
blow down (BBD) it
was in the range of
9.0 and 10.
FW pH
9.7
6/28/05
Hydrazine
7/12/05
Limit
9.4
9.2
9
8.8
8.6
8.4
8.2
5/17/05
5/31/05
Carbohydrazide
6/14/05
6/28/05
Hydrazine
7/12/05
Limit
8/9/05
34
34
Boiler Chemistry
14
12
10
DAO Disol. O2
Dissolved Oxygen
8
6
4
2
0
5/17/05 5/31/05 6/14/05 6/28/05 7/12/05 7/26/05 8/9/05 8/23/05 9/6/05 9/20/05 10/4/05
Date
CHDZ
Hydrazine
250
200
BHC Disol. O2
150
100
50
0
5/17/05 5/31/05 6/14/05 6/28/05 7/12/05 7/26/05 8/9/05 8/23/05 9/6/05 9/20/05 10/4/05
Date
CHDZ
Hydrazine
35
35
Boiler Chemistry
40
FW Copper (ppb)
35
30
25
20
15
10
5
0
5/17/055/31/056/14/056/28/057/12/057/26/05 8/9/05 8/23/05 9/6/05 9/20/0510/4/05
Date
CHDZ
50
45
40
35
30
25
20
15
10
5
0
36
36
Boiler Chemistry
Control of Iron levels
25
15
10
5
0
5/17/05 5/31/05 6/14/05 6/28/05 7/12/05 7/26/05 8/9/05 8/23/05 9/6/05 9/20/05 10/4/05
Date
CHDZ
60
50
40
FW Iron (ppb)
20
30
20
10
0
5/17/05 5/31/05 6/14/05 6/28/05 7/12/05 7/26/05 8/9/05 8/23/05 9/6/05 9/20/05 10/4/05
CHDZ
Date
37
37
Corrosion studies
The exposed coupons were
visually examined. A uniform
and non-porous oxide film
was found to be adhered on
the coupons indicating the
protective nature of the
films. The corrosion rate of
0.044 mpy determined for
carbon steel coupons fixed
in drum at water side with
hydrazine dosing indicates
extremely low corrosion.
Coupons
in Boiler
Drum
Before
test
Coupons
in Boiler
Drum
after test
Coupons
in HP
heaters
after test
Coupons in
HP heaters
Before test
38
38
Front
Back
Steam side
The
corrosion
rates
determined
with
carbohydrazide dosing for
carbon steel coupons fixed
in drum at water side and
steam side were 0.384 mpy
and 0.444 mpy respectively,
whereas that determined for
carbon steel and 70/30
cupronickel in HP heaters
were 0.251 mpy and 0.128
mpy
respectively.
The
corrosion rates of the
material appear to be low
and effect of corrosion
appears to be insignificant.
Water side
Corrosion studies
Front
Back
Carbon steel coupons after exposure in water drum under Carbohydrazide dosing boiler
#81
Back
Front
39
39
CONCLUSIONS
The results indicated the suitability and efficiency of
Carbohydrazide oxygen scavenger as an alternative to
hydrazine in SWCC high pressure boiler provided the
concentration of residual hydrazine (decomposition byproduct of Carbohydrazide) is maintained at levels
between 30-40 ppb in the feed water.
No harmful degradation by-products were found.
CONCLUSIONS
Iron levels measured at economizer inlet (boiler
feed water) were reduced by 75% whereas for
copper it was found to be maintained at the
baseline value. In the boiler water (drum) the
reduction in Fe and Cu were 10% and 33%,
respectively.
The corrosion rates indicated very little or
negligible corrosion due to either hydrazine or
Carbohydrazide. However hydrazine showed much
lower rates compared to Carbohydrazide.
41
41
Acknowledgment
The authors gratefully acknowledge:
The cooperation of Jubail Plant personnel.
42
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