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Experimental Study on Boiler Scales Cleaning Using Hydrochloric and Citric

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 Eng. & Tech. Journal, Vol. 30 , No.3 , 2012

Experimental Study on Boiler Scales Cleaning Using

Hydrochloric and Citric Acids

Dina Raheem
Engineering College, University of Al Mustansiriya /Baghdad
Email:[email protected] lazer
Janet Lazer
Al Doura power station/Baghdad

Received on: 26 /5 / 2011 & Accepted on: 5 /1/ 2012

ABSTRACT
The effect of hydrochloric acid and citric acid was studied experimentally for
boiler chemical cleaning to determine the dissolved scale by using carbon steel
samples of water-side boiler tubes sections ,different concentrations of hydrochloric
acid HCL and citric acid were used
(2%,3%,4% and 5%) to calculate the weight loss of samples then determined the
dissolved scale in gm/m2. The more efficient acid for the chemical cleaning, was
found to be HCL acid at 5% concentration by using 0.3% rodin inhibitor at temp.
60 and time 30 minute to obtain 248 gm/m2 of dissolved scale while the citric
acid at 5% concentration by using 0.3% hexamine inhibitor and temp.70 and
2
time 240 minute to obtain 168 gm/m of scale dissolved.

Keywords: boiler chemical cleaning, Hydrochloric acid, Citric acid

‫ﯾﺪراﺳﺔ ﻣﺨﺘﺒﺮﯾﺔ ﻋﻠﻰ ﺗﻨﻈﯿﻒ ﺗﺮﺳﺒﺎت اﻟﻤﺮﺟﻞ ﺑﺎﺳﺘﻌﻤﺎل ﺣﻮاﻣﺾ اﻟﺴﺘﺮﯾﻚ‬

‫واﻟﮭﯿﺪروﻛﻠﻮرﯾﻚ‬
‫اﻟﺨﻼﺻﺔ‬
‫ﺗﻤ ﺖ دراﺳ ﺔ ﺗ ﺄﺛﯿﺮ ﺣ ﺎﻣﺾ اﻟﮭﯿ ﺪروﻛﻠﻮرﯾﻚ وﺣ ﺎﻣﺾ أﻟﺴ ﺘﺮﯾﻚ ﺑﺎﺳ ﺘﺨﺪام اﻟﺘﺠ ﺎرب ﻹﺟ ﺮاء ﻋﻤﻠﯿ ﺔ‬
‫اﻟﻐﺴﻞ اﻟﻜﯿﻤﺎوي ﻟﻠﻤﺮاﺟﻞ وﺗﺤﺪﯾﺪ ﻧﺴﺒﺔ اﻟﺘﻜﻠﺴﺎت اﻟﻤﺬاﺑﺔ ﺑﺎﺳﺘﻌﻤﺎل ﻣﻘ ﺎﻃﻊ ﻣ ﻦ ﻧﻤ ﺎذج اﻧﺎﺑﯿ ﺐ اﻟﻤﺮﺟ ﻞ‬
‫ اﺳ ﺘﻌﻤﻠﺖ ﺗﺮاﻛﯿ ﺰ ﻣﺨﺘﻠﻔ ﺔ ﻣ ﻦ ﺣ ﺎﻣﺾ‬, ‫اﻟﻤﺼ ﻨﻮﻋﺔ ﻣ ﻦ ﻛﺮﺑ ﻮن ﺳ ﺘﯿﻞ ﻣ ﻦ ﻧ ﻮع اﻟﺠﺎﻧ ﺐ اﻟﻤ ﺎﺋﻲ‬
‫( ﻟﺤﺴ ﺎب ﻓﻘ ﺪان اﻟ ﻮزن ﻟﻠﻨﻤ ﺎذج‬%5 ‫ و‬%4 , %3, %2)‫اﻟﮭﯿ ﺪروﻛﻠﻮرﯾﻚ وﺣ ﺎﻣﺾ أﻟﺴ ﺘﺮﯾﻚ ھ ﻲ‬
‫ أﻛﺜﺮ ﺣ ﺎﻣﺾ ﻛﻔ ﺎءة ﻟﻌﻤﻠﯿ ﺔ اﻟﻐﺴ ﻞ اﻟﻜﯿﻤﯿ ﺎوي‬. ‫ﻣﺘﺮﻣﺮﺑﻊ‬/ ‫وﺗﺤﺪﯾﺪ ﻧﺴﺒﺔ اﻟﺘﻜﻠﺴﺎت اﻟﻤﺬاﺑﺔ ﺑﻮﺣﺪة اﻟﻐﺮام‬
‫ رودﯾﻦ ﻛﻤﺎﻧﻊ ﺗﺄﻛ ﻞ ودرﺟ ﺔ‬0.3 %‫ ﺑﺎﺳﺘﻌﻤﺎل‬5%‫ﺗﻢ ﺗﺤﺪﯾﺪه ﻟﯿﻜﻮن ﺣﺎﻣﺾ اﻟﮭﯿﺪروﻛﻠﻮرﯾﻚ ﻋﻨﺪﺗﺮﻛﯿﺰ‬
‫ﻣﺘ ﺮ ﻣﺮﺑ ﻊ ﻣ ﻦ اﻟﺘﻜﻠﺴ ﺎت‬/ ‫ ﻏ ﺮام‬248 ‫ دﻗﯿﻘ ﺔ ﻟﻜ ﻲ ﻧﺤﺼ ﻞ ﻋﻠ ﻰ‬30 ‫ درﺟ ﺔ ﻣﺌﻮﯾ ﺔ ووﻗ ﺖ‬60 ‫ﺣ ﺮارة‬
%5‫ﻣﺘﺮﻣﺮﺑﻊ ﻣﻦ اﻟﺘﻜﻠﺴﺎت اﻟﻤﺬاﺑﺔ ﻟﺤﺎﻣﺾ اﻟﺴﺘﺮﯾﻚ ﻋﻨﺪ ﺗﺮﻛﯿ ﺰ‬/‫ ﻏﺮام‬168 ‫اﻟﻤﺬاﺑﺔ ﺑﯿﻨﻤﺎ ﻧﺤﺼﻞ ﻋﻠﻰ‬
.‫ دﻗﯿﻘﺔ‬240 ‫ درﺟﺔ ﻣﺌﻮﯾﺔ ووﻗﺖ‬70 ‫ ھﯿﻜﺴﺎﻣﯿﻦ ﻛﻤﺎﻧﻊ ﺗﺄﻛﻞ ودرﺟﺔ ﺣﺮارة‬0.3% ‫ﺑﺎﺳﺘﻌﻤﺎل‬

INTRODUCTION

C
hemical cleaning is a process which primarily uses chemical solutions to
remove fouling from inside plant and equipment. Metal equipment must be
cleaned from time to time to prevent damage and maintain efficiency of
operation. The chemical cleaning of metals has a number of advantages over
mechanical cleaning methods. The greatest of these are that the metal equipment to
be cleaned doesn't need to be dismantled and reassembled, and the cleaning doesn't
damage the equipment, leaving areas that are more affect to corrosion than before,[1].
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 Eng. & Tech. Journal, Vol. 30, No.3, 2012 Experimental Study on Boiler Scales Cleaning
Using Hydrochloric and Citric Acids

Acid cleaning is essential after installation of a thermal power unit because the
pipelines and other auxiliary equipment are contaminated by scale or corrosion,
sediments, weld flash, different cutting, oil ad greases, atmospheric dust particles like
mud , Sio2 and clay. if much impurities are not removed from boiler these may cause
further scaling or corrosion .
[2]
Poulson has studied the possibilities of stress corrosion cracking during boiler
[3]
acid cleaning operation. French has used hydrofluoric acid for boiler cleaning and
shenker has described an economical method of boiler cleaning. Phelan, Novitsky
,Yongshu ,flemming, Japan described different techniques for boiler chemical
cleaning and corrosion protection.
In boilers of water-side the build-up of scale is a progressive, inevitable process.
Even with stringent control of feed water and condensate chemistry, scale and
deposition will occur. The main problems caused by boiler scales are:
1.Increase in tube wall temperature, hence, boiler tube ruptures.
2.Decrease in overall boiler efficiency, hence, increase in energy cost and loss of
reliability.
The increase in tube wall temperature is a result of the low thermal conductivity of
scales as compared to metal. The reduction in heat-transfer can lead to the design
temperature of the tube wall being exceeded, which in turn may lead to failure of the
tube by creep rupture. Overall efficiency can be defined as the ratio of steam output
to the fuel consumption ratio. Again, since scaling impedes heat transfer, more fuel is
required to produce a given amount of steam, thus reducing overall efficiency and
loss of energy. [4,5]
If fouling is allowed to continue, in some cases catastrophic failure of plant can
occur resulting in complete and extended loss of use. This is the main concern with
magnetite (Fe3O4) foulings in steam generator plants such as those in power station
boiliers. As the magnetite scale grows with service time it increases the thermal
resistance of the generator tube to the imposed heat flux. Once the magnetite gets
thicker than 50 m this can result in the metal temperature of the generator tube
exceeding the yield temperature for the given stress conditions.
In Figure(1) show Tube failure results and hundreds of thousands of dollars per day
of power generation capacity is lost in downtime.

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 Eng. & Tech. Journal, Vol. 30 , No.3 , 2012

The primary constituent of boiler scales is magnetite (Fe3O4), which is formed as a

result of the reaction of metallic iron with high-temperature steam. Copper is present
due to corrosion of the copper alloy, aluminum bronze feed water condensers and pre
heaters, often because of oxygen ingress into these systems. Copper is transported
through the steam cycle where it forms on the boiler internals. Table (1) shows the
compounds generally found and transported through the steam cycle and deposited on
boiler internals either from contaminants contained in the boiler feed water system or
from use of outdated phosphate-based water treatment chemicals. In addition to these
crystalline inorganic compounds, there may be organic residuals present in the
scale.[4]
Table (1) The Compounds Found in Boiler Scales
Compound Formula
Anhydrite CaSO4
Aragonite CaCO3
Brucite Mg(OH)2

Copper Cu

Calcite CaCO3

Hematite Fe2O3
Hydroxyapetite Ca10(OH)2(PO4)6

Magnetite Fe3O4

Quartz SiO2
Thenardite Na2SO4

Wollastonite CaSiO3

Selection of the acid is primarily dependent on scale (deposit) type, although the
physical turbulence available, solution temperature, and the metallurgy of the
equipment are also of importance. Generally there are two types of acids : minerals
and organic . Mineral acids are cheaper and, because of their high ionization, can be
used at room temperature, such as H2SO4 Sulphuric , HNO3 nitric, HCl
hydrochloric, H3PO4 phosphoric and NH2SO3H sulfamic, whereas organic acids,
being much less strongly ionized, are used at temperatures around 90oC to affect their
chelating (complexforming) properties on the scale,such as HCOOH formic, Oxalic,
EDTA and Citric .Organic acids are only used when there is a probability of
corrosion damage by a mineral acid.
Most internal deposits can be removed with mineral acid and organic acid .The
most widly used solvent is a 5% hydrochloric acid solution with inhibitor and
complexes. Phosphoric,sulfuric and sulfamic acid are also used in boilers that operate
at 2000psig. Inhibited ammonium citrate and a combination of hydroxyacetic and

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 Eng. & Tech. Journal, Vol. 30, No.3, 2012 Experimental Study on Boiler Scales Cleaning
Using Hydrochloric and Citric Acids

formic acids are commonly used organic .Salts of EDTA (ethylene-diamin-tetraacetic

acid) have been used for both off-line and on-line cleaning. [1,6]
The need to chemically clean an operating boiler is usually determined from an
inspection of a particular unit performed during planned inspections. Other factors
influencing the decision of whether or not to chemically clean include:
1. overall efficiency
2. hot spots - as evidenced by infrared inspection
3. tube failure during normal operation
Tube samples should be removed from locations where heavy scaling is suspected.
The tube sample should be at least three feet long so the method of removal (cut-off
wheels and cutting torches) does not contaminate the scale at the center of the sample
with slag or filings.
The scale is then analyzed using several different techniques in order to determine
its composition. The scale density is determined gravimetrically after dissolution of
scale in inhibited HCL . Loss of weight on firing in a furnace will measure the
percentage of hydrocarbons present, which then determines the need for alkaline
degreasing. The need to clean is based on the scale density. Table(2) shows the range
of scale density encountered, along with the appropriate action required.

Table(2): Scale density ranges and required action

Scale density g/ft2 or mg/cm2 Recommended action

< 23 (25) No action required

23 – 70 (25-75) Chemically clean within one year
70 – 93 (75 -100) Chemically clean with three months
> 93 (100) Chemically clean before further operation

EXPERIMENTAL PROCEDURE
A laboratory test used in this investigation in Al-Dhoura power station ,
Different carbon steel specimens of boiler water side tubes (pressure 80 bar and
Temp.350 ) were obtained and coated with scale of hematite ,magnetite and copper
type. as shown in fig.(2) and fig.(3).
Acid solution preparation:
1. 2% concentration of Hydrochloric acid HCL with 0.3% of Rodin as corrosion
inhibitor, using
for 2% HCl

Then calculated 3%, 4%,5% and obtained ( 24.3, 32.4 and 40.5ml)
respectively.

-0.3 gm for 100 ml then → 0.9 for 300ml for rodin.

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 Eng. & Tech. Journal, Vol. 30, No.3, 2012 Experimental Study on Boiler Scales Cleaning
Using Hydrochloric and Citric Acids

2. 2% concentration of citric acid with

0.3% of hexamine were prepared as for HCL acid.
Cleaning by HCL
Weighing the specimen (1) and record w1 ,then immersed in 2% HCL with 0.3%
Rodin inhibitor in water bath at temp. 60 and for 60 min. ,then after 60 min. the
specimen was removed and rinsed with distilled water then dried in oven and cooled
in discator then record the w2 ,repeat the procedure by using 3%,4% and 5% then
calculated the dissolved scale in (gm/m2) by using the following equation:

…(1)

As shown in table (4).

CLEANING BY CITRIC ACID:

Weighing the specimen (5) and record w1 ,then immersed in 2% citric acid with
0.3% hexamine in water bath at temp. 60 and for 60 min. ,then after 60 min. the
specimen was removed and rinsed with distilled water then dried in oven and cooled
in discator then record the w2 ,repeat the procedure by using 3%,4% and 5% then
calculate the dissolved scale (gm/m2) as shown in table (5) .
Repeat the procedure of citric acid and take specimen(9) then change the immersion
time from (90,120,180 and 240 min.) at temp. 70 then calculate the dissolved scale
as shown in table(5) .

Figure (2) Sample before acid cleaning

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 Eng. & Tech. Journal, Vol. 30, No.3, 2012 Experimental Study on Boiler Scales Cleaning
Using Hydrochloric and Citric Acids

Figure (3) Samples with boiler scales

RESULTS AND DISCUSSION

HCL cleaning: HCL is the most commonly used for cleaning tubes made of carbon
steel ,The samples of water-side boiler tubes coated with hematite and magnetite and
when immersed in HCL acid solutions, the reactions that occur through the chemical
cleaning with HCL are shown in the following equations:[1]
(a) Fe3O4 + 8HCl → FeCl2 + FeCl3 + 4H2O
(b) Fe3+ + Cu° → Fe2+ + Cu+
(c) Fe3+ + Cu+ → Fe2+ + Cu2+
(d) 2Fe3+ + Fe° → 3Fe2+ (corrosion)
(e) Cu2+ + Feo → Fe2+ + Cu° (corrosion)
(f) 2H+ + Fe° → Fe2+ + H2(g) (corrosion)
In (a) the magnetite is two-thirds Fe3+ (ferric) and one-third Fe2+ (ferrous).
However, as the scale is removed to reveal bare metal, the metal rapidly reduces the
ferric ion while further corroding itself (d). Any copper present will be oxidized by
the Fe3+ acting as an oxidant (b,c). Cupric ions are also unstable with respect to bare
steel, and so they replate as metallic copper before the acid solution can be drained
(e).
The classic acid corrosion mechanism (f) can occur when the base metal
underneath the scale is uncovered. This reaction is easily minimized (up to a 99% rate
reduction) by addition of a corrosion inhibitor blend. These inhibitors (often cationic)

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 Eng. & Tech. Journal, Vol. 30, No.3, 2012 Experimental Study on Boiler Scales Cleaning
Using Hydrochloric and Citric Acids

tend to adsorb to the electronegative metal surface to form a thin film that inhibits
attack.
Ferric and cupric ions from the dissolved scale attack the bared steel surface by
pitting corrosion (d,e). This can sometimes result in localized damage and greater
weight losses than the inhibited acid corrosion. To overcome this, reducing agents
can be added to the cleaning solution to reduce the ferric ions before they attack the
base metal.
According to table(3) the weight loss of samples effected by increasing HCL
concentration with inhibitor rodin (i.e.) the dissolved scale increased from (117.4 –
248) gm/m2 at 2% - 5% concentration of HCL and a linear relation shown in fig.(6).
The scale completely remove after acid immersion as shown in fig. (4) .The result
show the 5% of HCL is more efficient to remove the scales at temp. 60 and 30
2
minute and the value 248 gm/m recommended to clean the boiler within one year
according to table(3) .
Citric acid cleaning: According to table(4) the weight loss of samples effected by
increasing the concentration of citric acid with 0.3% hexamine as a corrosion
inhibitor, the dissolved scale increased from 30.8 to 58.82 gm/m2 at 60 minute and at
temp. 50 . This result show that the dissolved scales are very little at this time (60)
min. as shown in fig.(5 )
While table (5) and fig(8) show the dissolved scale increased from 85. 6 to 168.06
gm/m2 as time from 90min. to 240min respectively at 5% concentration of citric acid
0.35 hexamine and temp.70 .Because of citric acid as organic acids and less
strongly ionized and used at temp. around 90 to effect their chelating (complex
forming ) properties on the scale and used more time (i.e.240 min.) so citric acid is
less efficient for chemical cleaning.
Another results that obtained, the effect of 5% HCL concentration on weight loss of
the sample to dissolve 4.7gm of scale at 60 minuet.[7]

CONCLUSIONS
The over all experimental results show that the HCL acid work more efficiently
than citric acid because the one is cheap and easily to ionized . Since the solubility of
the scale is increasing with concentration ,It is reported that the optimum
concentration is 5% for scale removal to be 248 gm/m2 at time 30 minuet , while the
citric acid need more time for scale removal to be 58.82gm/m2 at time 60
minuet.

Table (3) Dissolved scale for different conc. of HCL with 0.3%
Rodine at temp. 60 and time 30 min.
Sample Conc.% W1 gm W2 gm Area/cm2 Dissolved
scale(gm/m2)
1 2 115.5 115.2 0.3 25.55 117.7
2 3 125.8 125.3 0.5 27.69 180.5
3 4 130.7 130.08 0.62 29.6 209.4
4 5 127.8 127 0.8 32.2 248
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 Eng. & Tech. Journal, Vol. 30, No.3, 2012 Experimental Study on Boiler Scales Cleaning
Using Hydrochloric and Citric Acids

Table (4) Dissolved scale for different conc. of Citric acid

with 0.3% hexamine at temp. 50 and time 60 min.
Sampl Conc.% W1 gm W2 gm Area/cm2 Dissolved
e scale(gm/
m2)
5 2 120.28 120.2 0.08 25.9 30.8
6 3 118.9 118.8 0.1 26.64 37.5
7 4 129 128.85 0.15 30.34 49.4
8 5 134.2 134 0.2 34.0 58.82
Table (5) Dissolved scale for 5%conc. of Citric acid
with 0.3% rodine at temp. 70 and different times.
Sample Time/min. W1 gm W2 gm Area/cm2 Dissolved
scale(gm/m2)
9 90 130.5 130.25 0.25 29.2 85.6
10 120 125.6 125.3 0.3 27.2 110.2
11 180 126.8 126.43 0.37 27.4 135
12 240 117.6 117.2 0.4 23.8 168.06

Figure (4) The samples after the cleaning by HCL

acid

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 Eng. & Tech. Journal, Vol. 30, No.3, 2012 Experimental Study on Boiler Scales Cleaning
Using Hydrochloric and Citric Acids

Figure (5) The samples after cleaning by citric

acid

300
280
260
Dissolved Scale g/m2

240
220
200
180
160
140
120
100
2% 3% 4% 5%
Concentration of HCL +0.3% Rodin (percent Unit)
Fig. (6 ) Effect of HCL concentrations on the scales
in presence of 0.3% rodin

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 Eng. & Tech. Journal, Vol. 30, No.3, 2012 Experimental Study on Boiler Scales Cleaning
Using Hydrochloric and Citric Acids

65
60
55
Dissolved Scale g/m 2

50
45
40
35
30
25
2% 3% 4% 5%

Concentration of citric acid +0.3% hexamin (percent Unit)

Figure ( 7) Effect of Citric acid concentrations on

the scales in presence of 0.3%hexamin

185
175
165
155
g/m2

145
Dissolved Scale

135
125
115
105
95
85
75
65
90 120 180 240
Time (minuts)
Fig. ( 8 ) The relation between dissolved scale and
Time

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 Eng. & Tech. Journal, Vol. 30, No.3, 2012 Experimental Study on Boiler Scales Cleaning
Using Hydrochloric and Citric Acids

REFERENCES
[1] Ken Dibble and Philip Battaglia , "Chemical Cleaning of metals",
International water conference, no.43,p.30-37,July,2001.
[2] M Azad Sohail and AIsmail Mustafa "Acid cleaning of impurities in
natural circulation high pressure drum boiler" Malaysian journal of
chemistry,vol.8,no.1,p. 80-86, 2006.
[3] Jeffery, F. and Basset, J. "Chemistry control of thermal power plants
training materials", Chemical engineering ,vol.6,no.32,p.34-40,1987.
[4] E. Jaffer and D. Majnouni ," Chemical cleaning of an industrial
boiler – an overview" International Water conference, no.64,p.19-23,
October, 2003.
[5] Mel J. Esmacher and George H. Bodman, "Use of Comprehensive
Deposit Analysis Techniques to Evaluate Boiler Deposits Prior to Chemical
Cleaning," International Water Conference, no.33, p.45-51, June,2000.
[6] J.O.Ribnson and B.C.Moore, "Industrial water conditioning",p.96-
104, New York,1991.
[7] M.Suleman Tahir and Mahmud Saleem,"Experimental study of chemical
de scaling –I:Effect of acid concentration", Engineering and Technology
journal ,vol. 5,no. 3, p.1-9,2008.

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