THE USE OF INHIBITORS FOR CHEMICAL CLEANING OF INDUSTRIAL EQUIPMENT

Andreas Lindert Ph. D.

Henkel Surface Technologies
32100 Stephenson Hwy
Madison Hts, Michigan 48071

ABSTRACT

Corrosion resistant alloys are frequently specified for the construction of industrial process equipment
such as heat exchangers, digesters in paper mills, reactors, and condensing units as well as in many
critical applications in electrical power generating plants. Of equal importance to the longevity of this
costly equipment is the maintenance and routine cleaning of the equipment for the removal of scale
and deposits. Inorganic acids, organic acids and chelating solvents are typically employed for this
purpose. The addition of corrosion inhibitors to reduce attack on the base metal is vital in a cleaning
operation and their operation and use will be discussed below.

KEYWORDS

corrosion, inhibitor, acid, EDTA, cleaning

INTRODUCTION

In the construction of industrial plants and process equipment great care is given in the proper design
and construction of an industrial unit in order to minimize corrosion of critical process equipment and
to maximize the operational life and maintain efficient production to meet the desired efficiency and
throughput of the plant. Corrosion resistant alloys and stainless steels are often specified particularly in
critical plant processes or where equipment downtime is expensive or cannot be easily accommodated
by the industrial process.

Equipment failure due to corrosion can be quite troubling to the Design Engineer particularly when a
considerable capital investment has been made in costly corrosion resistant alloys to reduce the
likelihood of its occurrence. The equipment failure often is not due to faulty design or materials of
construction but to improper operation and maintenance of the equipment. Scheduled cleaning of
equipment can greatly increase the efficiency and service life of a plant. The importance of scheduled
cleaning becomes evident in power generating plants, paper mills and refineries where industrial units,
boilers, condensers and heat exchangers should be routinely cleaned in order to maintain efficiencies
of the designed equipment. The removal of surface deposits is important for reducing the corrosion of
the equipment. Of equal importance is to maintain the heat transfer of the equipment. Table I, lists the
Thermal Conductivity of commercial metals as well as some scales that may be encountered in a
typical plant operation.

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 1
Table I. Thermal Conductivity of Metals and Refractory Materials
Material Temp (oK) W/m2 K/m
Commercial pure iron 273 76
Carbon Steel (AISI 1020) 273 65
Nickel (80%)-Cr (20%) 273 12
Magnetite (Fe3O4) 304 7
Dry Brick 273 0.04
Dry Silica (Sand) 273 0.33
Copper, electrolytic 273 390

Refractory deposits not only restrict and reduce the flow of process fluids but silicate and corrosion
products such as Magnetite can reduce heat transfer by two orders of magnitude or more; resulting in
hot spots which contribute to increased corrosion and early equipment failure.

Therefore, in order to maximize flow rates, minimize corrosion and maintain the desired heat transfer
capabilities of industrial equipment, it is necessary to periodically clean the heat transfer surfaces to
remove scale formed during normal operation. Industrial equipment will develop scales from the
oxidation of metal surfaces operating at high temperatures resulting in the formation of iron oxides as
well as oxides of other alloying metals. Deposits can also come from process water, resulting in
calcium, magnesium and silicate deposits, while metallic copper deposition can occur from the
migration of copper used in the manufacture of valves and other auxiliary components incorporated
into boiler equipment. These unwanted deposits will result in decreased efficiency of the equipment
but more troublesome is the further promotion of corrosion resulting from the generation of cathodic
and anodic sites on the metal surfaces.

In order to remove these unwanted deposits, a large variety of cleaning solutions have been developed.

CHEMICAL CLEANING SOLVENTS

Many different and in some cases, proprietary cleaning solutions have been developed and are in
commercial use today.2,3 The first cleaning systems were based on mineral acids and have proved
very effective in the efficient removal of scales and deposits on industrial equipment. Hydrochloric
acid has been shown to be particularly efficient in the removal of scales, iron oxide and copper oxide
deposits, and is still used to a large extent in the cleaning of industrial process equipment and power
generating units. Since most metal ions form soluble chloride salts, (See Table II), hydrochloric will
readily dissolve most deposits of iron oxides.
Table II. Solubility of Common Metal Chlorides Found in Scales
Metal Chloride Solubility(100 Parts)
Calcium Chloride 59.5 ( 00C)
Magnesium Chloride-6H2O 281 ( 00C)
Ferric Chloride-6H2O 246 ( 00C)
Ferrous Chloride-4H2O 160 (10oC)
Copper Chloride-2 H2O 110.4 ( 00C)
Nickel Chloride 180 (Cold Water)

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. Typically, the dissolution of the scale deposits (metal sulfides, sulfates, and phosphates) takes place
as shown by the following equations:
Fe2O3 + 6 HCl ® 2 Fe(III)Cl3 + 3H2O
CaCO3 + 2 HCl ® CaCl2 + H2O + CO2

In recent years, organic solvents and mixtures of various organic solvents and chelating solutions have
been used to a much greater extent. Although mineral acids are very efficient at removal and
solubilization of scales, it is often desirable to use less aggressive cleaning solvents or to conduct the
cleaning operation under alkaline solution conditions. Ammoniated solutions Citric acid and EDTA
are frequently used for this purpose, since the pH of these cleaning solvents can be adjusted to a less
aggressive range. Since these solvents dissolve the metal scales by the formation of multi-dentate
bonds, and do not exclusively rely of acidic attack on the scale surface for solubilization, this method
of chemical cleaning has been shown to be less aggressive and very favorable in many cases.

A multi-dentate chelate is shown below for ferrous chelate-EDTA system.

Fe2O3 +2( NH4 )4 EDTA ® 2 Fe[EDTA(NH4)2 +4NH3 +xH2O

Strong and chemically stable complexes are generated which dissolve and keep the metal ions, present
in scales and deposit, in solution as can be demonstrated by the Stability Constants in Table III below.
Table III. Stability Constants (log K) for select metal ions
Metal Ion Log K - EDTA Reference
Fe(III) 25.1 4
Fe (II) 14.3 5
Ni (II) 18.6 5
Mn (II) 14.0 5
Ca (II) 10.7 5
Mg (II) 8.7 6

Citric acid and ammoniated citrate are also commonly employed either alone or in combination with
other organic acids for the cleaning of industrial equipment. Although the Stability Constants for
Ferrous and Ferric ions is considerably lower (Log K=4.4 for Fe(II) and 11.5 for Fe(III)) considerable
success has been achieved in the use of citrate cleaning solutions.

CHEMICAL CLEANING INHIBITORS

Chemical cleaning solvents are corrosive to the base metal and can result in corrosion and pitting of
equipment unless inhibitors are employed to prevent this unwanted metal attack. Inhibitors are usually
used at very low concentrations from 1000 to 3000 ppm and can give 99.8%+ inhibition on a metal
surface even in highly corrosive hydrochloric acid solutions. Specific corrosion inhibitors have been
developed to aid the removal of scale and deposits from industrial equipment while preventing or
minimizing attack on the base metal. The corrosion inhibitors listed in Table IV are based on a
proprietary polymeric inhibitor synthesized by the Mannich reaction of amines (based on natural
products), aldehydes and ketones and also contain additional synergistic ingredients for increased
inhibition and stability in the chemical cleaning solutions.

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 Table IV. Premium Cleaning Inhibitors based on Polymeric Mannich Derivatives
PRODUCT ACID TEMP.- % INHIBITOR REMARKS
0
C

Rodineâ Hydrochloric (Muriatic) To 0.1 to 0.3 Premium

213/214 104 C Protection
Inhibitor
Rodineâ Hydrochloric(Muriatic) To 0.1 to 0.3 Low Toxicity
426/428 104 C Version of R-
213/214
Rodineâ 2000 Tetra-Ammoniated EDTA To 0.1 to .03 Low Toxicity
176 C for chelant
Cleanings @pH
7.0 or higher
Rodineâ 2002 Tetra-Ammoniated EDTA, Citric To 0.1 to 0.4 Low Toxicity
Acid 176 C Use at pH 3.5 or
higher

Inhibitors based on these polymeric bases are known to operate by the formation of chelating
structures on the metal surfaces and have proven to be one of the most effective inhibitors for chemical
cleaning operations. The polymeric component employed in the above inhibitors has been optimized
through the synthesis of the Mannich adducts, proper hydrophobic/hydrophilic balance, chelating
functionality, metal reactivity, molecular weight control, resulting in a system having outstanding
corrosion resistance in both strongly acidic cleaning solvents as well as alkaline EDTA and Citric acid
systems.7

Graph A demonstrates the excellent corrosion resistance attainable with the use of very low levels of
Rodineâ 213 in 10% Hydrochloric Acid. This product has been used for Industrial Cleaning for many
years and has been shown to give outstanding corrosion resistance. Recently, a low toxicity
formulation also based on the polymeric Mannich inhibitor, has been developed. This product,
Rodineâ 426, has demonstrated equal performance in both laboratory testing (see Graph B) and in
commercial use. Rodineâ 426 is presently being used for an increasing number of industrial chemical
cleaning operations due to the lower level of toxicity of this product.

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 80

Corrosion Rate (g/sqM/day)

70
60
50 66C (150F)
40 79C (175F)
30 93C (200F)
20
10
0
0.25 0.5 0.75 1 1.5 2 2.5 3 4
Inhibitor Concentration (ml/liter)

Graph A. Rodineâ213 –10% Hydrochloric Acid-1010 –HRS

130
Corrosion Rate (g/sqM/day)

120
110
100
90
80 66C (150F)
70
60 82C (180F)
50 93C (200F)
40
30
20
10
0
0.25 0.5 0.75 1 1.5 2 2.5 3 4
Inhibitor Concentration (ml/liter)
Graph B. Rodineâ426-10% HCl – 1008 CRS
The Mannich polymers have been employed as key ingredients in the development of new inhibitors
for Tetra-Ammoniated EDTA (Rodineâ 2000). This inhibitor has demonstrated excellent corrosion
resistance over a wide pH range, inhibitor concentration and alloy composition (see Table V).
0
Table V. Rodineâ2000- pH=10, 24 hr test, Ammoniated EDTA, Temp.=148.9 C
Rodineâ2000 Cleaning Solvent Alloy Corrosion
Lbs/ft2/day
0.1% 4% Am. EDTA CRS 1020 0.002
0.1% 4% Am. EDTA UNS-N04400 0.000
0.1% 4% Am. EDTA SS-304 0.000
0.1% 4% Am. EDTA SS-316 0.000
0.1% 4% Am. EDTA Boiler Tubes 0.008

Further work has resulted in a more versatile inhibitor (Rodineâ 2002) which has shown excellent
performance in both acid and alkaline media, and has demonstrated good inhibition with a variety of
chemical cleaning solvents over a range of metal alloys (see Table VI and VII).
0
Table VI. Rodineâ 2002-Ammoniated EDTA & Citric Acid-24 Hr/148.9 C
Rodineâ 2002 Cleaning pH Alloy Corrosion
Solvent Lbs/Ft2/day
0.1% 4%Ammon. 6.0 CRS 1020 0.003
Citric Acid
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 0.1% 4%Ammon. 6.0 UNS-N04400 0.000
Citric Acid
0.05% 4%Ammon. 6.0 CRS 1020 0.005
Citric Acid
0.025% 4%Ammon. 6.0 CRS 1020 0.022
Citric Acid
0.1% 4%Ammon. 5.0 CRS 1020 0.008
Citric Acid
0.1% 4%Ammon. 4.0 CRS 1020 0.037
Citric Acid
0.1% 4%Ammon. 10.0 CRS 1020 0.003
EDTA
0.1% 4%Ammon. 10.0 UNS-NO4400 0.000
EDTA

Table VII. Rodineâ 2002-Varied Acid Cleaning Solvents-6 Hr Test Duration

Rodineâ 2002 Cleaning Acid Temp. 0C Alloy Corrosion
Lbs/Ft2/day
0.1% 10% Sulfamic 65.6 C CRS 1020 0.005
0.1% 10% Sulfamic 65.6 C SS-304 0.000
0.1% 10% Sulfamic 65.6 C SS-316 0.002
0.1% 10% Formic 82.2 C CRS 1020 0.005
0.1% 10% Acetic 82.2 C CRS 1020 0.044

0.1% EDTA 65.6 C COPPER 0.002

pH=5
0.2% 10% Oxalic 82.2 C CRS 1020 0.005
0.2% 10% Sodium 82.2 C CRS 1020 0.004
Bisulfate
0.1% 10% Tartaric 82.2 C CRS 1020 0.002

The development of these outstanding new products further demonstrates the versatility and robustness
of the use of the Mannich derivatives as key components in industrial chemical cleaning operations.

In applications such as sugar mills and in the cleaning of municipal water lines and wells, the toxicity
of the inhibitor is of prime importance due to the possibility of human exposure to trace amounts of
inhibitor if the rinsing step is insufficient for the removal of all cleaning ingredients. For these special
applications, inhibitors have been developed which contain ingredients that are Generally Recognized
as Safe to humans. The components of these products are selected from ingredients which are
recognized as safe or which are approved for human consumption. These inhibitors are listed in Table
VIII.

Table VIII. Low Toxicity Inhibitors-All Ingredients Generally Regarded As Safe

PRODUCT ACID TEMP INHIBITOR REMARKS
0C Concentration
Rodineâ 100* Hydrochloric, Sulfamic To 25-50lbs per Water well grade
AQUA HIB 65.6 C 1,000gal. Or 1 to inhibitor-All
4 gal. Per 100 ingredients Generally
lbs. Regarded As Safe

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 Rodineâ 102 Sodium Bisulfate, Sulfamic To 1.5 to 5 % All ingredients
82.2 C Generally Regarded
As Safe
Rodineâ103* Acetic, Citric, Formic, 38 C 2 to 4 % Low Toxicity All
Hydrochloric, to ingredients Generally
Oxalic,Phosphoric,Sodium Regarded As Safe
Bisulfate,Sulfamic, Sulfuric, 65.6 C
Tartaric
· EPA approved for use in acidizing potable water wells.

Two inhibitors, Rodineâ 100 Aqua-Hib and Rodineâ 103 are EPA approved for use in acidizing
potable water wells. As can be seen from Table IX comparing the inhibition of Rodineâ103 to that
attainable with Rodineâ213, a Premium Inhibitor, very good inhibition can be demonstrated with
these non-toxic systems, but the temperature of operation is lower and increased concentrations of
inhibitor are sometimes required. Nevertheless, excellent inhibition has been demonstrated in many
end use applications requiring non-toxic ingredients for chemical cleaning.

0
Table IX. Potable Water Well Cleaning Test- 15%V/V HCl 26.6 C – 6 hrs
PRODUCT INHIBITOR ALLOY %PROTECTION
%V/V
Rodineâ103 0.1 CRS 1010 87
Rodineâ103 1.0 CRS 1010 93
Rodineâ103 5.0 CRS 1010 96
Rodineâ213 0.1 CRS 1010 99.8
.

As shown in Table VIII , Rodineâ103 is also an effective and useful inhibitor in a variety of acids
which may be employed in the cleaning of equipment where toxicity of all ingredients is important.

SUMMARY

Hydrochloric acid cleaning as well as organic acid solutions such as Ammoniated Citric Acid and
Ammoniated EDTA in Chemical Cleaning of Industrial Equipment were discussed. The importance
of Chemical Cleaning and the use of Corrosion Inhibitors to reduce the attack on the base metal were
reviewed. In addition, recommendations were made for the use of non-toxic Inhibitors in critical
cleaning environments, where inhibitor toxicity is important in the end use of the industrial and
municipal equipment.

REFERENCES

1. 1. D. R. Lide & H. P. R. Frederikse, CRC Handbook of Chemistry and Physics, 75th Edition, CRC
Press, Boca Raton, 1994.

2. A. D. Nesbitt, “A History of Chemical Cleaning in Business,” CORROSION/93, paper No. 362

(Houston TX: NACE International, 1993).

161
3. W. W. Frenier, “20 Years of Advances in Technology for Chemically Cleaning Industrial
Equipment: A Critical Review,” Corrosion/98, paper No. 338(Houston, TX: NACE International,
1998).

4. G. Schwarzenbach, and J. Heiler, Helv. Chim. Acta. 34, 576 (1951).

5. G. Schwarzenbach, et. Al.; Helv. Chim. Acta, 37, 937 (1954).

6. G. Schwarzenbach and H. Ackermann; Helv. Chim. Acta; 30, 1798 (1947).

7. J. P. Bershas, Henkel Surface Technologies, Patent Pending.

162