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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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) 156

. Typically, the dissolution of the scale deposits (metal sulfides, sulfates, and phosphates) takes place as shown by the following equations: Fe2O3 + 6 HCl CaCO3 + 2 HCl 2 Fe(III)Cl3 + 3H2O 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 Fe(III) Fe (II) Ni (II) Mn (II) Ca (II) Mg (II) Log K - EDTA 25.1 14.3 18.6 14.0 10.7 8.7 Reference 4 5 5 5 5 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.0 C To 104 C To 104 C To 176 C To 176 C % INHIBITOR REMARKS

Rodine 213/214 Rodine 426/428 Rodine 2000

Hydrochloric (Muriatic) Hydrochloric(Muriatic) Tetra-Ammoniated EDTA

0.1 to 0.3 0.1 to 0.3 0.1 to .03

Rodine 2002

Tetra-Ammoniated EDTA, Citric Acid

0.1 to 0.4

Premium Protection Inhibitor Low Toxicity Version of R213/214 Low Toxicity for chelant Cleanings @pH 7.0 or higher Low Toxicity 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 Rodine 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, Rodine 426, has demonstrated equal performance in both laboratory testing (see Graph B) and in commercial use. Rodine 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 70 60 50 40 30 20 10 0 0.25 0.5 0.75 1 1.5 2 2.5 3 4 Inhibitor Concentration (ml/liter)

Corrosion Rate (g/sqM/day)

66C (150F) 79C (175F) 93C (200F)

Graph A. Rodine213 10% Hydrochloric Acid-1010 HRS

130 120 110 100 90 80 70 60 50 40 30 20 10 0 0.25 0.5 0.75 1 1.5 2 2.5 3 4

Corrosion Rate (g/sqM/day)

66C (150F) 82C (180F) 93C (200F)

Inhibitor Concentration (ml/liter) Graph B. Rodine426-10% HCl 1008 CRS

The Mannich polymers have been employed as key ingredients in the development of new inhibitors for Tetra-Ammoniated EDTA (Rodine 2000). This inhibitor has demonstrated excellent corrosion resistance over a wide pH range, inhibitor concentration and alloy composition (see Table V).
Table V. Rodine2000- pH=10, 24 hr test, Ammoniated EDTA, Temp.=148.9 C
Rodine2000 0.1% 0.1% 0.1% 0.1% 0.1% Cleaning Solvent 4% Am. EDTA 4% Am. EDTA 4% Am. EDTA 4% Am. EDTA 4% Am. EDTA Alloy CRS 1020 UNS-N04400 SS-304 SS-316 Boiler Tubes Corrosion Lbs/ft2/day 0.002 0.000 0.000 0.000 0.008
0

Further work has resulted in a more versatile inhibitor (Rodine 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).
Table VI. Rodine 2002-Ammoniated EDTA & Citric Acid-24 Hr/148.9 C
Rodine 2002 0.1% Cleaning Solvent 4%Ammon. Citric Acid pH 6.0 Alloy CRS 1020 Corrosion Lbs/Ft2/day 0.003
0

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0.1% 0.05% 0.025% 0.1% 0.1% 0.1% 0.1%

4%Ammon. Citric Acid 4%Ammon. Citric Acid 4%Ammon. Citric Acid 4%Ammon. Citric Acid 4%Ammon. Citric Acid 4%Ammon. EDTA 4%Ammon. EDTA

6.0 6.0 6.0 5.0 4.0 10.0 10.0

UNS-N04400 CRS 1020 CRS 1020 CRS 1020 CRS 1020 CRS 1020 UNS-NO4400

0.000 0.005 0.022 0.008 0.037 0.003 0.000

Table VII. Rodine 2002-Varied Acid Cleaning Solvents-6 Hr Test Duration Rodine 2002 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.2% 0.2% 0.1% Cleaning Acid 10% Sulfamic 10% Sulfamic 10% Sulfamic 10% Formic 10% Acetic EDTA pH=5 10% Oxalic 10% Sodium Bisulfate 10% Tartaric Temp. 0C 65.6 C 65.6 C 65.6 C 82.2 C 82.2 C 65.6 C 82.2 C 82.2 C 82.2 C Alloy CRS 1020 SS-304 SS-316 CRS 1020 CRS 1020 COPPER CRS 1020 CRS 1020 CRS 1020 Corrosion Lbs/Ft2/day 0.005 0.000 0.002 0.005 0.044 0.002 0.005 0.004 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 Hydrochloric, Sulfamic To 25-50lbs per Water well grade Rodine 100* 65.6 C 1,000gal. Or 1 to inhibitor-All AQUA HIB 4 gal. Per 100 ingredients Generally lbs. Regarded As Safe

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Rodine 102 Rodine103*

Sodium Bisulfate, Sulfamic Acetic, Citric, Formic, Hydrochloric, Oxalic,Phosphoric,Sodium Bisulfate,Sulfamic, Sulfuric, Tartaric

To 82.2 C 38 C to 65.6 C

1.5 to 5 % 2 to 4 %

All ingredients Generally Regarded As Safe Low Toxicity All ingredients Generally Regarded As Safe

EPA approved for use in acidizing potable water wells.

Two inhibitors, Rodine 100 Aqua-Hib and Rodine 103 are EPA approved for use in acidizing potable water wells. As can be seen from Table IX comparing the inhibition of Rodine103 to that attainable with Rodine213, 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.
Table IX. Potable Water Well Cleaning Test- 15%V/V HCl 26.6 C 6 hrs PRODUCT Rodine103 Rodine103 Rodine103 Rodine213
.
0

INHIBITOR %V/V 0.1 1.0 5.0 0.1

ALLOY CRS 1010 CRS 1010 CRS 1010 CRS 1010

%PROTECTION 87 93 96 99.8

As shown in Table VIII , Rodine103 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).
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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.

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