Coatings to Prevent Fouling in Heat Exchangers, Condensers and Process Equipment : Manoj Saraf, Multicoat Coating Technologies Pvt.Ltd.

, Kolkata, India

Coatings to Prevent Fouling in Heat Exchangers, Condensers and Process Equipment

Paper presented by Mr.Manoj Saraf (Nominated Vice-Chairmen of National Corrosion Council of India), Managing Director of Multicoat Coating Technologies Pvt.Ltd., Kolkata, India, at the 5th International Symposium on Surface Protective Coatings-2007 organised by SSPC India, Dept of Corrosion Science & Engineering, Indian Institute of Technology, Mumbai.
Introduction
Over the last two decades the industry had made huge strides and technical achievement in the design and manufacture of heat exchangers; however the problem of fouling on heat exchanger surfaces still remains one of the major unresolved problems in Thermal Science. Fouling in heat transfer and recovery equipments cost the industry billions every year. Technological progress in prevention, mitigation and removal techniques in industrial fouling was investigated in a study conducted at the Battelle Pacific Northwest Laboratories for the U.S. Department of Energy. Two hundred thirty one (231) patents relevant to fouling were analyzed. The amount of patent activity in fouling reveals the importance of the problem as also the importance and effort that the academia and industry are making to prevent fouling on heat exchanger surfaces. Various steps can be taken to prevent or mitigate the impact of fouling problems during the following stages: 1. 2. 3. 4. Plant Design Plant Construction Plant Operation & Plant Maintenance.

A review of the patent activities indicates that most of the work deals with fouling removal and exchanger cleaning techniques, which is part of the maintenance phase, and the design of process equipment for easier and faster disassembly. What this shows is that many heat exchanger and process equipment manufacturers face problems after they appear rather than proactively preventing problems from occurring, which can be done during the plant design stage by various methods, one amongst them being by specifying use of anti-fouling and fouling release coatings. A study of recent patent data however shows an increasing number of patents for coatings to prevent fouling in process equipments, which is an encouraging trend. Before we discuss about Coatings to prevent fouling in heat exchangers and process equipment, we would briefly discuss about the different types of fouling that are encountered in various processes. Fouling, which is the undesirable deposition of materials on a surfaces, can be described as the major unresolved problem in the process industry. Fouling is a phenomenon that occurs with or without a temperature gradient in most natural, domestic and industrial processes. In these processes, fouling causes an increase in resistance. This can be a resistance to flow in pipes or a resistance to heat transfer in heat exchangers. The increase in resistance causes an increase in

Coatings to Prevent Fouling in Heat Exchangers, Condensers and Process Equipment : Manoj Saraf, Multicoat Coating Technologies Pvt.Ltd., Kolkata, India

cost. This cost increase is reflected in the additional material, which must be used to overcome the efficiency drop; fabrication, which is more complex; installation, which is more difficult; and energy which is lost. The loss of production when the fouling must be cleaned and the cleaning itself are additional cost brought about by fouling. The buildup of sediments and debris on the surface area of a heat exchanger inhibits heat transfer, impede fluid flow, and increase the pressure drop across the heat exchanger. As with many operational concerns, proper planning at the design stage can minimize the effects of fouling down the road. Designers use fouling factors to maximize the lifespan, runtime and efficiency of a heat exchanger by accounting for the amount of fouling an exchanger will sustain over a period of time. This often results in increasing the surface area of a heat exchanger, so that fouling will not have as much of an effect. In many applications, such as in refineries, heat exchangers will have to perform for several years without a cleaning. This means that the heat exchanger must be able to function efficiently for long periods of time. Compensating for fouling by enlarging surface area allows heat exchangers to function with years of fouling Fouling can cause degradation upto 80% or complete failure in thermal and hydraulic performance as well as a pressure drop over the equipment; studies indicate that a fouling layer of 3.2 mm can reduce the heat transfer rate in the heat exchanger by 20% while heavier deposits can create a 90% loss in efficiency.

Types of Fouling
There are several types of fouling, each forming depending on the type of fluid and conditions or according to the mechanism by which it is formed. The following are some of the more common fouling mechanisms;

Crystallization (Precipitation) fouling: This type of fouling involves crystallization of dissolved material in the flowing fluid and occurs whenever the fluid becomes supersaturated with respect to the deposition material. Inorganic salts can show normal solubility (solubility increasing with temperature increase) When precipitation fouling involves the deposition of inorganic salts from water it is called scaling. Scaling mostly involves inverse soluble salts such as calcium carbonate, calcium sulphate, various forms of calcium phosphates, calcium and magnesium silicate, calcium and magnesium hydroxide, sodium sulphate and lithium sulphate. For these inorganic salts scaling occurs on super heated rather that sub-cooled surfaces. Usually such type of fouling is found in process equipment, cooling tower waters, steam generation etc.
Freezing Fouling: This type of fouling is the solidification of a pure liquid in contact with a subcooled heat transfer surfaces, or the deposition of a high-melting point constituent of a liquid in contact with a cold heat transfer surface. Sedimentation Fouling: This type of fouling involves the deposition of dirt, sand, rust, and other small matter; it is also common when fresh water is used. This can be controlled to a degree by the heat exchanger design. [Common Solution: velocity control] Biological Fouling (Bio-Fouling): Biofouling is a general term that refers to the undesirable accumulation of biotic deposits on a surface. This type of fouling occurs from growth of organic materials which attach themselves to the heat exchanger surface and grow. These organisms range from algae and microbial slimes to barnacles and mussels, even a very thin film of such organisms present can result in very high heat transfer resistance. Chemical Reaction Fouling or Coking: This type of fouling occurs when chemical reaction take place at a heat transfer surface and the solid products of the reaction are deposited on the surface, such as deposition of hydrocarbons in high temperature applications.

Coatings to Prevent Fouling in Heat Exchangers, Condensers and Process Equipment : Manoj Saraf, Multicoat Coating Technologies Pvt.Ltd., Kolkata, India

Corrosion Product Fouling: If a stream corrodes the metal of the heat transfer surface, the corrosion products may be essential to protect the remaining metal against further corrosion, in which case any attempt to clean the surface may only result in accelerated corrosion and failure of the exchanger, such corrosion result in the increase in thermal resistance and also an increase of surface roughness. Combined Mechanism: Most of the above fouling processes can occur in combination. A common example is the combination of crystallization and sedimentation fouling in cooling tower water. Fouling affects industry in varying intensity and several methods for mitigation and correction of the problem have been recommended and practiced, many with success. One common prevention technique is estimating a fouling factor at the systems design stage; that is, allowing extra heat transfer surface to compensate for the surface loss caused by fouling. These traditional oversized heat exchangers are often operated at 80% or even below 50% of their designed fluid flow. This excess area can result in problems during start-up and bring about conditions that may encourage fouling beyond what is specified in the design. On the other hand, if a fouling factor is not considered at design stage, loss of heat transfer can exceed 50%, resulting in an energy imbalance within the entire operation. Today a fouling factor is considered necessary but it is not sufficient in preventing fouling. In many cases, even the right design of a heat exchanger will not prevent fouling problems. For example, solid iron sulfides can be produced by direct reaction between dissolved sulfides and metal, but this may not be predictable at the design stage. In this case, adherent sulfide films are produced which moderate but do not prevent continued corrosion. Some portions of the sulfide film are thickened and this becomes similar to other foulants that reduce heat transfer. Today with the increasing environmental awareness and stricter legislation, almost every plant engineer is working toward reducing discharge. Newer production facilities are required to severely limit their disposal volume. One means of complying with such a requirement is to use wastewater in cooling systems. Implementing the technique accomplishes two goals. First, it provides an inexpensive cooling medium and second, it substantially reduces liquid waste volume. However, the side effect of using wastewater is increased fouling due to contaminants in the wastewater. In essence, reducing a disposal problem can lead to an increased fouling problem. Fouling impedes the heat transfer of tube bundles, with capacity being an important parameter. At the design stage of tube bundles, the so-called fouling factor is taken into account. This is the reason that the capacity of the tube bundle has to be increased by up to 20% depending on the water quality. This approach, of course, incurs additional costs. Tube surfaces became incrusted from fouling, while corrosion to the tube material intensifies. Operators must regularly clean the tube bundles so that the unit can continue to function. The length of the cleaning intervals depends on the amount of deposits accumulated in the tube bundle. Cleaning a tube bundle is particularly costly and time consuming if incrustation must be removed. In many cases, the unit must be taken out of the plant and be transported to a repair site where it can be re-tubed, which constitutes a considerable cost factor for operators.

Coatings to Prevent Fouling in Heat Exchangers, Condensers and Process Equipment : Manoj Saraf, Multicoat Coating Technologies Pvt.Ltd., Kolkata, India

Some cleaning cost figures published by refineries in Saudi Arabia, Korea, and southern Italy confirm the high cleaning costs caused by fouling and incrustation. The annual total lies between US$8 and $20 million depending on the capacity of the refinery. The figures for each heat exchanger range from US$30,000 to $40,000 per year. Because of heavy fouling, the units have to be built over-sized, again involving considerably higher investment costs. Although the stronger flow velocity induced by incrustation may remove some of the deposits, it also reduces the cooling performances and thus the efficiency of the tube bundles. Fouling and incrustation can be reduced by changing the flow velocity, the kind of cooling water, and the quality of other materials. Hence by adjusting these parameters, the designer can economically optimize a tube bundle. Heat exchangers using cooling water usually suffer from bio-fouling on the heat transfer surfaces. Chlorination of cooling water has been the most widely used process to control condenser biofouling and most large modern plants generally chlorinate at regular intervals 2-4 times per day for period of 15-30 min/application. The generation and use of such large amounts of chlorine can lead to the pollution to the environment. The use of various types of biocides and water treatment chemicals do help in controlling the problem to a certain extent, but also mean a recurring cost for the plant and environmental pollution. The deposition of insoluble mineral scales on down-hole and surface equipment presents a major problem for the oil industry. The presence of scale reduces operational efficiency and increases the risks to production, while remedial work can be costly both in terms of direct costs and loss of production. Wax deposition in oil pipeline system is even more serious. Cost Due to Fouling Despite the enormous costs associated with fouling; only very limited study has been done in this area. Reliable knowledge of fouling economics is important when evaluating the cost efficiency of various mitigation strategies. The total fouling-related cost can be broken down into four main areas: Capital expenditure, which includes excess surface area (10-50%, with an average around 35%), costs for stronger foundations, provisions for extra space, increased transport and installation costs. Extra fuel costs, which arise if fouling leads to extra fuel burning in furnaces or boilers or if more secondary energy such as electricity or process steam is needed to overcome the effects of fouling.

Coatings to Prevent Fouling in Heat Exchangers, Condensers and Process Equipment : Manoj Saraf, Multicoat Coating Technologies Pvt.Ltd., Kolkata, India

Recurring cost of use of treatment chemicals and biocides as also the recurring maintenance cost of frequent cleaning of fouling depositions. Production losses during planned and unplanned plant shutdowns due to fouling. These are often considered to be the main costs of fouling and are very difficult to accurately estimate.

Coatings have been used to mitigate the problems of corrosion, fouling and erosion in various industries since the last almost 40 years and there are many study and research reports in this regard. The Electric Power Research Institute (EPRI) has published reports about Heat Exchanger Tube Coatings and liners (GS-6203 - 03/15/1989), In-Situ Coating of Condenser Tubes as an Alternative to Re-tubing (TR-107068 12/31/1996). The reports suggested that full length tube coatings were a possible solution to the problems of corrosion because they had worked so well in preventing corrosion of water boxes tube-sheets, and tube ends. In 1990, both Japan and Germany offered shop-coated new copper tubing; shop coating of petrochemical HX tubes was done in many countries, including the U.S.; and in Europe (Italy), in-situ coating of condenser tubes was a common practice. Florida Power Corporation and EPRI conducted a six-year study culminating in a final report, In-Situ Coating of Condenser Tubes as an Alternative to Retubing. This extensive report included heat transfer studies and coatings applications in three plant units and a side-by-side test of two water-boxes, one with coated tubes and one with uncoated tubes. The findings in the EPRI study supported the use of coatings. While the uncoated water-box required regular maintenance and cleanings, the coated box did not. The uncoated tubes continued to deteriorate, doubling plugged percentage within five years, while the plug rate of the coated tubes remained low. Heat transfer results showed that coatings resistance typically compares with that of a slightly fouled tube, and, while coatings do reduce the tube diameter (3-6 mils), this is compensated by an increase in the water flow rate in the tube. Coating tubes is less costly than re-tubing.

Coatings for prevention and mitigation of fouling:

Modification of the surface of heat exchanger tubes by the means of application of a film or coating is today finding wide acceptance to mitigate the problem of fouling in process equipment, such coatings not only improve processing performance and the overall heat transfer efficiency, they also help in minimizing environmental pollution caused by chemical cleaning agents. Historically, to combat fouling, marine antifouling paints have used compounds toxic to marine organisms, particularly tributyl tin (TBT) compounds, however now use of such toxic tin-based biocides have been prohibited because of their adverse environmental impact on marine species and because of concerns about the toxicity of these paints to workers who handle them. Copper

Coatings to Prevent Fouling in Heat Exchangers, Condensers and Process Equipment : Manoj Saraf, Multicoat Coating Technologies Pvt.Ltd., Kolkata, India

based antifouling coatings are viewed as less toxic; however, these coatings operate by slowly leaching copper into the sea/process water, killing barnacles and other (non-target) marine life. Studies have shown that these compounds persist in the water, harming the environment and possibly entering the food chain. For the prevention and mitigation of fouling in heat exchangers and process equipment, thermally cured liquid thermosetting resinous coatings formulated from synthetic resins, have been used for now more that 40 years for coating of heat exchanger tube surfaces. These anti-fouling coatings exhibit very good chemical resistance, are resistant to many aggressive media, and exhibit excellent hardness and surface smoothness. Depending on the particular type, heat-cured coatings are physiologically harmless pressure resistant and can be exposed to continuously high temperatures. These heat-cured coatings are being widely used in the oil industry, in the petrochemical and chemical process industry, in fertilizer plants, geothermal power plant, in steel plant and in pharmaceutical industries as well as in the food producing and processing industry for the last more than 40 years and have proven their performance by finding application on thousands of heat exchangers, condensers and air-coolers, on the tube side and the shell side. Such Thermally cured resinous coating in heat exchanger tubes reduces investment and operating costs by a significant margin because low cost carbon steel may be used even under aggressive conditions instead of using brass or high grade steel and special alloys which are costly. Thermally cured coating of the tube side of the tubes and, in some cases, the shell side mitigates fouling and incrustation to the tube bundles over the long term. There is certainly a small loss in the heat transfer efficiency of a coated tube compared to an un-coated tube, but when this loss is factored by the loss in heat transfer due to fouling in an un-coated tube over a coated tube, and then the initial loss in heat transfer is insignificant. Saekaphen and Heresite are some well known thermally cured resinous coatings which have been successfully used world-wide, more so in America and Europe since the last many decades.

We in India, have developed Molcoat SPGC-14 & SPGC-18 modified thermally cured liquid thermosetting resinous coating formulated from a complex mix of resins exhibiting biocidal decontamination properties, the coating is free from any tributyl tin or copper based pigments, this coating can be classified as an anti-fouling coating as well as a fouling release coating. It exhibit very good chemical resistance, hardness, good thermal conductivity, temperature resistance, low contact angle, low surface energy etc. amongst other properties. These coatings have been very successfully used in various process equipments in the Steel Industry and are being further tested and evaluated for application in other process industries.

Molcoat Coated tubes bundles are essentially superior to un-coated tubes:

1. Molcoat thermally cured resinous coatings exhibit biocidal decontamination properties in the sense that it inhibits the attachment of micro and macro fouling organisms to its surface, without the use of any toxic biocides and pigments. 2. Coating on the tube side does initially reduce the heat transfer efficiency, but the initial reduction in heat transfer is insignificant when compared to the loss due to fouling deposits in an uncoated tube. This initial loss is reduced to some extent by the addition of special very high thermally conductive filler and ceramic material in the Molcoat coating composition thereby increasing the thermal conductivity of the cured film. 6

Coatings to Prevent Fouling in Heat Exchangers, Condensers and Process Equipment : Manoj Saraf, Multicoat Coating Technologies Pvt.Ltd., Kolkata, India

3. Molcoat thermally cured resinous coating is applied in a flooding process, in 4-6 individual layers, each of which is pre-cured at temperatures between 110oC - 130oC in special polymerization furnaces. After the last individual layer is applied, final curing is carried out at 200o C. With this coating technology, a homogeneous, hydrophobic, rigidly elastic, and non-porous surface of a total thickness of 160-240 um can be achieved. The coated tube surfaces are inspected with measuring probes and holiday detectors to ensure a holiday free surface. Furthermore, the friction resistance for flowing media is reduced as well due to the very smooth and hydrophobic nature of the cured film. 4. Molcoat thermally cured resinous coating exhibits resistance against all kinds of water, including sea water and brackish water, and against many chemical media, at temperatures up to 200o C. This high temperature resistance is the result of a special heat curing process applied to the protective coating. It forms an impervious barrier and prevents corrosive currents to pass.
Apart from the thermally cured resinous coatings discussed here above, which have been very successful in the industry over the last many decades in mitigating the problem of fouling in heat exchangers, condensers and process equipment, there are also other coating systems which find application in heat exchangers and process equipments to mitigate the problem of fouling corrosion, such as Fluoropolymer coatings, Polyphenylenesulfide coatings, Polysiloxane Fouling release coatings etc. The problem of fouling being so acute that it has generated a lot of interest amongst researchers who are now working on new coating techniques based on Nano-technology, to modify the surface properties of common construction materials for equipments and devices in order to improve the processing performance and fouling resistance. It has been realized that the surface physicochemical properties (e.g. surface energy, surface charge etc.) of construction materials have significant influence on fouling adhesion. For example, it was found that there exists an optimum value of the surface free energy of materials, on which foulant adhesion is minimal:
LW Surface (1 / 2)(

LW foulant

LW fluid

where foulantLW, fluidLW and SurfaceLW are Lifshitz-van der Waals (LW) surface free energy of foulant, fluid and material surface respectively. As the equation isolates the effect of surface free energy upon particulate adhesion from the numerous parameters in the DLVO theory (The DLVO theory is named after Derjaguin, Landau, Verwey and Overbeek who developed it in the 1940s. The theory describes the force between charged surfaces interacting through a liquid medium. It combines the effects of the van der Waals attraction and the electrostatic repulsion due to the so called double layer of counterions), it appears relatively simple. An effective and desired approach to prevent or limit fouling adhesion is to alter the surface properties of the construction materials and to make it repulsive or less attractive for the fouling components. Obviously, this will involve many various research areas, including surface and materials science, surface modification techniques, surface analysis, the DLVO theory and transport phenomena, fouling and cleaning techniques, quantum chemistry and CFD, and microbiology etc. Researchers aim to minimize foulant adhesion forces by altering the surface properties of processing equipment and devices, using Nano-composite coating techniques, so that fouling formation can be reduced significantly or even prevented.

Coatings to Prevent Fouling in Heat Exchangers, Condensers and Process Equipment : Manoj Saraf, Multicoat Coating Technologies Pvt.Ltd., Kolkata, India

Some of the Coating techniques for Surface modification of construction materials with defined physical-chemical characteristics, on which considerable work in being done world-wide include the following : Novel Ni-PTFE Nano-Composite Coatings : The coating has excellent wear and corrosion resistance. Unlike other coating techniques such as ion beam implantation, which can only treat the outside surface, the cost-effective electroless plating technique can treat internal porous surfaces uniformly. This is particularly important for membrane treatment, as fouling could occur on and within the porous matrix of the membranes. In addition, as the nano-composite coating is ultra-slippery, bacteria or other types of foulant are unlikely to attach/cling to the surface permanently, and are easily swept off by flowing water even at low flow velocity. Obviously this coating technique can also be used to treat any type of construction materials (e.g. stainless steel, polymer etc.). DLC+elements Nano-composite coatings : It has already been demonstrated that the surface energy of Diamond Like Carbon (DLC) coatings can be altered in a wide range by adding small amount of elements such as F, N, O, Si or Ti into the coatings. The modification can be done either by co-sputtering the elements or by adding adequate reactive gases (e.g. C2F2, Si(CH3)4, O2 or N2 etc) to the working gas during DLC coating process. DLC+element nanocomposite is extremely hard and has excellent wear and corrosion resistance, so it is an ideal coating to prevent fouling in process equipments. Thin film coatings by sol-gel techniques: The sol-gel process allows the development of thin films comprised of nanoparticle dispersed inorganic-organic composite materials. In addition to molecular inorganic-organic hybrid network, the physical, electronic or catalytic properties of nano-particles can be used for the material tailoring. Sufficiently thin (thickness of order 100 nm), coherent films can be obtained with desirable surface properties, e.g., hydrophilicity, hardness, corrosion resistance. Si-, Ti- and Zr- oxides are usual nanoparticles in composites produced through such sol-gel processes. Significant R&D is required to exploit the potential of these techniques for surface modification. Conclusion The mitigation and prevention of fouling by use of coatings is certainly and effective and viable tool in the hands of the process engineer and today there are many different coating systems available to suit different process conditions and it is high time that the Indian Industry took a serious view about the problem of fouling in process equipment and the solutions available to mitigate the same.

References 1. Knudsen, J.G., Coping with Cooling Water Fouling in Tubular Heat Exchangers, AIChE Symposium Series, Vol. 85, no. 269, 1989, p. 1-12. 2. King, R.A., Smith J.S., and Miller, J.O.A., Corrosion of Mild Steel by Iron Sulfides, British Corrosion Journal, Vol. 8, May, 1973. 3. Hays, G. F., Fouling Allowances are Self-Fulfilling Prophecies, presented at the 1989 National Heat Transfer Conference, Philadelphia, PA, August 6-9, 1989. 4. Various EPRI Reports RP-1689-18