How To Control Kiln Shell Corrosion

SUMMER IN-PLANT TRAINING REPORT
Shree Cement Ltd., Beawar(Rajasthan)

Starting From 7th May 2012-1st July 2012
Project Title:How to Control Kiln Shell Corrosion

Submitted to: Shri Sanjay Jain HOD,Mechanical Dept. Shree Cement Ltd.,Beawar How to control kiln shell corrosion, SCL Beawar (Raj.) Submitted by:Ankit Karwa 4th year UG, MSE IIT Kanpur Page 1
I take immense pleasure in thanking Shri Vinay Saxena, Plant head, Shri Sanjay Jain, HOD Mechanical Department, and Shri Atul Sharma for having permitted me to carry out this project work. I wish to express my deep sense of gratitude to Shri R.P.Pareek and Shri S.Hawa for their able guidance, useful suggestions and providing me necessary data which helped me in completing the project work, in time. Needless to mention Shri Manoj Sharma, who has been a source of inspiration and for his timely guidance in the conduct of project work. I would also like to thank Shri sanjay Baldwa, Shri Harshwardhan, Shri Manish Purohit for all their valuable and timely assistance in the project work. Id also like to express my gratitude towards the Mechanical Library and Shri Pankaj Sharma, Librarian for helping me to make available different references during the project. Words are inadequate in offering my thanks to Shri Gopal Tripathi, Sr. Manager HRD for providing us such good facilities during the project. I would like to express my heartfelt thanks to Shri Vijay Vyas, Officer HRD, for his sincere helps throughout the project without which it seemed impossible to complete the project. Finally, yet importantly, I would like to express my heartfelt thanks to my institute, INDIAN INSTITUTE OF TECHNOLOGY, KANPUR and its Material Science and Engineering Department for providing me this opportunity to interact with this organization and understand the intricacies of the corporate world.
Acknowledgment
Ankit Karwa, 4th year under graduate, Material science and Engineering, IIT Kanpur
How to control kiln shell corrosion, SCL Beawar (Raj.)
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Index
1) 2) 3) 4) 5) 6) 7) 8) Acknowledgment Abstract Introduction About Shree Cement Manufacturing Process General Chemistry of Cement Manufacturing The Kiln System Literature Review A) What is Corrosion B) Types of Corrosion C) What are Refractories D) Types of Refractories ..2 ..4 ..5 ..6 14 19 22 30 30 31 38 41 45 48 51 51 52 53 55 60 62 72
9) Type and Composition of refractory used at SCL, Beawar 10) Full details of Refractory linings, Coating and SS Plate Used 11) Corrosion of Kiln shell A) Introduction B) Corrosion of Cement Kiln C) Mechanism of Cement Kiln shell Corrosion D) Role of Refractories in tackling shell corrosion E) Role of Process Parameters on Shell Corrosion 12)Recommendations 13)References
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Abstract
Corrosion damage is a major issue in cement plants. The serious consequences of the corrosion process in cement plants have become a problem of worldwide significance. Corrosion causes plant shutdowns, waste of valuable resources, loss or contamination of product, reduction in efficiency, costly maintenance, and expenses over design can jeopardise safety. Typically, once a plant or any piece of equipment is put into service, maintenance is required to keep it operating safely and efficiently. This is particularly true for aging systems and structures, many of which may operate beyond the original design life. The type of corrosion mechanism and its rate of attack depend on the nature of the atmosphere in which corrosion takes place. The first step in preventing corrosion is to understand its specific mechanism. The second and most important as well as most difficult step is to design an effective type of protection mechanism. The Cement kilns are operating at higher thermal and volumetric loadings and utilizing alternate raw materials and fuels which are rich in volatiles creating thereby severe service conditions inside the rotary kiln. Such conditions cause the corrosion of the rotary kiln shell to take place in hot running conditions. Therefore investigations reported in the paper were unique in nature with a very specific target to understand the mechanism of such corrosion, the role of various service conditions and process parameters on corrosion phenomena and establish such remedial measures which could impede / reduce corrosion of rotary kiln shell in running conditions.
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Introduction:-
Cement is a common construction material; a binder in mortars and concretes that hardens in the presence of water. Cement is called hydraulic, when the hardened product is stable in an aqueous environment. The most widespread hydraulic cement today is portland cement a finely ground gray-to-white powder composed primarily of calcium silicates, calcium aluminates, and calcium ferrites, derived from mineral ingredients (Figure below).
Fig 1:Cement Powder Cement is made by heating limestone (calcium carbonate) with some other materials such as clay to about 1400C in a kiln, where a molecule of carbon dioxide is liberated calcium oxide, or quicklime, is formed, which is then blended with the other materials that have been included in the mix. The resulting hard substance, called 'clinker', is then ground with a small amount of gypsum into a powder to make 'Ordinary Portland Cement' or Portland Cement, often referred to as OPC, the most commonly used type of cement in the world. Portland cement or clinker can be blended or interground with other materials to achieve certain properties. There are five classes of blended cement commonly used. They are as follows: Portland blast-furnace slag cement Portland-Pozzolan Cement(PPC) Pozzolan-modified Cement
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Slag Cement Slag-modified Portland The blended cement are gaining popularity because they require less energy to manufacture, they can be made with by-product materials that would normally be disposed in a landfill, thus reducing solid waste, and offer performance benefits for certain applications. When mixed with water, portland cement sets (stiffens) in a few hours and hardens over a period of weeks and months. These phenomena are caused by chemical reactions associated with hydration between the components of cement and water. The most common use of portland cement is in the production of concrete. Concrete is a composite consisting of aggregate (gravel and sand), cement, and water. As a construction material, concrete can be cast in almost any shape desired, and once hardened, can become a structural (load bearing) element. Portland cement is also used in mortars (with sand and water only) for plasters and screeds, and in grouts (cement water mixes) placed into gaps to consolidate brick walls, foundations, etc.
About Shree Cement:Cement industry falls in the category of manufacturing industry. With the growth of economy, cement industry is also taking substantial leaps. One amongst the companies, helping the cement industry to achieve its fast growth, is Shree Cement Ltd. It is located in central Rajasthan, catering to the entire Rajasthan market with the most economic logistics cost. An ISO 9001:2000 Company, established in the Year 1984 & the Commercial Production of Unit-I started in the Year 1985. Shree Cement Limited has its registered office located at Beawar (Raj) & Corporate Office at Kolkata (W.B.). JO SOCHE VOH PAAVE SHREE CEMENT LIMITED is an energy conscious & environment friendly business organization. Having ten Directors on its board under the chairmanship of Shri B.G. Bangur, the policy decisions are taken under the guidance of Shri H.M. Bangur, Managing Director. Shri M.K. Singhi, Executive Director of the company, is looking after all day to day affairs. The company is managed by qualified professionals with broad vision who are committed to maintain high standards of quality & leadership to serve the customers to their fullest satisfaction.
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The largest cement manufacturing plant at a single location in Northern India, under the flagship of Executive Chairman Shri B.G. Bangur & Managing Director Shri H.M. Bangur. The Company is aiming for 20 Million Ton Annual production by the year 2015. The plant is located near the city of Beawar, Dist. Ajmer in Central Rajasthan, sate ling the Beawar city at radius of 10 Kms. However the Beawar subdivision is will connected through Rail and Road both, situated on National Highway No. 8.
Fig 2: Shree Cement Unit I & II, Beawar(Raj.) Shree Cement is manufacturing 33, 43, 53 & Shree ultra Red Oxide grade Cement in Ordinary Portland Cement (OPC) and Portland Pozzolana Cement (PPC). Pozzolana used in the manufacture of Portland cement is burnt clay of fly-ash generated at thermal power plants. While Ordinary Portland cement is grey fine powder which is the result from crushing a dry mix made of clinker and gypsum. Shree cement manufactures both kinds of cement. How to control kiln shell corrosion, SCL Beawar (Raj.)
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Cement Industry in India poised for healthy growth supported by following factors: Growth of the Indian Cement industry directly influenced by GDP which is expected to grow at the rate of 7%. With various infrastructure projects like roads and highways, railways, port power projected and real estate being implemented, the demand for cement is expected to grow at a fast rate. Tax relief against interest on housing loans, stable interest rates and increasing competition in housing finance would significantly help in growth of this sector. 16% Share in Rajasthan Cement Production. Some of another plant located in RAS. The RAS plants are far from Beawar at least 35 kms. All the same activities are doing in this plant & this plant is uses High grade material our compression in BEAWAR plant and this material send in BEAWAR plant & mix both the Material & get the superior quality product. One of newly grinding unit started in KHUSHKHERA Distt-Bhiwadi, the plant is far from the BEAWAR plant almost 500 KM. UNIT -1 at Beawar Distt: Ajmer Incorporated in 1979, Established in 1985 Cement Production (Expected)-1.20 million tones UNIT -3 at Ras Distt: Pali Incorporated in 2005 Cement Production - 1.0 million tones UNIT -5,6,7 & 8 at Ras Distt: Pali Production 1.00 million tons each (also having a world record of 367 days) Khuskheda Grinding unit (Distt. Alwar) Suratgarh , Jaipur & Roorkee Grinding units: one grinding unit each UNIT -4 at Ras Distt: Pali Cement Production - 1.0 million tones UNIT -2 at Beawar Distt: Ajmer Put up in 1997 Cement Production -2.10 million tones
Green Power Project of 43 MW at Beawar & RAS, Thermal Power Plant of 100 MW at RAS How to control kiln shell corrosion, SCL Beawar (Raj.)
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Production with Efficiency It has a track record of over 100% capacity utilization in the 18th yr of its existence. Against the national industry average of 84% it has registered the highest record production of 3.02MT with 116% of capacity utilization. The commercial production of Unit I started in the year 1985. The production augmented exponentially from the capacity of 0.6 MTPA in 1985 to around 4.8 million ton presently through modification, capacity enhancement and continuous improvement. The revised target is 25 MTPA by 2015. Innovative & Cost Conscious Management Leadership in the use of alternative waste fuel. Initiatives for Global warming reduction. Partial utilization of waste heat. Initiator in the use of pet coke for power generation in India. PROGRAMES: Celebration of National Safety Day. Celebration of National Safety Week. Staff Training in the subject of Safety. Environment Safety Day.
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Policies of the Company
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Fig 4: Typical process flow diagram of a cement plant
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Manufacturing Process:
Minning Limestone is the main raw material of cement and is obtained from the mines. Bore holes are made in the mines at various locations, and samples are collected to test the CC% (CaCO3 percentage) in the mines. Limestone is retrieved by blasting the mines and then the rock material obtained from the mines is crushed. This crushed limestone (raw material) is sent to the plant with the help of conveyer belts and/or transportation. Stacking and Reclaiming A stacker is a large machine used in bulk material handling applications. It is mainly used to arrange the incoming feed in piles. It is important to maintain the homogenous and uniformity before discharging to further process. A stacker usually operates on a rail-like structure with movable wheels, but the main operation is performed on a fixed place. The main function of a Reclaimer is to recover the material and at the same time maintain uniformity. At this stage the material is collected in hoppers via conveyer belts. Reclaimers are volumetric machines and are rated in m3/h (cubic meters per hour) for capacity, which is often converted to t/h (tonnes per hour) based on the average bulk density of the material being reclaimed. Reclaimers normally travel on a rail between stockpiles in the stockyard and are generally electrically powered by means of a trailing cable. Pile of limestone is made by horizontal stacking of different CC% limestone to get the required CC%. To obtain homogenized limestone for cement production, vertical reclaiming is done. Raw Material Grinding Raw mill (Vertical Roller Mill) is a grinding equipment which is used to grind the incoming feed fed through hoppers. There are three hoppers in each unit. The first two carrying limestone and third hopper containing Laterite (zinc slag i.e. molten residue at the bottom of zinc smelter). Laterite has a high percentage of iron. Raw mill is tall unit containing a horizontally movable disc and three vertical disc, assembled a way to stand the vibrations with the virtue of the state of art suspension system. Raw mill grinds the feed to very small size and the output is sucked through the provided vents. The output is generally known as Raw Meal. This raw meal is stored in Silos.
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Coal Grinding The heat required for heating and conversion is obtained by burning of grinded pet coke. Pet coke is the residue of petroleum refining and is grinded again in a VRM (Coal mill). This grinded pet coke is stored in a storage bin. Clinkerisation The raw material powder is fed into a preheater in which suction is created with the help of suction gas pump. This provides a larger residence time in the cyclonic preheaters, which are placed in a zigzag manner. The material reaches approximately 880oC at the end of the preheater. In the preheater major reaction taking place is the decomposition of CaCO3 to produce CaO. This material then enters the rotary kiln, in which hot air is blasted from the opposite direction at a temp of about 1500oC. CaO (C), Al2O3 (A), SiO2 (S), Fe2O3 (F) react in various parts of the kiln to produce C3A (10%), C4AF (10%), C2S (30%), C3S (50%). This mixture is called as clinker. Clinker formed above is cooled with the help of the air in Grate coolers, and then stored in clinker silos. The key component of the gas-suspension pre-heater is the cyclone. A cyclone is a conical vessel into which a dust-bearing gas-stream is passed tangentially. This produces a vortex within the vessel. The gas leaves the vessel through a co-axial "vortex-finder". The solids are thrown to the outside edge of the vessel by centrifugal action, and leave through a valve in the vertex of the cone. Cyclones were originally used to clean up the dust-laden gases leaving simple dry process kilns. If, instead, the entire feed of raw meal is encouraged to pass through the cyclone, it is found that a very efficient heat exchange takes place: the gas is efficiently cooled, hence producing less waste of heat to the atmosphere, and the raw meal is efficiently heated. This efficiency is further increased if a number of cyclones are connected in series. The number of cyclones stages used in practice varies from 1 to 6. Energy, in the form of fan-power, is required to draw the gases through the string of cyclones, and at a string of 6 cyclones, the cost of the added fan-power needed for an extra cyclone exceeds the efficiency advantage gained. It is normal to use the warm exhaust gas to dry the raw materials in the raw mill. The hot feed that leaves the base of the pre-heater string is typically 20% calcined, so the kiln has less subsequent processing to do, and can therefore achieve a higher specific output.
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Fig 6:Pyro Process Cement kilns are used for the pyro-processing stage of manufacture of cement, in which calcium carbonate reacts with silica-bearing minerals to form a mixture of calcium silicates. Cement kilns are the heart of the cement production process: their capacity usually defines the capacity of the cement plant. As the main energy-consuming and greenhouse-gas emitting stage of cement manufacture, improvement of their efficiency has been the central concern of cement manufacturing technology. The rotary kiln consists of a tube made from steel plate, and lined with firebrick. The tube slopes slightly (14) and slowly rotates on its axis at between 30 and 250 revolutions per hour. Raw mix is fed in at the upper end, and the rotation of the kiln causes it gradually to move downhill to the other end of the kiln. At the other end fuel, in the form of gas, oil, or pulverized solid fuel, is blown in through the "burner pipe", producing a large concentric
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flame in the lower part of the kiln tube. As material moves under the flame, it reaches its peak temperature,before dropping out of the kiln tube into the cooler. Air is drawn first through the cooler and then through the kiln for combustion of the fuel. In the cooler the air is heated by the cooling clinker, so that it may be 400 to 800 C before it enters the kiln, thus causing intense and rapid combustion of the fuel.
Fig 7: Cement Rotary kiln Note: - The details of Cement Rotary kiln are discussed in detail in later part of the report. Cement grinding The clinker leaving the cooler has a variable particle size, typically of diameter 3-25 mm. Thus it is necessary to grind the clinker to a more uniform particle size. This can either be done directly after the cooler, or the clinker can be transferred to a silo until it is needed, see Figure 2-1. Cement clinker is, however, not a stable material: It reacts readily with water/water vapour and CO2 from the air. This will result in pre-hydration and carbonation. Extended storage periods may therefore have an effect on the cement properties. In connection with the clinker grinding, 3-6 wt-% gypsum (CaSO42H2O) is added to the clinker. The gypsum has a marked effect on both the strength and the setting of cement. Additives such as coal fly ash, sand or raw material may also be added at this point in order to contribute positively to the strength-giving properties of the cement. Some of these Additives can replace a significant fraction of the clinker, thereby saving energy needed for calcinations and clinker reactions. Thus the additives have a great potential to reduce energy consumption and CO2-emissions per kg cement produced. For this reason, many cement companies seek to minimize their environmental impact by exploring the use of new Supplementary Cementitious Materials (SCM), examples being volcanic ashes or kaolinite clays. The grinding of clinker and additives can be performed with several different mill systems. When a sufficient fineness is reached, the final Portland cement product is transferred to a cement silo. It is stored in this silo until it is being packed and shipped to the end users. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 17
Fig 8: Detail flow sheet of whole process
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General Chemistry of cement manufacturing

The Portland cement is made by heating a mixture of limestone and clay, or other materials of similar bulk composition and sufficient reactivity, ultimately to a temperature of about 1450oC. Partial fusion occurs, and nodules of clinker are produced. The clinker is mixed with a few per cent of calcium sulphate and finely ground, to make cement. The calcium sulphate controls the rate of set and influences the rate of strength development. It is commonly described as gypsum, but this may be partly or wholly replaced by the other forms of calcium sulphate. Some specifications allow the addition of other materials at the grinding stage. The clinker typically has a composition in the region of 67% CaO, 22% SiO2, 5% Al2O3, 3% Fe2O3 and 3% other components, and normally contains 4 major phases: 1. Alite 2. Belite 3. Aluminate 4. Ferrite Alite: Alite is the most important constituent of all normal Portland cement clinkers, of which it constitutes 50-70%. It is tricalcium silicate (Ca3SiO5) modified in composition and crystal structure by ionic substitutions. Reaction of this phase with water is very quick and in normal Portland cements it is the most important of the constituents phases for strength development; it ages up to 28 days, it is by far the most important. Belite: Belite constitutes 15-30% of normal Portland cement clinkers. It is di calcium silicate (Ca2SiO4) modified by ionic substitutions and normally present wholly or largely as the polymorph. It reacts slowly with water, thus contributing little to the strength during the first 28 days, but substantially to the further increase in strength that occurs at later ages. By one year, the strengths obtainable from pure alite and pure belite are about the same under comparable conditions.
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Aluminate: Aluminate constitutes 5-10% of most normal Portland cement clinkers. Basically it is tri calcium aluminate (Ca3Al2O6) substantially modified in composition and sometimes also in structure by ionic substitutions. It has a rapid reaction with water. This phase causes an undesirable rapid setting so we need a controlling agent for this phase (like Gypsum). Ferrite: It is tetra calcium alumina ferrate i.e. Ca2AlFeO5, substantially modified in composition by variation in Al/Fe ratio and ionic substitution. It has variable reaction rate with water.Initially it reacts rapidly with water but reaction goes on slowing down with time which is due to the difference in the compositions or other characteristics. Clinker consists of MgO up to 4-5 %. If there is an excess of only 2% then it can cause expansion of hardened concrete on reaction with water. This excess can occur as periclase (MgO). Same problem might happen with SO3 if it is not under the limit of 3.5 % . To produce white cement we increase the ratio of Al2O3 to Fe2O3. Dark color of the cement is due to ferrite. Reaction of cement with water is exothermic. This total heat can be reduced by lowering alite and aluminate content in coarser grinding. This can also be done by the addition of fly ash. Clinker Reactions After having passed the calciner, the calcined raw meal is admitted to the rotary kiln where the remaining cement clinker reactions take place. Calcined raw meal is also called hot meal in cement terminology in order to distinguish it from raw meal not yet calcined. The names, chemical compositions and abbreviations used in cement nomenclature for the four main constituents of Portland cement clinker are shown in Table 1. Belite and alite are the strength-giving minerals. Alite reacts fast with water during hydration and accounts for the early strengths while belite reacts slower and gives the cement its late strengths. Ferrite and aluminate do not contribute to the strengths of the cement. But they possess important properties when burning clinker. These properties of ferrite and aluminate will be explained later in this section. Name Chemical Composition Belite 2Cao.SiO2 Alite 3Cao.SiO2 Aluminate 3CaO.Al2O3 Ferrite 4CaO.Al2O3.Fe2O3 Table 1: Main Constituents of Portland Cement Nomenclature C2S C3S C3A C4AF Page 20
Free lime (CaO), free periclase (MgO), earth alkali sulfates (CaSO4, MgSO4), Alkali sulfates (Na2SO4, K2SO4) and other minor components may also be found in the clinker. The requirements for the Portland cement clinker are: a) > 67 wt.-% calcium silicates (C2S and C3S). The remainder must mainly be Fe2O3, Al2O3 and other oxides. b) < 5 wt.-% MgO c) The CaO/SiO2 ratio by mass shall not be less than 2.0. Clinker reactions occur at temperatures between 700-1450C, see Figure 9. The reactions forming the final clinker involve intermediate compounds, and the clinker reactions may be affected by minor compounds. The overall clinker reactions are described, while a detailed overview of the chemistry, phase relations etc.
Fig 9: Phase Diagram for cement clinker production
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The kiln system
The Production of cement may be divided into three parts: 1) Preparation of raw materials,2)pyro-processing and 3)clinker processing, storage and shipment. Pyroprocessing covers the thermal treatment of the raw materials necessary to obtain the cement clinker. Pyro-processing takes place in the preheater, calciner, rotary kiln and cooler. These sections are commonly referred to as the kiln system. Rotary kiln The rotary kiln is often referred as heart of cement plant. This is where the chemical clinker formation reactions take place. The rotary kiln is simply a long, cylindrical tube consisting of an outer shell and an inner refractory lining. Typical lengths and diameters for modern rotary kilns are between 40-100 m, and 3-6m, respectively. Rotary kilns are inclined 1-4 and rotate 1-5rpm in order to facilitate mass transport and ensure clinker forming processes such as nodulization. Production capacity is typically 2000-4000 tonnes of clinker per day (tpd), but may be as high as 12000 tpd. In the material outlet, the rotary kiln is equipped with a burner. The burners main function is to form a flame to provide energy for clinker reaction to takes place. The flame of the rotary kiln burner should be short, narrow and strongly radiant in order to achieve a good heat transfer from the flame to materials in the bed. Modern rotary kiln burners are often designed to burn a variety of fuels. This is today achieved by using multi-channel burners with separate channels for fuels and primary air which make it possible to adjust primary air amounts, injection velocities and momentum independently of the fuel flows. Swirl may be used to enhance mixing and stabilize the flame. The recent trend in multiple fuel burners is to use a single common fuel channel which allows more flexibity towards fuel particle size and type. Fig 10: Left: Outer view of rotary kiln seen from above. Right: Inner view seen from burner end. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 22
In early cement plants, the kiln system consisted only of a rotary kiln: Raw materials were dried, preheated, calcined and burned to clinker on their way through the rotary kiln. This process required very long rotary kilns, often significantly longer than 100 m. The raw materials were either introduced as dry raw meal or as water/raw material slurry, and this type of plants were therefore commonly referred to as dry long kilns or wet long kilns, respectively. Due to a low energy efficiency, this type of cement plants is very expensive to operate, and are rarely constructed today. The rotary kiln consists of an outer steel shell and an inner refractory lining for thermal insulation, in order to maintain and resist the high process temperatures. In a rotary kiln, the refractory usually consists of bricks of special composition and sizes, able to withstand high temperatures. However, the refractory may also be a cast lining of concrete. The refractory lining is subject to a wide range of destructive influences through the mechanical dynamics of the rotary kiln, the chemistry of the cement clinker process and the type of fuels used. The intensity of these stresses varies according to the operating conditions and kiln sections. The rotary kiln is therefore equipped with a range of refractory bricks with different properties to ensure appropriate kiln zone lining. The burning zone refractory lining usually suffers the greatest wear due to the higher temperatures in the burning zone. However, the burning zone lining is protected by a coating layer which prolong the lifetime of the refractory lining. The coating is a mass of clinker or dust particles that adheres to the wall of the kiln, having changed from a liquid or semiliquid to a solidified state. Generally, the burning zone refractory lifetime is 9 to 12 months depending on the specific kiln type and operating conditions. The refractory lifetime of the colder rotary kiln material inlet zone is typically 12 to 48 months. Thus, these different rotary kiln zones do not have to be replaced quite as frequently. The most used brick types today are chromium-free magnesia-alumina-spinel bricks with MgO content of 80-95 wt.-% and Al2O3 content of 3-18 wt.-%. Minor compounds are typically Fe2O3, Mn2O3, SiO2, CaO and ZrO2. These brick types are regarded as having the longest service life and the best price/performance ratio. The increased use of alternative fuels in the cement industry may lead to higher levels of recirculating alkali metals and sulfur within the kiln system.Recirculating alkali metals and sulfur cause large quantities of salts to condense in and on the refractory lining, predominantly in the temperature window 750C to 1,100C . Salt compounds enter into reactions with refractory bricks that contain alumina and the bricks can be destroyed by salt How to control kiln shell corrosion, SCL Beawar (Raj.)
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crystallization and alkali spalling. Sulfur oxides make the reactions even worse, by formation of alkali sulfate salt. Various strategies are used by the refractories industry to counteract these wear processes. These include use of additives that produce low gas permeability and reduce the infiltration tendency of alkalis. Other solutions are sealing or impregnating the refractory material to form a protective zone. One of the most successful and widespread solutions is addition of 3-6 wt.-% Silicon carbide, SiC, which leads to an appreciable resistance to alkali attack. The addition of SiC leads in situ to formation of liquid phases, which seal the refractory surface and protect against alkali infiltration. Increased circulation of inorganic volatiles such as sulfur and chlorine in the kiln system, due to increased alternative fuel utilization also entails a higher risk of kiln shell corrosion (Jns and stergaard, 2001). Efforts have been made to identify suitable refractory steels for cement rotary kilns, with characteristics that are a compromise between good creep resistance, high corrosion resistance in the presence of chlorine and sulfur, and strong resistance to abrasion when hot. Thermal profile and kiln subdivisions The rotary kiln thermal profile varies throughout its length, depending on the temperature and chemical reactions involved during the process (see in Table 2). The rotary kiln can be subdivided into several zones or regions that are exposed not only to thermal and chemical wear but also to mechanical stresses. The influence of one or several of these factors, to minor or greater proportion determines the refractory lining type required for each zone: A. Decarbonation zone: from 300C to 1000C (+) This stage can occur either inside of the old wet process rotary kilns or in the preheater tower of modern units consisting of two steps: Firstly, between 300C and 650C where the raw meal heating occurs, accompanied by a dehydration reaction; Secondly, between 650C and 1000C, when the limestone decarbonation takes place generating CO2 and CaO. The first step is characterized by the following aspects: How to control kiln shell corrosion, SCL Beawar (Raj.) Presence of raw meal (there are no new mineral phases development); Page 24
Erosion (due to raw meal flow at high velocities); low temperature; Evaporation and dehydration (of water) chemically bonded to the raw material.
In this zone it is very important that the refractory products have the capability to protect the rotary kiln drive (good insulation degree) and good resistance to impacts of anomalous build-ups. Bricks with less than 45% Al2O3 content are suitable. Besides that, when alkaline salts are present, a vitreous glassy layer can develop with the alkali on the brick surface, preventing its propagation or later infiltration.
In the second stage of these reactions, the development of new mineralogical phases occurs: Formation of CaO and CO2; Formation of CA, C12A7 and C2S; Temperature variation; Alkali attack.
Usually, the use of bricks with a 70% Al2O3 content is recommended, which offers a high mechanical resistance, low porosity, and low thermal conductivity. However, the risk of eutectic reactions formations on the Al2O3-CaO- SiO2 , system and alkali resistance is a limiting factor.
B.
Upper transition zone: from 1000C to 1238C (+)
It is the most unstable and difficult area for refractory specification. Although the temperature range varies from 1000C to 1338C, incidences of thermal overloads are frequent. This fact is linked on the flame shape, to the fuel type and to the design of the kiln main burner. Therefore, it is in this area where coating starts to develop as soon as first drops of liquid phase appear. Coating becomes very unstable if the operational conditions present high variability.
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Table 2 C. Sintering zone: from 1338C to 1450C (+) In this area a full development of coating at 1450C(+) is expected. The presence of some liquid phase facilitates the dissolution of C2S in the same what promotes the reaction that generates C3S. The highest temperature in the kiln is reached at this area. Usually it should be around 1450C for ordinary Portland Cements. Liquid phase is also around 25% at 1450C. If process is under control, coating will be stable and able to protect the lining during the whole campaign. However, if there is a big variability at ram meal control parameters or uneven fuels types shifting, coating will be unstable and refractories submitted to an enormous thermo-chemical wear. The refractory products must resist high temperatures, infiltration of molten liquid calcium silicates, and/or alkaline sulfates, and be able to hold a stable coating. Usually at this kiln zone it is possible to find: Presence of incipient liquid phase from 18 to 32%, free lime and C2S; Development of C3S by the reaction of CaO and C2S. Clinker liquid phase infiltration and coating formation; Chemical attacks by alkaline sulfates; High operational temperature.
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D. Lower transition zone from: 1400C to 1200C (+) This area usually operates between 1400C and 1200C. Around 1200C begins the crystallization of the clinker the mineral phases, but not. Although the liquid phase can still be present, it is a stage of low chemical activity, considering that most of C3S has already been formed with a remaining amount of free lime around 1%. Nevertheless, it is a zone submitted to temperature variations since it is right under the influence of the secondary air temperature coming from the cooler. This area is characterized by the following aspects: Presence of the clinker liquid phase; Chemical attacks by alkaline sulfates; Frequent temperature variations when flame impinges over the brick; Continuous thermal shock; Redox atmosphere when using alternative fuels with poorly designed burner; Mechanical stress imposed by the tire station and kiln shell ovality. In order to support the temperature variations under mechanical stress, this part of the process requires the use of basic bricks with high structural flexibility, low permeability to gas, high hot modules of rupture and abrasion resistance. E. Pre-cooling zone from: 1200C to 1000C (+) Originally, many kilns have been designed to promote the end of freezing and crystallization of the just developed clinker phases. However, nowadays, the existence of this zone into the kiln depends of the clinker cooler type and the secondary air temperature entering into the kiln. With old grate coolers it was around 700C, and for the modern high efficiency ones from 1150C to 1100C. In this zone at that temperature range, there is high abrasion (clinker nodules), accentuated discharge erosion (by the clinker dust carried by secondary and tertiary airs) and mechanic stresses (nose ring plates and retention ring for refractory products). The main characteristics of this kiln zone are: High abrasion / erosion; Frequent thermal shocks; High mechanical stresses (compression/traction). In most of the modern furnaces equipped with high efficiency coolers, this zone is not inside the rotary kiln but in the first cooling compartment. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 27
Wet Process The original rotary cement kilns were called 'wet process' kilns. In their basic form they were relatively simple compared with modern developments. The raw meal was supplied at ambient temperature in the form of slurry. A wet process kiln may be up to 200m long and 6m in diameter. It has to be long because a lot of water has to be evaporated and the process of heat transfer is not very efficient. The slurry may contain about 40% water. This takes a lot of energy to evaporate and various developments of the wet process were aimed at reducing the water content of the raw meal. An example of this is the 'filter press' (imagine a musical accordion 10-20 metres long and several metres across) - such adaptions were described as 'semi-wet' processes. The wet process has survived for over a century because many raw materials are suited to blending as slurry. Also, for many years, it was technically difficult to get dry powders to blend adequately. Quite a few wet process kilns are still in operation, usually now with higher-tech bits bolted on. However, new cement kilns are of the 'dry process' type.
Dry Process In a modern works, the blended raw material enters the kiln via the pre-heater tower. Here, hot gases from the kiln, and probably the cooled clinker at the far end of the kiln, are used to heat the raw meal. As a result, the raw meal is already hot before it enters the kiln. The dry process is much more thermally efficient than the wet process. Firstly, and most obviously, this is because the meal is a dry powder and there is little or no water that has to be evaporated. Secondly, and less obviously, the process of transferring heat is much more efficient in a dry process kiln. An integral part of the process is a heat exchanger called a 'suspension preheater'. This is a tower with a series of cyclones in which fast-moving hot gases keep the meal powder suspended in air. All the time, the meal gets hotter and the gas gets cooler until the meal is at almost the same temperature as the gas. The basic dry process system consists of the kiln and a suspension preheater. The raw materials, limestone and shale for example, are ground finely and blended to produce the How to control kiln shell corrosion, SCL Beawar (Raj.) Page 28
raw meal. The raw meal is fed in at the top of the preheater tower and passes through the series of cyclones in the tower. Hot gas from the kiln and, often, hot air from the clinker cooler are blown through the cyclones. Heat is transferred efficiently from the hot gases to the raw meal. The heating process is efficient because the meal particles have a very high surface area in relation to their size and because of the large difference in temperature between the hot gas and the cooler meal. Typically, 30%-40% of the meal is decarbonated before entering the kiln. A development of this process is the 'precalciner' kiln. Most new cement plant is of this type. The principle is similar to that of the dry process preheater system but with the major addition of another burner, or precalciner. With the additional heat, about 85%-95% of the meal is decarbonated before it enters the kiln.
Fig 11: Preheater Precalciner Kiln
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Since meal enters the kiln at about 900 C, (compared with about 20 C in the wet process), the kiln can be shorter and of smaller diameter for the same output. This reduces the capital costs of a new cement plant. A dry process kiln might be only 70m long and 6m wide but produce a similar quantity of clinker (usually measured in tonnes per day) as a wet process kiln of the same diameter but 200m in length. For the same output, a dry process kiln without a precalciner would be shorter than a wet process kiln but longer than a dry process kiln with a precalciner.
Literature Review
Corrosion
What is corrosion Types of corrosion
Refractories
What is refractory Types of refractories What is the composition of refractories used at SCL,Beawar
What is corrosion
Corrosion is the gradual destruction of material, usually metals, by chemical reaction with its environment. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen. Rusting, the formation of iron oxides, is a well-known example of electrochemical corrosion. This type of damage typically produces oxide(s) or salt(s) of the original metal. Corrosion can also occur in materials other than metals, such as ceramics or polymers, although in this context, the term degradation is more common. Corrosion degrades the useful properties of materials and structures including strength, appearance and ability to contain a vessel's contents. Many structural alloys corrode merely from exposure to moisture in the air, but the process can be strongly affected by exposure to certain substances. Corrosion can be concentrated locally to form a pit or crack, or it can extend across a wide area more or less uniformly corroding the surface. Because corrosion is a diffusion controlled process, it occurs on exposed surfaces. As a result, methods to reduce the activity of the exposed surface, such How to control kiln shell corrosion, SCL Beawar (Raj.)
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as passivation and chromate-conversion, can increase a material's corrosion resistance. However, some corrosion mechanisms are less visible and less predictable.
Types of corrosion
1) Uniform Corrosion or General Corrosion This type of corrosion is chemical or electrochemical in nature. However, there are no discrete anode or cathode areas. This form of corrosion is uniform over the surface of the metal exposed to the environment. The metal gradually becomes thinner and eventually fails. The energy state of the metal is basically what causes this reaction. Referred to as the dust-to-dust process, high levels of energy are added to the raw mmaterial to produce the metal. This high energy level causes an unnaturally high electrical potential. One law of chemistry is that all materials will tend to revert to its lowest energy level, or its natural state. After high levels of energy are added to the metal, when it is exposed to the environment (an electrolyte), it will tend to revert to its natural state. This process is normally extremely slow, and is dependent on the ion concentration of the electrolyte that it is exposed to. Only under very extreme conditions (acidic electrolyte) can this form of corrosion be significant. The corrosion rate for steel climbs drastically at a pH below 4, and at a pH of about 3 , the steel will dissolve. General corrosion tends to slow down over time because the potential gradually becomes lower. Failures of pipelines or tanks would not quickly occur from this type of corrosion since no pitting or penetration of the structure occurs, just a general corrosion over the entire surface (except under very extreme circumstances where the metal could dissolve in an acid electrolyte). However, in nature, the metal is not completely uniform and the electrolyte is not completely homogeneous, resulting in electrochemical corrosion cells that greatly overshadow this mild form of corrosion.
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Fig 12: Uniform corrosion
2) Concentration Cell Corrosion This type of corrosion is caused by an electrochemical corrosion cell. The potential difference (electromotive force) is caused by a difference in concentration of some component in the electrolyte. Any difference in the electrolyte contacting the metal forms discrete anode and cathode regions in the metal. Any metal exposed to an electrolyte exhibits a measurable potential or voltage. The same metal has a different electrical potential in different electrolytes, or electrolytes with different concentrations of any component. This potential difference forces the metal to develop anodic and cathodic regions. When there is also an electrolyte and a metallic path, the circuit is complete, current flows, and electrochemical corrosion will occur. Soil is a combination of many different materials. There are also many different types of soil, and even the same type of soil varies greatly in the concentration of its constituents. Therefore, there is no such thing as truly homogeneous soil. These soil variations cause potential differences (electromotive force) on the metal surface resulting in electrochemical corrosion cells. Liquids tend to be more uniform, but can vary in the concentration of some components such as
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Fig 13: Concentration Cell Caused by Different Environments oxygen varies by depth and flow rates. Biological organisms are present in virtually allnatural aqueous environments, these organisms tend to attach to and grow on the surface of structural materials, resulting in the formation of a biological film, or biofilm. These films are different from the surrounding electrolyte and have many adverse effects. Following are examples of common forms of concentration cell corrosion.
I. II. III. IV. V. VI. VII.
Dissimilar Environment Oxygen Concentration Moist/Dry Electrolyte Non-Homogeneous Soil Concrete / Soil Interface Backfill Impurities Biological Effects
3) Galvanic Corrosion This type of corrosion is caused by an electrochemical corrosion cell developed by a potential difference in the metal that makes one part of the cell an anode, and the other part of the cell the cathode. Different metals have different potentials in the same electrolyte. This potential difference is the driving force, or the voltage, of the cell. As with any electrochemical corrosion cell, if the electrolyte is continuous from the anode to the cathode and there is a metallic path present for the electron, the circuit is completed and current will flow and electrochemical corrosion will occur. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 33
I.
Dissimilar Metals The most obvious form of this type of corrosion is when two different kinds of metal are in the electrolyte and metallically bonded or shorted in some manner. All metals exhibit an electrical potential; each metal has its distinctive potential or voltage (paragraph 2-4). When two different metals are connected, the metal with the most negative potential is the anode; the less negative metal is the cathode. An active metal is a metal with a high negative potential, which also means it is anodic when compared to most other metals. A noble metal is a metal with a low negative potential, which also means it is cathodic when compared to most other metals. Dissimilar metal corrosion is most severe when the potential difference between the two metals, or driving voltage, is the greatest.
Metals
Fig 14: Galvanic Corrosion Cell Caused by Different
Examples of active metals are new steel, aluminum, stainless steel (in the active state), zinc, and magnesium. Examples of noble metals are corroded steel, stainless steel (in the passivated state), copper, bronze, carbon, gold, and platinum. One example of this type of corrosion occurs when coated steel pipelines are metallically connected to bare copper grounding systems or other copper pipelines (usually water lines) II. Dissimilar Alloys The most obvious example of this type of corrosion is different metal alloys. For example, there are over 200 different alloys of stainless steel. Also, metals are not 100 percent pure. They normally contain small percentages of other types of metals. Different batches of a metal vary in content of these other metals. Different manufacturers may use different raw materials and even the same manufacturer may use raw materials from different sources. Each batch of metal may be slightly different in electrical potential. Even in the same batch of metal, the
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concentration of these other materials may vary slightly throughout the finished product. All these differences will produce the electromotive force for this type of corrosion to occur. III. Impurities in Metal No manufacturing process is perfect. Small impurities may be mixed into the metal as it is produced or cooled. Impurities at the surface of the metal may become part of the electrolyte causing concentration cell corrosion, or if metallic, they may be anodic (corrodes and leaves a pit behind), or cathodic (corroding surrounding metal). Temperature Metal that is at an elevated temperature becomes anodic to the same metal at a lower temperature. As previously discussed, a more active metal is anodic to a more noble metal. Since elevated temperature makes a metal more active, it becomes anodic to the rest of the metal. This electrochemical corrosion cell may cause accelerated corrosion on metals that are at elevated temperatures.
IV.
4) Stray Current Corrosion This type of electrochemical corrosion cell is caused by an electromotive force from an external source affecting the structure by developing a potential gradient in the electrolyte or by inducing a current in the metal, which forces part of the structure to become an anode and another part a cathode. This pickup and discharge of current occurs when a metallic structure offers a path of lower resistance for current flowing in the electrolyte. This type of corrosion can be extremely severe because of very high voltages that can be forced into the earth by various sources. The potential gradient in the electrolyte forces one part of the structure to pick up current (become a cathode) and another part of the structure to discharge current (become an anode). Stray current corrosion occurs where the current from the external source leaves the metal structure and enters back into the electrolyte, normally near the external power source cathode. The external power source is the driving force, or the voltage, of the cell. Stray current corrosion is different from natural corrosion because it is caused by an externally induced electrical current and is basically independent of such environmental factors as concentration cells, resistivity, pH and galvanic cells. The amount of current (corrosion) How to control kiln shell corrosion, SCL Beawar (Raj.)
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depends on the external power source, and the resistance of the path through the metallic structure compared to the resistance of the path between the external sources anode and cathode.
External Anode and Cathode
Fig 15: Stray Current Corrosion Cell Caused by
An example of stray current corrosion is caused by impressed current cathodic protection systems, where a foreign electrically continuous structure passes near the protected structures anodes and then crosses the protected structure (cathode). This corrosion is usually found after failures in the foreign structure occur. Stray current corrosion is the most severe form of corrosion because the metallic structure is forced to become an anode and the amount of current translates directly into metal loss. If the amount of current leaving a structure to enter the electrolyte can be measured, this can be directly translated into metallic weight loss. Different metals have specific amounts of weight loss when exposed to current discharge. This weight loss is normally measured in pounds (or kilograms) of metal lost due to a current of one amp for a period of one year (one ampyear). For example, if a stray current of just two amps were present on a steel pipeline, the result would be a loss of 18.2 kilo grams (40.2 pounds) of steel in one year. For a coated pipeline, this could result in a penetration at a defect in the coating in an extremely short period of time, sometimes only a few days.
5) Crevice Corrosion Crevice Corrosion refers to the localized attack on a metal surface at, or immediately adjacent to, the gap or crevice between two joining surfaces. The gap or crevice can be formed between two metals or a metal and non-metallic material. Outside the gap or without the gap, both metals are resistant to corrosion. The damage caused by crevice corrosion is normally confined to one metal at localized area within or close to the joining surfaces. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 36
Fig 16: a type 316 stainless steel tube and tube sheet from a heat exchanger in a seawater reverse osmosis (SWRO) desalination plant suffered crevice corrosion due to the presence of crevice (gap) between the tube and tube sheet.
6) Pitting Corrosion Certain conditions, such as low concentrations of oxygen or high concentrations of species such as chloride which complete as anions, can interfere with a given alloy's ability to reform a passivating film. In the worst case, almost all of the surface will remain protected, but tiny local fluctuations will degrade the oxide film in a few critical points. Corrosion at these points will be greatly amplified, and can cause corrosion pits of several types, depending upon conditions. While the corrosion pits only nucleate under fairly extreme circumstances, they can continue to grow even when conditions return to normal, since the interior of a pit is naturally deprived of oxygen and locally the pH decreases to very low values and the corrosion rate increases due to an auto-catalytic process. In extreme cases, the sharp tips of extremely long and narrow corrosion pits can cause stress concentration to the point that otherwise tough alloys can shatter; a thin film pierced by an invisibly small hole can hide a thumb sized pit from view. These problems are especially dangerous because they are difficult to detect before a part or structure fails. Pitting remains among the most common and damaging forms of corrosion in passivated alloys, but it can be prevented by control of the alloy's environment.
Fig 17: Scheme of pitting corrosion
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What are Refractories
Any material can be described as a refractory, if it can withstand the action of abrasive or corrosive solids, liquids or gases at high temperatures. The various combinations of operating conditions, in which refractories are used, make it necessary to manufacture a range of refractory materials with different properties. Refractory materials are made in varying combinations and shapes depending on their applications. General requirements of a refractory material are:
Withstand high temperatures Withstand sudden changes of temperatures Withstand action of molten metal slag, glass, hot gases, etc Withstand load at service conditions Withstand load and abrasive forces Conserve heat Have low coefficient of thermal expansion Should not contaminate the material with which it comes into contact
Depending on the area of application such as boilers, furnaces, kilns, ovens etc, temperatures and atmospheres encountered different types of refractories are used. Some of the important properties of refractories are: a) Melting Point Pure substances melt instantly at a specific temperature. Most refractory materials consist of particles bonded together that have high melting temperatures. At high temperatures, these particles melt and form slag. The melting point of the refractory is the temperature at which a test pyramid (cone) fails to support its own weight. b) Size The size and shape of the refractories is a part of the design of the furnace, since it affects the stability of the furnace structure. Accurate size is extremely important to properly fit the refractory shape inside the furnace and to minimize space between construction joints. c) Bulk Density The bulk density is useful property of refractories, which is the amount of refractory material within a volume (kg/m3). An increase in bulk density of a given refractory increases its volume stability, heat capacity and resistance to slag penetration. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 38
d) Porosity The apparent porosity is the volume of the open pores, into which a liquid can penetrate, as a percentage of the total volume of the refractory. This property is important when the refractory is in contact with molten charge and slag. A low apparent porosity prevents molten material from penetrating into the refractory. A large number of small pores is generally preferred to a small number of large pores. e) Cold Crushing Strength The cold crushing strength is the resistance of the refractory to crushing, which mostly happens during transport. It only has an indirect relevance to refractory performance, and is used as one of the indicators of abrasion resistance. Other indicators used are bulk density and porosity. f) Pyrometric cones and Pyrometric cones equivalent (PCE) The refractoriness of (refractory) bricks is the temperature at which the refractory bends because it can no longer support its own weight. Pyrometric cones are used in ceramic industries to test the refractoriness of the (refractory) bricks. They consist of a mixture of oxides that are known to melt at a specific narrow temperature range. Cones with different oxide composition are placed in sequence of their melting temperature alongside a row of refractory bricks in a furnace. The furnace is fired and the temperature rises. One cone will bends together with the refractory brick. This is the temperature range in oC above which the refractory cannot be used. This is known as Pyrometric Cone Equivalent temperatures.
Fig 17: Pyrometric cones g) Creep at high Temperature Creep is a time dependent property, which determines the deformation in a given time and at a given temperature by a refractory material under stress. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 39
h) Volume stability, expansion, and shrinkage at high temperatures The contraction or expansion of the refractories can take place during service life. Such permanent changes in dimensions may be due to: The changes in the allotropic forms, which cause a change in specific gravity A chemical reaction, which produces a new material of altered specific gravity The formation of liquid phase Sintering reactions Fusion dust and slag or by the action of alkalies on fireclay refractories, to form alkali-alumina silicates. This is generally observed in blast furnaces
i) Reversible thermal expansion Any material expands when heated, and contracts when cooled. The reversible thermal expansion is a reflection on the phase transformations that occur during heating and cooling. j) Thermal Conductivity Thermal conductivity depends on the chemical and mineralogical composition and silica content of the refractory and on the application temperature. The conductivity usually changes with rising temperature. High thermal conductivity of a refractory is desirable when heat transfer though brickwork is required, for example in recuperators, regenerators, muffles, etc. Low thermal conductivity is desirable for conservation of heat, as the refractory acts as an insulator. Additional insulation conserves heat but at the same time increases the hot face temperature and hence a better quality refractory is required. Because of this, the outside roofs of open-hearth furnaces are normally not insulated, as this could cause the roof to collapse. Lightweight refractories of low thermal conductivity find wider applications in low temperature heat treatment furnaces, for example in batch type furnaces where the low heat capacity of the refractory structure minimizes the heat stored during the intermittent heating and cooling cycles. Insulating refractories have very low thermal conductivity. This is usually achieved by trapping a higher proportion of air into the structure. Some examples are: Naturally occurring materials like asbestos are good insulators but are not particularly good refractories Mineral wools are available which combine good insulating properties with good resistance to heat but these are not rigid Porous bricks are rigid at high temperatures and have a reasonably low thermal conductivity. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 40
Type of Refractories
Refractories can be classified on the basis of chemical composition, end use and methods of manufacture as shown below. Classification method Chemical Composition ACID, which readily combines with bases BASIC, which consists mainly of metallic oxides that resist the action of bases NEUTRAL, which does not combine with acids nor bases Special End use Method of manufacture Example Silica, Semisilica, Aluminosilicate Magnesite, Chrome-magnesite, Magnesitechromite, Dolomite Fireclay bricks, Chrome, Pure Alumina Carbon, Silicon Carbide, Zirconia Blast furnace casting pit Dry press process, fused cast, hand moulded, formed normal, fired or chemically bonded, unformed (monolithics, plastics, ramming mass, gunning castable, spraying) Table 3: Classification of refractories based on chemical composition
a. Fireclay refractories Firebrick is the most common form of refractory material. It is used extensively in the iron and steel industry, nonferrous metallurgy, glass industry, pottery kilns, cement industry, and many others. Fireclay refractories, such as firebricks, siliceous fireclays and aluminous clay refractories consist of aluminum silicates with varying silica (SiO ) content of up to 78 percent and Al O content of up to 44 percent. Table 4 shows that the melting point (PCE) of fireclay brick decreases with increasing impurity and decreasing Al O . This material is often used in furnaces, kilns and stoves because the materials are widely available and relatively inexpensive. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 41
2 3 2 3 2
Brick Type Super Duty High Duty Intermediate High Duty Siliceous Low Duty
Percentage SiO2
49-53 50-80 60-70 65-80 60-70
Percentage Al2O3
40-44
Percentage other constituents 5-7 5-9 5-9 3-8 6-10
PCE C 1745-1760 1690-1745 1640-1680 1620-1680 1520-1595
35-40 26-36
18-30 23-33
Table 4: Properties of fireclay Bricks b. High alumina refractories Alumina silicate refractories containing more than 45 percent alumina are generally termed as high alumina materials. The alumina concentration ranges from 45 to 100 percent. The refractoriness of high alumina refractories increases with increase in alumina percentage. The applications of high alumina refractories include the hearth and shaft of blast furnaces, ceramic kilns, cement kilns, glass tanks and crucibles for melting a wide range of metals. c. Silica Brick Silica brick (or Dinas) is a refractory that contains at least 93 percent SiO2. The raw material is quality rocks. Various grades of silica brick have found extensive use in the iron and steel melting furnaces and the glass industry. In addition to high fusion point multi-type refractories, other important properties are their high resistance to thermal shock (spalling) and their high refractoriness. The outstanding property of silica brick is that it does not begin to soften under high loads until its fusion point is approached. This behavior contrasts with that of many other refractories, for example alumina silicate materials, which begin to fuse and creep at temperatures considerably lower than their fusion points. Other advantages are flux and stag resistance, volume stability and high spalling resistance. d. Magnesite Magnesite refractories are chemically basic materials, containing at least 85 percent magnesium oxide. They are made from naturally occurring magnesite (MgCO3). The properties of magnesite refractories depend on the concentration of silicate bond at the operating temperatures. Good quality magnesite usually results from a CaO-SiO2 ratio of less than two with a minimum ferrite concentration, particularly if the furnaces lined with the refractory operate in oxidizing and reducing conditions. The slag resistance is very high particularly to lime and iron rich slags. How to control kiln shell corrosion, SCL Beawar (Raj.)
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e. Chromite Refractories Two types of chromite refractories are distinguished: Chrome-magnesite refractories, which usually contain 15-35 percent Cr O and 42-50 percent MgO. They are made in a wide range of qualities and are used for building the critical parts of high temperature furnaces. These materials can withstand corrosive slags and gases and have high refractoriness. Magnesite-chromite refractories, which contain at least 60 percent MgO and 8-18 percent Cr O . They are suitable for service at the highest temperatures and for contact with the most basic slags used in steel melting. Magnesite-chromite usually has a better spalling resistance than chrome-magnesite. f. Zirconia Refractories Zirconium dioxide (ZrO2) is a polymorphic material. It is essential to stabilize it before application as a refractory, which is achieved by incorporating small quantities of calcium, magnesium and cerium oxide, etc. Its properties depend mainly on the degree of stabilization, quantity of stabilizer and quality of the original raw material. Zirconia refractories have a very high strength at room temperature, which is maintained up to temperatures as high as 15000C. They are therefore useful as high temperature construction materials in furnaces and kilns. The thermal conductivity of zirconium dioxide is much lower than that of most other refractories and the material is therefore used as a high temperature insulating refractory. Zirconia exhibits very low thermal losses and does not react readily with liquid metals, and is particularly useful for making refractory crucibles and other vessels for metallurgical purposes. Glass furnaces use zirconia because it is not easily wetted by molten glasses and does not react easily with glass. g. Oxide Refractories(Alumina) Alumina refractory materials that consist of aluminium oxide with little traces of impurities are known as pure alumina. Alumina is one of the most chemically stable oxides known. It is mechanically very strong, insoluble in water, super heated steam, and most inorganic acids and alkalies. Its properties make it suitable for the shaping of crucibles for fusing sodium carbonate, sodium hydroxide and sodium peroxide. It has a high resistance in oxidizing and reducing atmosphere. Alumina is extensively used in heat processing industries. Highly porous alumina is used for lining furnaces operating up to 1850oC. h. Monolithics Monolithic refractories are single piece casts in the shape of equipment, such as a ladle as shown in Figure 18. They are rapidly replacing the conventional type fired refractories in many applications including industrial furnaces. The main advantages of monolithics are: How to control kiln shell corrosion, SCL Beawar (Raj.) Page 43
2 3 2 3
Elimination of joints which is an inherent weakness Faster application method Special skill for installation not required Ease of transportation and handling Better scope to reduce downtime for repairs Considerable scope to reduce inventory and eliminate special shapes Heat savings Better spalling resistance Greater volume stability
Monolithics are put into place using various methods, such as ramming, casting, gunniting, spraying, and sand slinging. Ramming requires proper tools and is mostly used in cold applications where proper consolidation of the material is important. Ramming is also used for air setting and heat setting materials. Because calcium aluminate cement is the binder, it will have to be stored properly to prevent moisture absorption. Its strength starts deteriorating after 6 to 12 months.
Fig 18: A monolithic lining for Ladel
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Type and Composition of refractory used at SCL, Beawar (kiln 2) Brick Type TOPMAG A1 ALMAG 85 FERROMA G 90 MagnesiaMagnesiaMagnesiaFused Spinel Fused Spinel Hercynite Characteristi 77-81 MgO 85-89MgO 87-92MgO c Component in % bulk density 2.9-3.05 2.85-3 2.85-3 (g/cm3) Apparent 15-17 16-18 16-18 porosity % 65 50 50 Cold Crushing Strength N/mm2 Seger Cone >42 >42 >42 Thermal 400C 0.3 0.4 0.4 expansion 800C 0.9 0.8 0.9 Lin. % at 1200C 1.4 1.4 1.5 Thermal 100 100 100 Shock resistance at 950C/air Thermal 3.9 4 3.7 Conductivity 300C 700C 2.9 3 3 W/m.K at 1000C 2.6 2.7 2.6 upper transition upper and lower burning Typical field zone, tyre transition zones zone and of section subject subject to severe upper application
to high mechanical load with redox conditions and extreme alkali attack, chrome ore free service conditions with alkali attack and redox conditions, chrome ore free
PERILEX 83 MagnesiaChromite 81-85MgO 2.9-3.05 17-19 55
42 0.4 1.1 1.7 80
4 3 2.8
transition zone, good coatability, chrome ore free
burning Zones as well as upper and lower transition Zones subject to severe service conditions,low Chrome Content
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Above mentioned refractories are imported bricks. These bricks are basic bricks. Currently these bricks are using in Kiln-2(at outlet where temperature is very high) with addition of high Alumina bricks at kiln inlet where temperature is not so high. Where as in kiln-1 we are using only High Alumina bricks. Currently High Alumina Bricks (made in India) using in Kiln-1 and in inlet of kiln-2. Product name Maximum C.C.S. Recommended (Kg/Cm2) Temperature (C) 1420 1480 1460 395 545 720 Chemical analysis Refractoriness Pyrometric Cone.orton Material Req.
Al2O3 40.5 59.2 69.8
Fe2O3 2.15 2.5 3 30 35 36 2.21 2.42 2.61
AC 40S AC 60S AC 70S
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Fig 19: Refractory lining of kiln-1
For Kiln-1
Full details of Refractory linings, Coating and SS Plate Used:
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For Kiln-2
Fig 20: Refractory lining of Kiln-2
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Corrosion of Kiln Shell

Introduction With the ever increasing demand of cement due to the exponential growth of construction industry, Indian Cement Industry has been put to perform at its best than ever before. With the advances in understanding the cement chemistry and material behavior in side rotary kiln, lot many alternate raw materials and fuels have been either in use or being investigated for their suitability. While these alternate raw materials and fuels proved to be beneficial in terms of financial aspects associated with them, but the presence of deleterious volatile compounds posed equally serious threats to cause problems such as kiln shell corrosion, build ups and rings besides attacking the refractory lining and reducing their campaign lives. Amongst these, kiln shell corrosion is most serious problem as it acts silently and reduces the shell thickness to below critical structural and mechanical limits of stability of kiln shell. Corrosion can be defined as the destruction or deterioration of material due to the reaction with its environment. The grades of steel used for kiln shell range from general engineering steel to low alloy steels. The minimum shell plate thickness is around 20 mm for the shell section between two supports and those under the tyres (riding rings) may be between 6080 mm thick. A reduction of the shell thickness due to corrosion can be presumed to be critical when the thickness of the shell becomes 15 mm or so. To overcome the problem of kiln shell corrosion, the best way could be to prevent the volatiles to reach upto kiln shell. To prevent the passage of volatiles, refractories play a vital role and the selection of proper quality, adequate installation measures and highly oxidizing conditions in hottest zone of the kiln, stable kiln operation at high speed proved as the key to reduce / minimize the extent of kiln shell corrosion. Here I will try to bring out the role of the refractories and process conditions to reduce / minimize the kiln shell corrosion based upon the studies carried out in the past.
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Corrosion of Cement Kiln Corrosion of cement kiln shell is influenced by a number of factors such as composition of the metallic shell and its environment, temperature of the shell, cleanliness or roughness of the shell surface, its contact with other materials and severe process conditions. Further, it is determined largely by the degree to which the scale formed under particular condition blocks further action between the shell and environment. Each steel or alloy behaves more or less individually and forms its own characteristic type of scale whose composition and imperviousness are specific to the given alloy, atmosphere, temperature and duration of exposure. Consequently, even a slight difference in composition of steel or atmosphere for instance, the presence of sulphur may have a substantial influence upon the type and progress of corrosion. It has been reported that carbon dioxide and sulphur dioxide are active scaling agents of iron and steel, carbon dioxide being less deterrent. The presence of sulphur dioxide increases rate of scaling and often results in deep intergranular penetration of the steel through the formation of a liquid iron oxide iron sulphide eutectic. The deleterious effects of sulphur dioxide can be offset by providing excess oxygen. Alloying elements such as chromium, aluminium and silicon present in steel may greatly affect the rate of scaling. When present in significant concentration, they oxidize rapidly yielding a relatively impervious film which retards the rate of further attack on the underlying metal. On the other hand a high concentration of sulphur increases the rate of attack just as does the sulphur in the atmosphere. The influence of carbon is relatively small. The main reason of shell corrosion can be attributed to alternate oxidation at high temperature and acidic reaction at low temperatures when the kiln is stopped for repairs. The corrosion phenomenon takes place mainly due to presence of oxides, chlorides and sulphide at high temperature. Various types of corrosion that affect the kiln shell are: (i) Corrosion due to oxidation under high temperature (ii) Corrosion due to sulphide under high temperature (iii) Corrosion due to chloride under high temperature (iv) Corrosion due to hygroscopic material The rate of corrosion depends on the material, the surface condition, the corrosion medium, the time available and the temperature. The resistance to scaling of steels also diminishes in consequence of frequent temperature changes. Investigations have shown that in the majority of cases the corrosive attack is intensified by frequent changes in temperature. In most cases, the damage due to high temperature corrosion manifests
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itself in general removal of material or in superficial cracking. Oxidation in the kiln atmosphere is possible due to the presence of O2, H2O/ H2, CO2/CO. The occurrence of high temperature corrosion under surface deposits is also an important factor. The damage due to corrosion is always intensified if the surface of the affected portion is covered with such deposits. During fairly long kiln shutdown for repairs, a rusting process is also presumed to be superimposed upon the high temperature corrosion (scaling) that has occurred during kiln operation. The deposit of salts containing potassium chloride in particular on the shell becomes active because being hygroscopic it absorbs atmospheric moisture. It is observed that the chloride can reach the kiln shell in the form of gases, the same is not the case for alkali oxides. Alkalis can only penetrate the lining as a part of liquid potassium and / or Sodium salt melts. If the corrosion products therefore contain substantial quantities of Potassium or Sodium, the form of corrosion is termed as Hot Corrosion indicating that liquid phase takes part in the corrosion reactions. Mechanism of kiln shell corrosion The reactions inside the kiln are different from reactions on the kiln shell surface since both the temperature and atmosphere are different. One of the most important reactions in the lining is the oxygen consumption where SO2 consumes oxygen and condenses as SO3: 2 SO2 (g) + O2 = 2 SO3 () The SO3 formed condenses as calcium or magnesium salts. The result can be that an oxidizing environment inside the kiln turns into a reducing environment at the kiln shell. Oxidation In an oxidizing atmosphere, the iron from the steel shell will react with oxygen to form an oxide scale. Generally, this oxide scale is formed by more or less firm layers of different iron oxides, the compound with the highest oxygen content, Fe2O3, being found at the scalebrick interface, and the compound with the highest iron content, FeO at the metal-scale interface. At normal kiln operating temperatures, the outer layer becomes relatively firm. Sulphidization When no oxygen is present, SO2 takes over as the oxygen donor and a different reaction occurs. The reaction may be written as follows: 4 Fe + 2 SO2 (g) = Fe3O4 + FeS2 How to control kiln shell corrosion, SCL Beawar (Raj.) Page 53
Accordingly, a sulphidization reaction can be identified by the occurrence of either pyrite (FeS2) or pyrrhotite (FeS) in the corrosion products. The oxidation by O2 and by SO2 alternates. As sulphide layers are more porous than oxide layers, the corrosion rate of the shell will increase. However, experience from different plants shows that, as long as chlorides are not present, the corrosion rate stays at an acceptably low level. Sulphidization is enhanced by the presence of chlorides, mainly because they affect the morphology of the corrosion scale, hindering the formation of a strong, protective oxide layer. The total reaction is a chain process taking place at different temperatures. A temperature gradient between the kiln atmosphere and the kiln shell is created by the porous deposit and the refractory lining. The first reaction of the chain process takes place in the kiln and can be described as high temperature hydrolysis of the thermally unstable alkali chlorides to form the more stable sulphates. This reaction step is followed by reoxidation of hydrogen chloride gas (by oxygen or SO2) at lower temperatures to produce elemental chlorine, which attacks the kiln shell. The basic reactions (with potassium as alkali) are: 2 KCl (g) + H2O (g) + SO2 (g) + O2 (g) = K2SO4 + 2 HCl (g) (T > 900oC) 2 HCl (g) + O2 (g) = Cl2 (g) + H2O (T < 400oC) The formation of free hydrochloric acid (HCl) gas in cement kilns is thus accompanied by formation of alkali sulphates. When this is the case, the formation is restricted to a quite narrow temperature between 1100 oC and 1300oC. The formation of hydrochloric acid is a consequence of the thermal instability of calcium sulphate and the thermal stability of potassium sulphate. The evaporation of alkali chlorides cannot begin until these temperatures are reached since gas and material move counter-current in the kiln. If most of the KCl in kiln feed can evaporate to KCl (g) at temperatures below 1000 to 1150 oC, the formation of HCl (g) will be quite limited because the tendency of KCl (g) to hydrolyse at such temperatures is low. The low temperature evaporation of chlorides explains why normal preheater kilns are less vulnerable to chloride-enhanced sulphidization. While, in most cases, chlorides in preheater kilns evaporate during or shortly after calcinations without substantial formation of hydrogen chloride gas, the case is different for kilns with tertiary air duct. Such kilns will show delayed alkali chloride evaporation and, consequently, evaporation will be followed by more extensive hydrolysis of the chlorides. Once Cl2 (g) is formed, it can reach the kiln shell through the refractory bricks or through the gaps/joints within and between rings and will react with either the oxide-sulphide How to control kiln shell corrosion, SCL Beawar (Raj.) Page 54
layers or, most likely, directly with the kiln shell according to the following reactions resulting in the corrosion of the kiln shell: reaction with the oxide-sulphide layers: FeS + Fe3O4 + 4 Cl2 = 4 FeCl2 + SO2 + O2 reaction with the kiln shell: Cl2 + Fe = FeCl2 Role of Refractories in tackling shell corrosion The role of refractories in cement kiln is primarily to protect the steel shell from the direct attack of deleterious gases and clinker melt and to reduce the shell temperature so that steel of the shell does not loose its properties. The reduction in shell temperature also leads to energy conservation besides providing a workable condition near kiln shell. The entire CRK system including, preheater, precalciner, rotary kiln and cooler is lined with suitable size and quality of refractories to achieve the above mentioned advantages. Amongst all the sections as mentioned above, the service conditions inside the rotary kiln are most severe thereby requiring special attention for the shape, type and quality of refractories to be used and installation practices to be employed. Passage of Volatiles through Bricks The various studies carried out by NCB have established that volatile pass through the body of the refractory bricks and reach up to kiln shell. The samples of worn out refractory bricks as collected during visits were cut into three sections, top, middle and bottom and these were subjected to chemical and mineralogical investigations to find out the mineral phases present and formation of new phases. The results of chemical analysis and XRD investigations are given in Table 5 and Table 6 respectively for all the cases.
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Brick Area
Al2O3 Fe2O3 K2O Fresh Brick 72.35 2.49 0.38 Worn out Brick-Top Layer Case I 60.57 3.56 15.08 0.76 0.17 6.75 Case II 69.40 2.33 16.39 0.96 0.29 3.35 Case III 62.10 4.00 19.81 0.37 0.44 5.20 Worn out Brick-Middle Layer Case I 65.86 3.47 14.21 0.24 0.19 6.86 Case II 70.70 3.37 14.31 0.52 0.55 2.21 Case III 63.20 3.77 19.48 0.21 0.22 3.70 Worn out Brick-Bottom Layer Case I 74.40 5.31 16.32 0.22 0.18 1.49 Case II 70.18 3.10 15.64 0.91 0.40 0.81 Case III 65.22 5.60 18.60 0.30 0.31 0.90 Table 5: Chemical Analysis of Different Layers of Worn Out Bricks
Chemical Constituents % SiO2 SO3 Na2O 17.85 0.07 0.16
Cl 0.01 1.00 0.41 0.35 1.30 0.46 0.24 0.06 0.12 0.32
The results of chemical analysis of the top layer indicate that bricks have undergone very severe chemical attack, which has resulted in decrease of Alumina content. The concentration of SO3, Na2O and K2O was in the range of 0.37 0.96, 0.17-0.44 and 3.35-6.75 percent respectively. The concentration of chloride was in the range of 0.35-1.00 percent. The results of chemical analysis of middle layer indicate that the volatiles have traveled through the bricks and have reached upto the middle layer of the bricks. Concentration of SO3, Na2O and K2O are in the range of 0.21-0.52, 0.19-0.55 and 2.21-6.86 percent respectively. The concentration of chloride was in the range of 0.24-1.30 percent.
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S. Plants No Top layer 1 Unused bricks Al2O3, Al6 Si2O13 2 Case I
Mineral compounds present in Middle layer Bottom layer Al2O3, Al6 Si2O13 Al2O3, Al6 Si2O13 Al2O3, KAlSi3O8, Al2O3, Al6 Si2O13, ,KCl KAlSiO4,
Al2O3, KAlSi3O8, Al6 Si2O13, KAlSiO4, Ca2.Al2SiO7 , KCl
Al6 Si2O13,
Ca2.Al2SiO7 ,KCl 3 Case II Al2O3, KAlSi3O8, Al2 SiO5, Na2SO4, Ca2.Al2SiO7 KCl Al2O3, KAlSi3O8, Al2O3, KAlSi3O8, Al2 SiO5, Ca2.Al2SiO7 Al2O3, Al2 SiO5, Ca3.Al6O12.CaSO4, KCl Al2O3, Al6Si2O13, Al2O3 Na2SO4,
NaCl 4 Case III Al2O3, Al6Si2O13, Ca.Al2Si2O8 , KCl
KAlSi2O6,Al2 SiO5,
Al2O3SiO2
,
Al6Si2O13, KCl, KAl.Si2O6 ,
NaCl
SiO2, SiO2 Fe2O3, KCl,
K2SO4, NaCl Table 6: XRD Investigations of different layers of Refractory Bricks The results of chemical analysis of bottom layer of refractory bricks indicate that the concentration and reactivity of these volatiles is so high that these are able to travel upto the bottom of the bricks thereby reaching upto the kiln shell. The concentration of SO3, Na2O and K2O are in the range of 0.22-0.91, 0.18-0.40 and 0.81-1.49 percent respectively. The concentration of chloride was in the range of 0.06-0.32 percent. The comparison with the top and middle layer indicates that the concentration of volatiles has decreased.
The results of XRD investigations of corresponding samples also indicate the interaction of bricks with deleterious volatile oxides leading to formation of feldsphatic compounds like Al6Si2O13, KAl.Si2O6 , Ca.Al2Si2O8, besides formation of most detrimental oxide i.e. KCl (sylvite). Formation of these compounds in the brick matrix led to volume expansion and breaking of ceramic bonds ultimately leading to breaking or loosening of bricks.
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The above investigations of worn out refractory bricks have provided very useful information for the possible causes of kiln shell corrosion. The chemical analysis of top layers of bricks indicate that these bricks have undergone severe interaction with calcined kiln feed or clinker and have absorbed volatiles through the open pores in the bricks. The bricks have three types of pores namely: Through pores Closed pores within brick body One side open and one side closed pores Out of all the three types of pores, one side open and one side closed pores basically create problem for brick failure and does not directly affect the phenomena of kiln shell corrosion. The closed pores are the ones which neither damage brick structure by way of interaction nor help in kiln shell corrosion.
The third types of pores are very dangerous from the point of view of damaging the brick structure as well as causing kiln shell corrosion. Because these thorough pores provide passage to volatiles to reach up to kiln shell. The best approach would be to check the permeability of these bricks before dispatch from the site of manufacturers. The permeability of bricks gives a very clear picture of through pores present in the bricks. Passage of Volatiles through joints/gaps The volatile rich kiln gases and clinker liquid are very prone to reach upto to kiln shell through the gaps between joints within individual rings or ring to ring joints as well. These gaps may occur due to various reasons such as: Individual brick behavior at working temperature Inadequate installation due to poor workmanship Actual service conditions prevailing inside the kiln In order to confirm the possibility of volatiles traveling through the gaps within and between rings and reaching at the interface of bricks and kiln shell, another exercise was carried out. While collecting brick samples during kiln stoppage, some of the rings have shown shifting and gaps created between rings. Samples of worn out bricks were carefully taken out ensuring the coatings on the side surfaces of bricks to remain intact. These coatings were scrapped carefully and analyzed for their chemical constituents. The results of analysis indicate that two types of reactions are taking place.
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chloride confirm severe reaction at the interface resulting in formation of highly aggressive liquid which entered through the gap and reaching up to kiln shell. At the interface of bottom layer of brick and kiln shell, this liquid has reacted with kiln shell and complex compounds have formed. This phenomenon is confirmed by increased Fe2O3 content (6.80 %) in the scrapings obtained from side bottom of brick. Figure 21 is showing the photograph of a brick having heavy coating on one of its side. In another case, the scrapping obtained from brick has shown totally different reaction mechanism. Here the volatile available at kiln surface have reacted with shell material and intermediate compounds of Fe2O3 and sulfur are formed in liquid state. The presence of chloride has further aggravated the situation and severe shell corrosion has taken place. These liquids then deposited on the gaps between and within rings. Figure 22 is showing the brick with heavy metallic deposit on one of its side.
In one case, the results indicate that severe interactions between brick, clinker liquid rich in volatiles and material of kiln shell have taken place. The scrapping of coatings on brick side-top has composition which indicates severe reaction with clinker melt and brick material. The enrichment of volatiles as high as 2.60 % SO3 and 7.11 % K2O and 0.39 %
Fig 21: Clinker melt deposit on side walls of brick
Fig 22: Metallic Deposit on one side of brick
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The above clearly confirm that the passage of clinker liquids rich in volatiles and hot volatile gases is much more dangerous as their concentration at the place of corrosion becomes alarmingly high and severe reaction takes place between kiln shell and clinker rich in volatiles / volatile gases leading to shell corrosion. Role of Process Parameters on Shell Corrosion The kiln shell temperature is of major importance to the speed of shell corrosion. In all the studies carried out by NCB, the shell temperature of the affected areas has been found to be on the higher side reaching as high as 400 0C thus providing a very conducive conditions at inner shell to form scale. As known, the carbon steel is poor in oxidation therefore rate of oxidation increase rapidly with the increase in temperature. It has been reported that the rate of oxidation at 400OC is almost fourteen times than that at 2000C and it increases manifolds with the increase in temperature. In a rotary kiln where the temperature of outside surface of shell is 300 4000C, the inside temperature is expected to be much higher and the oxidation rate at that temperature could be considerably high which is not desirable. Another factor influencing the problem of corrosion is the poor oxidizing conditions inside the kiln. It is quite clear that O2 and SO2 act alternately as oxygen donors for most of the corrosion with chloride gas acting as the main promoter, making the corrosion layers porous so that they offer no diffusion protection against further thermal and chemical attack. The gas analysis measurements indicate severe oxygen deficient conditions at kiln inlet in all the cases. The measurements of CO / O2 at kiln inlet were carried out and presented in Table 7 below: S.No. 1 2 3 O2% CO% Case I 0.79-1.67 0.10-2.12 Case II 0.60-2.00 0.20-0.60 Case III 0.19-0.31 0.90-1.66 Table 7: Measurement of CO/O2 at kiln inlet Plant Gas Analysis
From the above table it is clear that the O2 and CO levels are far from the recommended limits of 1.5 and 0.1 percent respectively. Sometime, it was found that the CO/O2 analyzer installed at kiln inlet is showing incorrect readings and their levels could not be maintained / controlled to the above recommended limits. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 60
The high rate of corrosion in the burning/pre-burning zone can be due to the fact that the sulphate bearing compounds gets recycled along with feed material and travel up to burning zone where they get partially dissociated and vaporized once again. Due to this, the increase in SO3 concentration takes place leading to the increase in partial pressure of these volatile gases over a period of time. As a result, they get diffused through the open pores of refractory lining reach upto the kiln shell and initiate the corrosion process. Many laboratory experiments conducted elsewhere have reported that high levels of carbon monoxide due to incomplete combustion of coal also increases the rate of corrosion. In one of the kiln where the inlet CO formation is going as high as 2.12%, it can easily be expected that the CO content in the burning zone will be much higher. Thus, it is essential to burn the fuel completely and as fast as possible to avoid any CO formation or reducing conditions to exist in any part inside the kiln and to have proper and sufficient oxidizing conditions. The chemical analysis of Kiln Shell Flakes indicate that these flakes are formed from the original material of kiln shell and heavy to severe interaction with volatile oxides have taken place at the interface. The concentration of SO3, Na2O and K2O are in the range of 0.443.46, 0.21-0.72 and 0.79-2.49 percent respectively. The concentration of chloride was in the range of 2.90-5.53 percent and is considered to be very high. Oxides LOI SiO2 Fe2O3 Al2O3 CaO MgO SO3 Na2O K2O Cl Plants Case I Case II 5.74 9.68 3.17 2.10 67.32 64.02 12.56 13.08 2.08 1.25 0.30 0.25 3.46 0.83 0.61 0.72 1.60 2.49 2.90 5.18 Table 8: Chemical Analysis of Kiln Shell Flakes Case III 23.40 1.62 63.48 2.50 1.71 0.38 0.45 0.21 0.80 5.63
The XRD investigations also confirms the formation of compounds FeS2, NaFeS2, NaCl,, KCl, FeS as major mineral phases in almost all the samples of kiln shell flakes and the other mineral phases present were Fe2O3, Fe3O4, Na2SO4,, MgFe2O4, Al0.5Si0.7O2.25, K6Na4Cl, etc. The presence of these compounds clearly indicates that the participating oxides for these compounds were Iron from kiln shell and volatiles reached to kiln shell surface through bricks and gaps/joints. How to control kiln shell corrosion, SCL Beawar (Raj.)
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Recommendations

The possible causes for the occurrence of shell corrosion in cement kiln could therefore be summarized as under: Penetration of refractories and attack of alkalis on kiln shell Poorly designed Brick shape and size, Poor Brick quality in terms of porosity and permeability Inadequate Installation quality Improper combustion of fuel leading to reducing conditions inside kiln
The possible preventive measures coming out from the above studies to minimize the tendency and rate of shell corrosion phenomenon are as discussed below: A) It seems to be more successful to apply different type of gas-tight coatings or paints on the inner kiln shell to lessen the chloride attack. The inner kiln shell should be coated with the available anti corrosive paint immediately after delining. This will also help in preventing the absorption of atmospheric moisture by hygroscopic compounds such as KCl. a) One coating KilnGard-600SCW which is manufactured by 3L&T Company has been proven a good Anti-Corrosive Coatings for cement kilns. This coating has been used in many cement plants of Mexico, Colombia and Brazil. The results obtained after using this coating in cement kilns are shown on next page. It shows that firstly they used SS plate to Combat Corrosion but just after 11 months there was a decrease of 1.3mm in thickness of Shell (Figure 1 on next page). After that they used KilnGard-600SCW and after 12 month the thickness of shell was practically same (Figure 6 on next page).
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B) Silicon Carbide compounds are an effective solution for corrosion resistance. At operating temperature, decomposition and oxidation form specific glass phasesblocking the porosity and forming new phases with the alkalis without disruptive growth. There is little to no spalling of the hot face and alkali penetration is reduced. Our CALDE RAM and CALDE PATCH ranges, present very good resistance to alkali corrosion. The alkalis may penetrate the surface, but they will not develop new expanding compounds.
C) Basic reason of corrosion is alkalis so to remove these alkalis we can use alkali by-pass system. Alkali Bypass is a duct between the feed end of the kiln and the preheater tower through which a portion of the kiln exit gas stream is withdrawn and quickly cooled by air or water to avoid excess buildup of alkali, chloride and/or sulfur on the raw feed. This may also be referred to as the kiln exhaust gas bypass. Currently at SCL we are using Rotary Kiln Manufactured by KHD.KHD also provide service of Bypass system. Bypass Systems of KHD The development of efficient KHD Bypass Systems significantly contributed to the success of the KHD preheater concept and, consequently, to a modern and energy-saving low alkali high quality clinker production system.
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For many years KHD plants have initially been provided with KHD Bypass Systems which are operating with raw materials of high chloride or sulfate content. Especially for using secondary raw materials and secondary fuels of significant chlorine and/or sulfur contents the KHD Bypass System enables a flexible kiln operation at varying fuel and/or raw-material mixtures.
A portion of the volatile components will be removed from in the area of the inlet chamber by means of a bypass and thus be withdrawn from the circuit. This will lower the level of the volatile circuit to such an extent that coatings remain controllable and operational reliability.
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D) The kiln shell temperature from outside should not exceed 300C.
Additional cooling fans should be provided for effective external cooling. In addition, the selection of bricks in this area should be reviewed with respect to their thermal conductivity and wear rate pattern. If there is no coating on bricks in that area, high wear rate leads to reduced residual lining thickness leading to higher shell temperature. Therefore, Refractory bricks with relatively lower thermal conductivity and high wear resistance should be preferred in the corrosion affected area. Here is attached the kiln shell Temperature profile of Kiln-2 at SCL,Beawar. We can see that Maximum Temperature is around 390C.which is very high compare to recommend above. So some extra cooling fans should be provided for effective external cooling. Note: - Shell Temperature Profile and max. min. Temp. of shell of Kiln-2 is attached at the end of this report.
E) As the investigations have confirmed that the intrusions of volatiles have
taken place not only through the bricks but also through joints and gaps created during the campaign. It is recommended that a thorough study of lining quality, design and installation be carried out with a view to ensure that the intrusion of volatiles through bricks and joints/gaps is reduced to minimal. In this connection, it is very important to mention here that besides other parameters, two characteristics should be given due attention namely, permeability and reversal thermal expansion of bricks, While permeability plays a role in allowing gases/liquids to reach up to kiln shell, the reversal thermal expansion gives an idea of extent of shrinkage a particular brick undergo when the kiln temperature is reduced from its normal operating temperature to any lower temperature.
F) The shell corrosion is attributed to a large extent to poor oxidizing conditions prevailing in the kiln. The best measure against chloride promoted sulphidization is to keep a steady supply of fresh air to the
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surface of the kiln shell. The CO/O2 analyzer installed at the kiln inlet should be made working properly to avoid incomplete combustion of coal which otherwise could lead to uncontrolled/unnoticed formation of CO and low oxygen level at kiln inlet. The oxygen at kiln inlet should be maintained at 1.5 % minimum to ensure proper oxidizing conditions with CO not exceeding 0.1 percent at this point. Here at SCL the % Composition of O2 and CO at Kiln-2 inlet is 5-6% and 0.010.15% respectively. So by looking at above composition we can say that here oxidizing conditions are not poor. These compositions are not aid in corrosion of kiln shell. So in future also company should maintain these conditions.
G) Currently in plant we are using combination Basic Magnesia Refractory and high Alumina refractories in Kiln-2.but we are not using basic refractory in kiln-1.In kiln-1 we are using only high Alumina Refractory. In view of corrosion and heat loss use of Basic refractory is highly recommended. Although basic refractories are costlier than neutral refractories but they provide more service time and more resistance to corrosion and alkali attack. H) Ultra-ZCoat is the family name for a series of refractory coatings designed to protect the bricks, monolithics, castables, ceramic fibers and steel shells in furnaces, boilers and various high temperature vessels. Ultra-ZCoat Refractories are characterised by a very high content of zirconia and other special ceramics which imparts extremely high resistance to the aggressive environments typically encountered at temperatures up to 1900C. UltraZCoat has better adhesion than most conventional zirconia based refractories. How to control kiln shell corrosion, SCL Beawar (Raj.) Page 68
A 3mm protective layer of Ultra Z coat can typically increase the working life of any underlying refractory by a factor of two to four times. Ultra Z Coat is supplied in the form of a powder which is mixed with cold water to the consistency of a paste, cement or slurry prior to application by trowel, brush or spray. This Coating is Manufactured by Wearresist Technologies Pvt. Ltd.. Problems Faced: High temperature and Chemical corrosion. Alkali Gases: Sodium, Sulpher and Chlorides. Wear On Kiln: Reduction in shell thickness of the Kiln Remedial Solution Suggested: Ultra-ZCoat N Temperature Range: Upto 1900C Finish: Matt, Buff colored, Non-Vitreous
Fig 26: The Kiln shell is dismantled for remedial repair. Procedure for Application 1.Surface is prepared by sand blasting upto 40-60 microns. 2. Ultra-ZCoat concoction is diluted upto 20% by water. 3. First coat is applied 1 mm thick by spatula. 4. Second coat is applied 1 mm thick after an interval of 6 hours. 5. Coverage Ratio: 2mm thickness gained by application of 4 Kgs over a 1 Sq. meter area.
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Fig 27: Application of 1st Coat of Ultra-ZCoat Benefits 1. Produced a gas tight surface and minimized energy losses. 2. Reduced the effects of thermal shock. 3. Protected the refractories against the aggressive effects of burning fuel oil, gas and solid fuels. 4. Reduced Spalling and eliminated cracking 5. Reduced Slag adhesion and increased resistance to corrosion 6. Increased the working life of kiln and reduced the costs of maintenance shutdowns. I) Application of spreader jack should be done in each ring at the time of closing the individual rings and due care should be taken so that bricks do not crush or develop internal cracks due to pressure applied by spreader jack. Further, jack should not be used on key bricks. By using Spreader jack we can fix the brick ring with very less gaps in between refractories. So chances of alkali attack through gap in between brick will be very less. In no case chiseling or hammering of bricks should be done. The ring should be closed using key bricks instead of cutting and fixing with the help of hammer.
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Kiln Shell Temperature Profile with max.min. and avg. shell temperature
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References
1. http://en.wikipedia.org/wiki/Shree_Cement 2. http://www.khd.com/bypass-systems.html 3. http://www.calderys.com/refractory-focus/wear-resistant.html 4. http://www.azom.com/article.aspx?ArticleID=2382 5. http://www.projectsmonitor.com/detailnews.asp?newsid=13713 6. http://corrosion-doctors.org/index.htm 7. http://met-engineering.blogspot.in/2009/10/types-of-corrosion.html 8. http://www.docstoc.com/docs/97075944/PETROLEUM-COKE# 9. Kiln Shell Corrosion by Ricardo Mosci 10.Investigation of cement rotary Kiln corrosion by E. s. Jons, M. J. L. 0stergard 11.http://www.3l-t.com/ 12.Combustion of large solid fuels in cement rotary kilns by Anders Rooma Nielsen 13.Mechanism of Shell Corrosion caused by volatiles in Cement Kilns and remedial measures by D Yadav, S K Chaturvedi, Y P Sethi, M M Ali and M Vasudeva,NCB India
Note: The Refractory Lining Data is made available by Shri R.P.Pareek. The Data for Kiln thickness with and without using SS plate is made available by Shri Harshwardhan of PMS,Cell. The data of outer Shell Temperature of Kiln and Different Chemical Composition at inlet is available from CCR, SCL, Beawar.
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How To Control Kiln Shell Corrosion

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Shree Cement Ltd., Beawar(Rajasthan)

Project Title:How to Control Kiln Shell Corrosion

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

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How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

Fig 4: Typical process flow diagram of a cement plant

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

Fig 8: Detail flow sheet of whole process

How to control kiln shell corrosion, SCL Beawar (Raj.)

General Chemistry of cement manufacturing

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

Fig 9: Phase Diagram for cement clinker production

How to control kiln shell corrosion, SCL Beawar (Raj.)

The kiln system

Upper transition zone: from 1000C to 1238C (+)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

Fig 11: Preheater Precalciner Kiln

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

Fig 12: Uniform corrosion

How to control kiln shell corrosion, SCL Beawar (Raj.)

I. II. III. IV. V. VI. VII.

Fig 14: Galvanic Corrosion Cell Caused by Different

How to control kiln shell corrosion, SCL Beawar (Raj.)

External Anode and Cathode

Fig 15: Stray Current Corrosion Cell Caused by

How to control kiln shell corrosion, SCL Beawar (Raj.)

Fig 17: Scheme of pitting corrosion

What are Refractories

Percentage other constituents 5-7 5-9 5-9 3-8 6-10

PCE C 1745-1760 1690-1745 1640-1680 1620-1680 1520-1595

Fig 18: A monolithic lining for Ladel

How to control kiln shell corrosion, SCL Beawar (Raj.)

PERILEX 83 MagnesiaChromite 81-85MgO 2.9-3.05 17-19 55

42 0.4 1.1 1.7 80

transition zone, good coatability, chrome ore free

How to control kiln shell corrosion, SCL Beawar (Raj.)

Al2O3 40.5 59.2 69.8

Fe2O3 2.15 2.5 3 30 35 36 2.21 2.42 2.61

AC 40S AC 60S AC 70S

How to control kiln shell corrosion, SCL Beawar (Raj.)

Fig 19: Refractory lining of kiln-1

Full details of Refractory linings, Coating and SS Plate Used:

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)

Corrosion of Kiln Shell

How to control kiln shell corrosion, SCL Beawar (Raj.)

How to control kiln shell corrosion, SCL Beawar (Raj.)