Kiln Burning Systems
Kiln Burning Systems
Kiln Burning Systems
239
by Con G. Manias*
Once raw materials have been selected and blended, and ground and homogenized into a fine and uniform kiln feed, they must then be subjected to enough heat to allow the clinkering reactions to proceed. This is the pyroprocessing stage of cement manufacture, beginning with the kiln feed material extracted from storage and weighed and transported to the kiln, and finishing with the clinker from the cooler going to clinker storage. A schematic diagram on different stages of cement manufacturing is shown in Figure 3.1.1
Control system
Cooler
*Managing Director, FCT Group of Companies, 20 Stirling Street,Thebarton, South Australia 5031 ph + 61 8 8352 9999, http://www.fctinternational.com
240
The main chemical reactions to produce the calcium silicates that later give cement its bonding strength occur in the kiln system. There is a combination of endothermic and exothermic reactions occurring in an extremely complicated chemical reaction sequence. The raw material composition, mineralogical composition and the time and temperature profile of these materials in the kiln determine the ultimate composition and mineralogy of the clinker, which in turn determines the performance of the cement produced. The pyroprocessing stage is generally regarded as the heart of the cement-making process. It is the stage in which most of the operating costs of cement manufacture appear, and is also therefore the stage where most of the opportunities for process improvement exist. There are many different kiln system designs and enhancements, but they are all in essence performing the following material transformation, in order from the feed end: 1. Evaporating free water, at temperatures up to 2. Removal of adsorbed water in clay materials 3. Removal of chemically bound water 4. Calcination of carbonate materials 5. Formation of C2S, aluminates and ferrites 6. Formation of liquid phase melt 7. Formation of C3S 8. Cooling of clinker to solidify liquid phase 9. Final clinker microstructure frozen in clinker 10. Clinker cooled in cooler 100C 100C - 300C 450C - 900C 700C - 850C 800C - 1250C >1250C 1330C - 1450C 1300C - 1240C <1200C 1250C - 100C
Figure 3.1.2 shows the transformation reactions taking place at different stages of raw material pyroprocessing. On the gas flow side, the sequence from the firing end is as follows: 1. Ambient air preheated by hot clinker from kiln 2. Fuel burns in preheated combustion air in kiln 3. Combustion gases and excess air travel along kiln, transferring heat to kiln charge and kiln refractories 4. Preheating system for further recovery of heat from kiln gases into the material charge in the kiln system 20C up to 600C to 1100C 2000C to 2400C 2400C down to 1000C 1000C down to 350C to 100C
5. Further heat recovery from gases for drying of raw materials or coal All kiln systems aspire to optimize heat exchange between the gas streams and material streams at various stages to minimize waste heat and maximize thermal efficiency.
241
CO2
Portions by weight
Liquid C 3A Liquid
200
400
600
800
1000
1200
1400
Temperature, C
KILN SYSTEMS
Early kiln systems for cement clinker manufacture were based on shaft kiln systems. However, as these are of little relevance to the world at large, this chapter will deal with rotary kilns only. The first rotary kiln was introduced to the cement industry by Frederik Ransome (1885) when he took out a patent in England titled Improvements in Manufacture of Cement. The first of these rotary kilns were up to 2.0 m in diameter and 25 m long, with an enormous production of 30 to 50 ton/day. Today, some kilns are producing as much in a day (>10,000 tpd) as these kilns produced in a year.
242
The main problem with long wet kilns is their poor fuel efficiency, because of the water to be evaporated from the slurry. This became a severe problem only when the cost of fuel escalated during the 1970s, and only a few wet kilns have been built since that time. However, there are some rare situations where raw material moistures, cheap (waste) fuels, low technology workforce, or other factors may still favor wet process production. Another disadvantage of a wet process kiln is that it is limited in production rate because of mechanical limitations on kiln size. A 1500 tpd wet kiln is a large kiln, with 2000 tpd being an upper economic limit without encountering severe maintenance problems. Apart from the sheer weight and stresses on mechanical drives and supports, shell deflection makes it increasingly difficult to achieve acceptable refractory life. Figure 3.1.3 depicts a typical long wet process kiln.
243
244
Material residence time in the preheater is in the order of 30 seconds and in the kiln about 30 minutes. Kiln speeds are typically 2 rpm. Preheater pressure drops range from 300 mm to 600 mm water, with gas duct velocities typically 20 m/s in the preheater and cyclones.
245
Kiln capacities up to 3500 tpd exist, with specific fuel consumption usually around 750 to 800 kcal/kg (3.2 to 3.5 MJ/kg). The larger capacity kilns are built with two preheater tower systems to keep cyclone sizes to economic proportions and required efficiency.
Precalciner Kilns
In precalciner kilns, the combustion air for burning fuel in the preheater no longer passes through the kiln, but is taken from the cooler region by a special tertiary air duct to a specially designed combustion vessel in the preheater tower. Typically, 60% of the total fuel is burnt in the calciner, and the raw meal is over 90% calcined before it reaches the rotary kiln section. Since the calciner operates at temperatures around the calcination temperature of raw meal (800C to 900C), there may not be a flame as such. The calciner efficiency is dependent on uniform air flow and uniform dispersion of fuel and raw meal in the air. Typically, average residence times calculated on gas flow for early units were about 1 to 2 seconds for coal and oil, and 2 to 3 seconds for natural gas. In recent years, though, there has been a trend toward larger calciner vessels to reduce some of the combustion problems of the earlier designs and provide greater flexibility for using lower grade fuels. Precalciner kilns can have very large outputs in excess of 10,000 tpd, with specific fuel consumption below 3 MJ/kg (700 kcal/kg). There are many different configurations, with one, two, or three preheater towers operating with one or two calciner vessels in either an in-line configuration or separate line configuration. Some (mostly recent) designs include a separate precombustion
246
chamber. An in-line calciner has kiln exhaust gases and tertiary air making up the combustion air (reduced oxygen levels) for the calciner as shown in Figure 3.1.7, while the separate line system has tertiary air only with 21% oxygen forming the combustion air as is shown in Figure 3.1.8. A separate line system therefore has a better combustion environment and may be preferred for difficult fuels. It has a further advantage when converting preheater kilns to precalciners in that there is minimal interference with the operating preheater kiln during the construction phase for the new separate line preheater tower and tertiary air duct.
Precalciner kiln systems can operate only in conjunction with grate coolers, as there is no provision for tertiary air off-take with planetary coolers. L/D ratios are typically low at 10 to 14, and kiln speeds are in the order of 3.5 rpm. Kiln residence time is typically 20 to 25 minutes.
Figure 3.1.8. Separate line calciner system with two preheater towers.
Other Systems
The rotary kiln has been the standard clinkering unit for cement production over the past century. During that time, there have been various attempts to produce clinker in other reactors including a flash calcining/clinkering and fluid bed calcining/clinkering vessels
247
The motivation has been to reduce capital and operating costs or to allow smaller economic clinkering plants to be built in remote locations. The author was involved with one such project during the 1980s, where clinker was produced in a fluid bed fed with raw meal. Although this did not proceed to commercialization, it was noted that the clinker produced from this pilot plant was much more reactive than any conventionally produced clinker, and gave cement strengths 20% higher than those produced from good quality rotary kiln clinker. This was thought to be due to the absence of overburning in the fluid bed clinker because of the more uniform temperature that can be achieved. The mineral structure certainly showed much finer alite and belite crystals in the 10 to 20 m range. This gives some indication of the potential quality improvement possible through better control of rotary kiln temperature. Critical data on the kiln systems discussed above are summarized in Table 3.1.1. The data reflects mechanical, operational, thermal, fuel, production, and efficiency parameters of each kiln system.
Table 3.1.1. Summary of Critical Data Information on Different Kiln Systems Kiln system Residence exit kWh/t time, min T, C
1725 2030 2025 25 25 180240 180240 30 3040 2030 150 230 380 400 100 120 350 300 360
Kiln systems
Long wet Long Dry Lepol Cyclone preheater Precalciner
rpm
1 1 1.5 2.0 3.6
tpd/m3
0.450.8 0.50.8 1.52.2 1.52.2 3.55.0
L/D
3035 3035 1215 1416 1014
SFC kcal/kg
1300 1650 1100 1300 950 1200 750 900 720 850
P, mm H2O
150 180 150 200 250 400 500 700 500 700
248
Where t = residence time, min L = kiln length, m p = kiln slope, degrees D = kiln diameter, m n = kiln speed, rpm = angle of repose of material, (40 degrees) F = constriction factor (usually1 if no dams, lifters etc.)
Kiln Slope
Rotary kilns slope from the feed end to the discharge end for material to travel in that direction utilizing gravitational force. The slope is typically 2% to 4%, or 1 to 2, and is decided in conjunction with the kiln rotational speed. A lesser slope with a higher rotational speed may improve heat transfer because of the greater tumbling of kiln charge.
Kiln Capacity
When designing a kiln for a certain capacity, or when evaluating an existing kiln for potential output, there are a number of key parameters that must be evaluated. These include: Burning zone heat loading Secondary air velocity Burning zone gas velocity Kiln exit gas velocity Kiln exit gas temperature Preheater tower gas velocities Preheater tower pressure drops Preheater tower exit gas temperature Volatile concentrations Material residence time Cooler grate loading
249
Cooler air supply Kiln dust cycles There are design limits for all of the above that may vary between different processes, but any of the above could be the limitation to a kilns output. These limitations will typically manifest themselves as kiln instability and ring or coating buildup, excessive dust loss, poor refractory life, poor clinker quality, or high fuel consumption. Usually, however, the limitation is found to be more a question of a fan capacity, a burner capacity, or milling of raw materials or coal.
CLINKER COOLERS
Cooling of clinker takes place at two locations: 1) in the kiln after the material passes the burning zone region, and 2) in the specially designed clinker coolers after the material falls out of the kiln. The rate of cooling can be critical to the clinker quality and performance of cement. The rate of cooling in the kiln is determined by the flame and resulting heat flux, flame temperature, and speed of material flow through the kiln. As the clinker temperature exiting the kiln is normally 1200C to 1250C, the clinker characteristics have been already largely established before the clinker enters the cooler. A long flame gives slow heat-up and slow cooling of the kiln charge before it falls from the kiln. This will tend to produce clinker with large alite and belite crystals, resulting in a coarse-grained clinker matrix with poor reactivity and poor grindability. Slow cooling can also result in reversion of C2S from the ' phase to the less reactive form, or in extreme cases even to the unreactive form, and can even allow C3S to revert to C2S and CaO. All of these have a negative impact on cement strength. A further quality problem can arise if there are high levels of MgO in the clinker, because slow cooling allows large periclase crystals to form such that when these hydrate slowly in concrete, the expansion can cause the concrete to rupture. There are two main types of coolers used in cement clinker production. These are the satellite (or planetary) type and the oscillating grate type. The 1990s saw tremendous advances in clinker cooler technology that greatly improved heat efficiency and potential output from a given kiln system. Clinker coolers perform the function of: Transporting clinker from the kiln to the clinker delivery system Cooling the clinker to a safe temperature for subsequent transport Finalizing the clinker mineralogy through rapid cooling Preheating combustion air by heat exchange with hot clinker Coolers are treated in more detail elsewhere in this publication and will not be elaborated on further here.
250
KILN BURNERS
Combustion and the Cement Process
Pyro-processing is the heart of the cement-making process. It is usually the major cost element and kiln performance dictates the efficiency, plant output, emissions, product quality, and plant run factors. Combustion will be the major factor in determining kiln performance, and seemingly small improvements here can have a major impact on the economics of running the whole plant. An additional 5% to 10% production in a year will impact spectacularly on the profit line given the large proportion of fixed costs at a cement plant. The cement kiln requires a particular heat transfer regime for best fuel economy, optimum product quality and maximum production. Generally, a short hot burning zone at the front of the kiln is optimal. This gives rapid heat up and cool down of clinker to give the best reactivity, reduced back end temperature for minimizing heat losses in the exit gases and from shell radiation, best use of I.D. fan capacity, and reduced NOx formation. This needs to be balanced against refractory heat load and kiln operating stability. The flame must not impact on the kiln charge or refractories and complete combustion must occur in the kiln to reduce potential for build up and ring formation. When deciding on a burner, it can be false economy to simply select on the basis of initial purchase price alone, and suffer long-term poor performance for the plant or extended commissioning times. The capital investment in a cement plant is substantial and it is high risk to entrust the performance of this investment to a relatively low-cost component (the burner system) without taking all reasonable steps to mitigate this risk. Sadly though, it is often the case that evaluation and choice of burners either for new kilns or replacement systems is based on capacity and purchase price only, without much indication of how they will perform with the specific kiln under consideration. The combustion system should be considered as an integral part of the pyro-processing system, including kiln, cooler, tertiary air ducts, calciner etc., and be designed with due consideration of this total system.
Kiln Aerodynamics
It is surprising how small differences in cooler throat, cooler bull nose, kiln hood, tertiary air offtakes, secondary air temperature and velocity, and air leakage points to name a few can have an enormous effect on the air flow patterns in the combustion environment of the rotary kiln. Tertiary air inlet design and location, and tertiary air temperature and velocity will likewise determine the airflow patterns in a flash calciner.
251
The fuel introduced by the burner will clearly be influenced by the secondary and tertiary air flow patterns, given that 85% to 100% of the combustion air comes from this source and the momentum of these large airflows dominates the combustion region. Typical aerodynamic patterns in two different kiln combustion zones are shown in Figure 3.1.9-a,b.
Hood
Flame
(a)
Flame
(b)
Figure 3.1.9-a,b. Some typical kiln aerodynamic patterns encountered during kiln studies.
252
Geometric design of cooler, cooler bull nose, cooler throat, kiln, off-take ducts, burner position, burner angle, burner channels (types, numbers and sizes), calciner size and shape, and tertiary air inlet Process design, such as fuel rate, type, properties; primary air mass and velocity; secondary air and tertiary air temperature, mass and velocity; production rates; heat transfer (convection, conduction, radiation); and heat flux profiles developed As no single modeling technique can provide all the answers, a combination of physical and mathematical modeling provides the best information for arriving at an optimized burner design. Observation from a fuel/air mixing model using acid-alkali techniques is shown in Figure 3.1.10. The overriding consideration when implementing results of modeling work is understanding the limitations and the conclusions that can be drawn from each technique, as well as ensuring that the techniques used have been adequately validated.
253
In a rotary kiln, the secondary air to be entrained into the fuel jet is limited to that coming from the cooler, and the expansion of the fuel jet is constrained by the diameter of the kiln. If the burner jet momentum (fuel and primary air) is less than that required for complete entrainment, then fuel/air mixing will be inadequate for good combustion, and a long, lazy flame with high CO is the likely result. If the burner momentum is greater than that required for complete secondary air entrainment, then the excess momentum of the fuel jet is dissipated in pulling back exhaust gases from further down the kiln into the flame. This so-called recirculation has a positive effect in stabilizing the flame (making it less susceptible to minor process fluctuations) and in protecting refractory surfaces from burning fuel particles. Note though, that too much recirculation can be detrimental to fuel efficiency and produce an overly aggressive combustion environment. An ideal flame from use of secondary air entrainment and recirculation is shown in Figure 3.1.11.
Figure 3.1.11. Idealized flame in rotary kiln showing secondary air entrainment and recirculation of combustion gases indicating adequate burner momentum for satisfactory fuel/air mixing.
Good burner design therefore requires optimizing fuel jet momentum and primary air mass and velocity to create a recirculatory flame while interacting with that particular kiln systems aerodynamics. The secondary air temperature, mass, velocity, and directional flows must all be considered in the design process as these affect the burner system design. The variables to optimize include primary air mass and velocity, axial and radial flow splits, fuel jet momentum, and burner insertion length and direction. A typical multi-fuel burner used in a rotary kiln is shown in Figure 3.1.12.
254
Flame Stability
Unstable flames adversely affect kiln operation as well as being unsafe to plant and personnel. An unstable flame is one that has a varying ignition point and a variable stand off distance from the burner tip as shown in Figure 3.1.14. There is a high risk of flame out, and substantial amount of unburnt fuel between the burner tip and the ignition point that is a potential explosion risk. Gas burners are more prone to instability because of the high ignition temperature, slow flame propagation speed, and narrow flammability limits for this fuel.
Flame envelope
Unburnt gas
Unstable flame results in uncontrolled heat transfer Risk of flame out and explosion
Ensuring early ignition of fuel entering the combustion zone enhances flame stability. In some applications, this can be by a continuous pilot burner, but in rotary kilns this is best achieved by ensuring recirculation of hot gases as the ignition source for new fuel. Once a kiln is up to operating temperature, radiation from refractory provides the ignition energy.
255
External circulation from properly designed burners brings hot combustion gases back into the combustion region to help stabilize the ignition point. Internal circulation can be even more effective. Internal circulation can be induced by the use of a bluff body to create a low pressure region in the center of the burner nozzle that then draws hot combustion gases back into this region. This can then act as the ignition source for the new fuel. Bluff bodies, though, can suffer heat damage in this demanding location (see Figure 3.1.15).
Reverse flow
Primary air
Gas
Primary air
Bluff body
Figure 3.1.15. Stabilization of flame with internal recirculation created by bluff body.
A more durable means of creating internal flame re-circulation is the use of swirl in either the fuel or primary air jet stream as shown in Figure 3.1.16. However, swirl would broaden the flame that can adversely affect refractory life due to flame impingement (see Figure 3.1.17). In gas firing, the most effective design uses limited swirl for both primary air and gas fuel. In oil firing, primary air swirl is typically used, while for solid fuel firing swirl is often unnecessary for producing a stable flame. Each case is designed on the merits of the fuel and the combustion environment in which it will operate.
Burner
Flame envelope
256
20,000 14,000 6000 5000 A 4750 Dia. N C L Primary jet J B 4290 Dia.
Gyro-Therm Burners
The Gyro-Therm Precessing Jet burner technology has been designed to be mechanically very simple, but the novel fluid-mechanical flow provides a genuinely new way of mixing fuel and air. This produces flames with different characteristics (compared to turbulent diffusion jet burners) that have been proven to give operational and environmental advantages in kiln firing. This emerging technology has so far been used in gas burning or gas/coal burning applications. However, a coal-only burner using Gyro-Therm technology is near commercialization. The precessing jet nozzle used in these burners produces a fuel jet stream exiting the burner nozzle that exhibits a stirring action into the combustion environment as shown in Figure 3.1.18.
Gas
Jet precession
Figure 3.1.18. Cross sectional diagram of the precessing jet nozzle and the flow field generated from it.
257
The flame itself does not precess. The effect is to produce large-scale mixing, via the stirring action of the jet and a rapidly spreading flame. This is in contrast to the fine scale mixing of turbulent jet diffusion burners. The precessing motion is generated without any moving parts within the Gyro-Therm nozzle. The resultant effects of this new technology include: Sub-stoichiometric combustion within flame envelope with complete combustion at the flame boundaries in a normal kiln environment Highly luminous flames enhancing heat transfer to kiln charge Low axial velocity of fuel jet giving short bulbous flame Low thermal NOx formation No primary air needed for gas fuel and a stable flame anchored to the nozzle Although the flame spreads more than that from a conventional turbulent jet nozzle, the amount of spread can be controlled. This fact is important in rotary kilns where direct impingement of a flame on the product could produce instability or reducing conditions which would be detrimental to product quality or damage the refractory. A simple but extremely effective flame shaping technique is built into the burner. The technique for flame shape adjustment is based on a high momentum gas jet injected at a critical point into the precessing jet flow field. This jet (termed the center body jet, CBJ) is expelled through the center body of the precessing jet nozzle, modifying the pressure fields within the vicinity of the burner in such a way that the fuel gas is directed more toward the kiln axis. As the proportion of gas is increased through the center body jet, the flame spread is reduced and the heat flux profile lengthened. An air channel is provided for burner cooling and for flame shaping during the warm-up phase. A schematic of Gyro-Therm burner with gas channel for flame adjustment and cooling air is shown in Figure 3.1.19.
PJ Gas
Figure 3.1.19. The design of the Gyro-Therm burner includes an additional gas channel for flame shape adjustment and optional cooling air.
258
CALCINER BURNERS
Calciner combustion is quite different from kiln combustion. Often, there is no defined flame in the vessel, with oxidation of the fuel occurring under flameless conditions. As for any combustion environment, satisfactory fuel/air mixing is the first requirement for good combustion. Calciner aerodynamics are dominated by the tertiary air due to its mass and comparatively high velocity at the calciner inlet. The airflow patterns can become quite complex with changes in the calciner cross section producing effects such as strong recirculation zones and streaming as depicted in Figure 3.1.20. With such prevailing conditions, the location and design of calciner burners can become extremely critical to the performance of the calciner. As for kiln burners, physical modeling can reveal the flow patterns within a calciner, and allow the location of burners and their design (injection velocities and momentum) to be determined for best performance. FurtherFigure 3.1.20. Typical aerodynamic problems encountered in more, modeling can often determine simple redesign of internal calciner operation that impair calciner combustion. refractory profiles to produce much improved calciner aerodynamics and hence greatly improve calciner combustion. Due to the short residence time in calciners (2 to 3 seconds), combustion can be sensitive to fuel properties. Some fuels such as petcoke because of its low volatile content, and natural gas because of its more stringent combustion prerequisites, require more residence time (larger calciner) for satisfactory combustion. Calciner burner designs can vary from a simple pipe through which to introduce fuel, to more sophisticated designs that are smaller versions of kiln burners. In most cases, a simple pipe will perform as well as the more complex designs if it is correctly located and designed. This is obviously a cheaper capital and operating cost solution. Only in rare cases will primary air be required in a calciner burner to overcome any serious aerodynamic problems.
259
OXYGEN INJECTION
The technical benefits available from using oxygen to replace air for combustion in cement kilns have long been recognized. These benefits arise from increased flame temperature (leading to improved heat transfer rates), faster reaction rates with some difficult fuels, and reduced combustion gas volume (due to less nitrogen). In general, this will lead to reduced specific fuel consumption (less waste gas volume and better heat transfer) and increased production from a particular kiln. The effect on NOx emissions will be variable, but with small amounts of oxygen substitution NOx will usually increase as a consequence of elevated flame temperature. However, the cost of oxygen has generally been prohibitive in the past, preventing the wholesale use of oxygen to enhance cement kiln performance. The availability of cheaper production methods for oxygen such as the vacuum swing adsorption process, together with increased demand for cement, have combined in some regions to make the strategic use of oxygen a viable alternative for increasing production. This is particularly so where short term peaks in demand are encountered and oxygen injection can be implemented without significant plant down time for modifications. Oxygen injection can be carried out either in the kiln or calciner. A process evaluation of the specific kiln system will reveal the most advantageous point. Generally, this will involve identifying bottlenecks to increased production and how these can be addressed through the use of oxygen. A modeling strategy for designing oxygen-injecting system for a calciner is shown in Figure 3.1.21. Strategic use of oxygen can impart the following processing benefits: Allow more fuel to be burned in either the kiln or calciner where fan capacity is limiting output, and therefore increase output Reduce gas velocity in the burning zone, kiln back end, calciner exit, through the preheater tower, or through the bag filter or electrostatic precipitator Reduce pressure drop through the kiln system because of reduced gas velocities Reduce preheater exit temperature because of higher feed-to-gas ratio Increase calciner residence time Increase flame temperature and heat transfer to material
Figure 3.1.21. Modeling to determine the design of the oxygen injection system into the calciner.
260
However, there are also potential risks of overheating refractories and kiln charge or calciner feed unless due consideration is given to the design of injection points and oxygen lances.
The hypothetical compounds are calculated using the Bogue equations to determine the percentage of calcium silicates (C3S and C2S), calcium aluminate (C3A) and calcium alumino ferrite (C4AF) phases, which would be present in the clinker if all reactions proceeded to completion under equilibrium conditions. In reality, the calculated or hypothetical composition differs from actual analysis of clinker by X-ray diffraction or microscopic analysis. This is because chemical
261
equilibrium is reached only occasionally, and the degree to which actual analysis differs from the calculated analysis is influenced by the heat treatment of the material. In addition, small amounts of trace elements can have a profound effect on the eventual mineralogical composition of clinker. In general, it is found that: Alite content is usually higher than the calculated amount by an average of 13% Belite is usually lower than the calculated amount by an average of 6% Aluminate and ferrite phases can be either higher or lower, but on average are 2% lower than calculated The critical stages for clinker quality are: The heat-up rate of the kiln charge after the calcination process The maximum temperature and residence time at that temperature The cooling rate to below 1200C These stages determine the size of alite and belite crystals and their reactivity, the formation of these crystals (, , ), and the nature of the liquid phase, as well as the position in the structure where minor elements such as Mg, Na, and K, are found; all are critical to cement quality. Some aspects of plant operation that help kiln performance are kiln feed size, homogeneity, kiln time/temperature profile, heat balance, and volatile and dust cycles; these are discussed in the following sections.
262
Time/Temperature Profile
The kiln charge must spend sufficient time at a high enough temperature to reach near complete reaction to form clinker minerals. There must be no material flushing or underburning, as this produces poor quality clinker. The material bed must tumble adequately to ensure uniform heating through the mass. If clinker is underburnt, it will form small crystals of alite surrounded by abundant (solidified) liquid phase, whereas the belite will exist in discrete clusters. There may also be significant free lime present together with alite and belite, which has not had the opportunity to completely react. Overburnt clinker will have large alite and belite crystals, and exhibit poor reactivity.
3275
5475
782
1307
263
The heat of formation (Q) of the clinker minerals is a function of the chemical composition and the mineralogical composition. It can be expressed as kcal/kg in a general equation as follows: Q = 2.22% Al2O3 +5.86% hH +6.48% MgO+7.646% CaO 5.116% SiO2 0.59% Fe2O3 Where hH = % water of crystallization in the clay, g/100g clinker, and all analyses are on clinker. If alkalies are present, the heat of formation is reduced by about 2 kcal/kg. (2)
264
Other less insidious factors are the sensible heat of introduced streams, the secondary air heat input to the kiln, the calcination reaction, and heats of formation of the various components. The heat exchange occurring within a kiln is therefore a multi-dimensional phenomenon.
Kiln Volatiles
The kiln volatiles referred to in cement manufacture are those compounds that volatilize in the burning zone of a rotary kiln and recondense in the cooler parts of the kiln or preheater. They are usually sodium or potassium sulfates and chlorides, but can also include certain calcium salts. Their melting points and relative volatilities in the kiln burning zone are given in Table 3.1.4.
Table 3.1.4. Melting Points and Relative Volatilities of Different Compounds in Kiln Burning Zone Volatile compounds KCl K2SO4 NaCl Na2SO4 CaCl2 CaSO4 Melting point, C 776 1069 801 884 772 1280 Range of volatility, % 60 to 80 40 to 60 50 to 60 35 to 50 60 to 80
These materials are not usually in the pure form, but form a eutectic mixture with an overall melting point below that of the pure salts. In practice, these salts generally will appear in the melt in the temperature range of 600C to 800C. The volatile compounds cannot readily escape from the kiln system because they condense (before they can be removed in the exit gas stream) and re-enter the kiln. Their concentration will therefore continue to build, sometimes reaching a concentration in the recycle stream significantly greater than the concentration in the raw materials. As they pass through a sticky condition during the melting/vaporization and recondensing stages, they can be catalysts for forming coating buildup in the preheater tower and rings in the back end of the kiln. These can be particularly disruptive to kiln operation in the cyclone preheater tower, and older preheater kilns can run into severe operational problems because the effect of the volatile cycle was unrecognized in their design.
265
As a guide, the acceptable concentration limits of these materials (as % of clinker) in the kiln riser are: Na2O and K2O SO3 Cl < 3% to 5% < 3% to 5% < 1.2% to 1.6%
The factors that influence the volatility of these materials are: The gas velocity in the burning zone has a strong influence on the volatility of these materials. A higher gas velocity reduces the vapor pressure of volatiles in the atmosphere, increasing their volatility. A kiln operating beyond its design limitations could be adversely affected. A higher burning zone temperature as required for harder burning mix will increase volatility. A higher CO2 concentration in the kiln will increase volatility of sodium and potassium. Reducing conditions will increase the volatility of sulfur, while higher oxygen levels will decrease it. The equilibrium reaction is Me(SO4)m = nMeO + mSO2 + m/2O2 A low oxygen level shifts the equilibrium to the right. The volatility of sodium and potassium is less affected by oxygen levels than that of sulfur. Increased water vapor promotes formation of alkali hydroxides that are more volatile than the sulfates. Potassium volatility is increased at 1200C, while sodium volatility is increased at 1400C. SO2 (from the fuel) reduces the volatility of potassium, while the sodium volatility is unaffected. The mineralogical composition of raw materials producing volatiles is a major determinant of the alkali volatility, depending on the alkali carriers. Mica > illite > feldspar. Also, an easier burning material means lower burning zone temperature and hence less volatility. The fineness of raw meal has an indirect effect if it produces an easier burning mix. A further factor is the alkali-to-sulfur ratio. Alkalies will preferentially combine with any chloride present. The best alkali-to-sulfur ratio is when there is just enough sulfur present to combine stoichiometrically with the remaining alkalies. If there is an excess of sulfur, then calcium sulfate will form from which the sulfur will volatilize completely. If there is an excess of alkalies, alkali aluminate can form which will cause stiffening problems in concrete and mortar. There are also likely to be rings and buildup formed in the kiln system from a variety of other alkali salts produced. In some cases, where low alkali cement is the target, and there is an alkali bypass installed. Alkali volatility is an advantage, and CaCl2 can be added to the mix to promote alkali volatility. (3)
266
Sinter Rings
Sinter rings form at the beginning of the burning zone, and they also have an appearance and composition like clinker. These rings establish at the point in the kiln where the liquid phase is beginning to form, but during the course of a kiln turn, the melt comes into contact with a cooler surface and resolidifies, binding clinker particles together. This process can repeat until a ring forms. This type of ring is most likely to develop where there is a long and flat heat flux profile in the kiln.
267
CONCLUSIONS
The heat transfer processes occurring inside a kiln are multi-dimensional and extremely complicated. There is no single factor that can be considered in isolation when seeking to optimize kiln performance and product quality. The raw materials and kiln feed preparation will have a major impact on kiln performance and will set the blueprint for fuel economy, kiln stability, clinker quality, refractory life, kiln throughput, and environmental impact. The kiln operation and the combustion system will determine as to what extent the potential inherent in the raw materials will be realized. An optimization approach to a cement manufacturing plant should therefore consider a total holistic approach from the quarry to the lorry, examining each stage in detail and the impact of each stage on the total plant operation and economics.
REFERENCES
Ransome, F., Improvement in Manufacture of Cement, English Patent #5442, May 2, 1885.
268