MIDTH INSTITUTE Operation and Optimisation of Kiln Systems NO, and SO, in Clinker Burning Installations; Formation, Utilisation and Reduction Asocem Page 1 August 2006 479ism DTH INSTITUTE Table of Contents 2.1 Introduction ee 3 2.2 Formation of NO and SO>...... 3 2.2.1 SOz Formation Mechanisms. 4 2.2.2. The Importance of Excess Air.. 6 2.3. Summary ~ the Formation Mechanisms. 9 2.4 Relationship Between Cement Kiln Operation and Content of NO, in Kiln Exit Gasses 10 2.4.1 Formation of NOx occ operon fll 2.4.2 Kiln Torque and NQ,....... sevvsnntinnntnnnnenannnetneeneseesesenesce 1D 2.4.3. Clinker Alkali vs. NOx... cereal sone 16 2.4.4 Free Lime and Litre Weight vs. NO, 7 2.4.5 Expansion of the Kiln Shell as a Function of NOx 2.4.6 Further Investigations 2.5. Conclusion. ‘Asocem, Page 2 August 2006 480ism DTH INSTITUTE NO, and SO, in Clinker Burning Installations; Formation, Utilisation and Reduction 2.1 Introduction This module describes how measurements of NO, and SO, emissions can bé exploited in order to improve control of the clinker burning process in the kiln. First, the formation con- ditions and mechanisms are described. Following this, a detailed study of the relationship between kiln operational parameters and NO, is presented. Lastly, the information con- tained in SO, content measurement is discussed. 2.2 Formation of NO and SO; NO and SO are formed during kiln operation. Sulphur compounds in raw materials and fuel are the sources of the SO:. The N-compounds in the fuel and the high flame tempera- ture in the kiln burning zone are the sources of the NO, Given the raw materials and fuel, several parameters affect the amount of SO) and NO formed. Part of the organic and pyritic sulphur in the raw material bums to form SO) at tempera- tures found in the upper stages in the preheater. Most of this SO; leaves the kiln system. The amount of SO, from the burning zone can partly be controlled by excess air. The amount of thermal NO formed in the burning zone depends on the flame condition. In precalciner systems the combustion gases contain not more but less NO - up to 100 ppm - afier passing the calciner. This effect is increased by high temperature operation of the cal- ciner, Increasing environmental awareness has drawn attention to the contribution made by ce- ment plants to the content of $O2 and NO in the atmosphere. Asocem Page 3 August 2006 481Gis IDOTH INSTITUTE This is discussed in the following using data from measurements taken at plants, and we point out the possibilities which exist within the production process for minimising emis- sion of these gases before resorting to other, more expensive solutions. 2.2.1 SO; Formation Mechanisms The SO, formed is derived from sulphur compounds in the fuel and the raw materials. The sulphur compounds in the fuel first of all form SOz which enters into the internal circula- tion of volatiles within the system. If the raw materials contain pyrite or organic sulphides, some of these sulphides will oxidise to SO; at temperatures as low as 450 - 600°C, corre- sponding to the top stages in a preheater. Here the absorption of SO) is extremely low, and a substantial part will pass out of the kiln system. In these cases therefore the kiln exit gases will always contain SO). Sulphur compounds deriving from raw materials and entering the kiln join the internal cir- culation on equal terms with sulphur from the fuel. The circulating sulphur forms sulphates able to leave the system with the clinker and reject dust Figure 1 shows SO; measurements from two ILC kilns with the same production, Kiln A operated at 50% bypass while on kiln B the bypass was closed. The concentrations were converted to ppm SO» at 10% oxygen. The abscissa is the sulphur content in the kiln feed calculated as percentage SOs on ignited basis. At both installations, kiln gases and bypass gases alike were passed to the main filter, and the measurements were taken after this filter. Asocem Page 4 August 2006 482Eiism DTH INSTITUTE PPM SO; after filter, 10% O2 1000} 500 0.5 1.0 1.5 2.0 SO, inkiln feed, loss on ign. free Figure 1. SO, emissions from nvo kiln as % of SOs in kiln feed. At kiln A two thirds of total sulphur content consisted of pyrites, while for kiln B this fig- ure was three quarters. Viewed on the curve, the measuring points for kiln A form two straight lines, and for kiln B one straight line. For kiln h, the slope of the line for low SOs values corresponds to the escape as SO> of just under half the pyrite in the kiln feed. This means therefore that if the sulphur input can be bound as alkali sulphates in the clinker, and as alkali and calcium sulphates in the reject dust, SO» will only be present in the exit gases when there is pyrite in the kiln feed. If the sulphur content exceeds this level, all the additional sulphur will produce SO;, as indicated by the slopes after the breakpoints. Note that after the breakpoints the slopes are identical. Asocem Page $ August 2006 483Giism DTH INSTITUTE | 2.2.2 The Importance of Excess Air PPM SO; in smoke chamber, 10% O2 2.0 3.0 0296 In smoke chamber Figure 2, SO, in exit gases as relative fo oxygen in smoke, The excess air in the kiln has a great effect on SO; emission, as can be seen in Figure 2. Here the amount of the sulphur input was constant, but the oxygen concentration in the kiln inlet varied, These measurements were taken in the smoke chamber of a long dry-process kiln equipped with one cyclone. As will be seen, the SO; concentration in the exit gases rises sharply as the oxygen percentage falls, Therefore to minimise the $O2 content in the gases, a large excess of oxygen is needed. This, however, has the reverse effect on NO for- mation, Figure 3 shows the results of simultaneous measurements of SO; and NO, in which SOs and NO are given as ppm at 10% Oz The figure shows clearly that the fall in SO content with the increase in oxygen concentration is accompanied by a rise in NO. These results were obtained from an ILC kiln without bypass. Asocem Page 6 ‘August 2006 484ismipra INSTITUTE PPM after filter, 10% O, 1000 . SO2 500 NO 0 07.0 8.0 9.0 .10.0 11.0 O2 % after filter Figure 3. Simultaneous measurements of SO2 and NO. NO formation takes place by means of two mechanisms: In the first mechanism, the ther- mal NO is formed in the kiln buming zone from the content of nitrogen in the atmosphere. ‘The quantity is determined mainly by temperature and excess oxygen. In the second mechanism the fuel NO is formed. In this instance, the content of volatiles and nitrogen in the fuel, as well as excess oxygen are the deciding factors. Asocem Page 7 August 2006 485Gismiorn INSTITUTE The fuel NO formation is of secondary importance in the burning zone as the temperature at this point is so high that considerable thermal NO will be formed anyway. With secon- dary firing, as in pre-calciners, the fuel NO is of importance Comparison of measurements obtained during periods of hard and less hard burning in an ILC kiln with 50% bypass showed a change from 350 ppm to 240 ppm, all at 10% oxygen, On a corresponding installation, but without bypass and with an easily burnable raw mix, 280 ppm NO at 10% oxygen was recorded Experiments carried out on both pilot and full-scale installations have shown that an in- crease in calciner temperatute causes a drop in NO concentration. The results have demon- strated that a reduction in NO of 100 ppm (10% O,) can be obtained by raising the tempera- ture 100°C. Analysis of data from the same tests has shown that the concentration from the calciner increases by 30 ppm (10% Oz) for each percent the oxygen increases. Figure 4 gives an example of the way in which the calciner temperature influences NO concentra- tion. The results are taken from a full-scale test on an SLC kiln, iat 1096 0, Calciner center temp. Se 2 = NO atter preheater ————___ roe Asocem Page 8 August 2006 486Giismiota INSTITUTE Figure 4, Calciner temperature influence on NO concentration. The amount of fuel NO formed increases with fuel nitrogen content. The volatiles content of the coal is also important. Figure 5 shows ppm NO (10% Oz) measured after the calciner on an SLC kiln. Two different coals were used for firing - nitrogen content was identical but the volatiles content was 13% and 34%, respectively. As will be observed, the NO con- centration almost halved after switching from coal with low volatiles content to coal with high volatiles content. PPM NO at 10% 02 1200 Caleiner center temp. eed | 1008 COaHA, S085 coslA+s0% coat [00% coal] 0% coals 5% coats NO ator preheater Figure 5. NO content affected by volatiles. 23° Summary - the Formation Mechanisms Careful control of excess air in both kiln and calciner is necessary to keep the Sz and NO concentration at a minimum. To achieve low NO concentration, a high precalciner and low Asocem Page 9 August 2006 487Giismivta INSTITUTE burning zone temperature should be used. If the kiln feed contains pyrites, SO; emis unavoidable. ion is, If the required limits for SO; and NO concentrations cannot be achieved within the actual production process, other documented methods must be used, e.g. the NH3 injection in pre- heater bottom to remove NO, and lime or limestone scrubbing to remove SOr, as is prac- tised at electrical power plants. 2.4 Relationship Between Cement Kiln Operation and Content of NO, in Kiln Exit Gasses In order to achieve satisfactory clinker quality and smooth kiln operation, it is necessary to keep the temperature of the burning zone stable. To achieve this, itis advisable to be able to determine the temperature, or at least changes in the temperature, without excessive time delay. In kilns with a clear burning zone, this can generally be achieved, unless the shape or position of the flame changes. Temperature changes are determined either by visual inspec- tion, or with the aid of an optical or two-colour pyrometer. These "measurements" are used to aid the operator in holding the temperature stable, so that the amplitude of the unavoid- able variations is minimised, The clinker quality, and thus whether a temperature change is required, is determined on the basis of the clinker litre weight or free lime. Such a system can be very stable. The advent of the large rotary kilns has changed the pic- ture, since the burning zones of these kilns are generally rather dusty. In these eases, it be- comes necessary to use indirect temperature determinations, such as kiln torque, kiln shell temperature, or the determination of temperatures elsewhere in the kiln. Although the kiln torque suffers least from the disadvantages, and has been of great service in the past, these indirect methods show the temperature with a significant time delay, and in addition are subject to possible misinterpretation, The only temperature variations that can be controlled in such kilns are those which have a duration several times that of the time delay; that is, variations which last several hours. It can be a mistake to try to correct more rapid varia- tions, since this is liable to make the kiln even more unstable, A need has therefore arisen for a method which detects rapid temperature variations in the burning zone. A determination of the content of NO, (oxides of nitrogen) in the exit gases from the kiln will often be able to fill this need, It has been shown that there is a strong de- pendence between the temperature in the burning zone and the NO, level, for kilns with a normal level of excess oxygen in the burning zone (2, 3). The time delay associated with the NO, measurement is under one minute, which represents the time required for the NOx formed to reach the analyser and be measured and registered, Asocem Page 10 August 2006 488Giism DTK INSTITUTE It should be emphasised that it is only a change in the burning zone temperature that can definitely be ascertained from a difference in the NO, level. One cannot determine the ac- tual temperature with a NO, monitor. Thus, the most practical use of the NO, data is to in- terpret NO, variations as an indication of changes in the burning zone temperature, and to adjust the kiln operation accordingly. Clinker quality tests, such as alkali, litre weight, or fice lime, can then be used to judge whether this temperature level is correct. In this module, a description of the mechanism of NO, formation in the flame will be given, together with an hypothesis for the effect of the material temperature, via the flame tem- perature, on the concentration of NO, in the combustion gases. In the subsequent discus- sions, this postulate will be confirmed by data comparing NO, data measured at several op- rating plants with other parameters known to depend on the temperature of the material in the burning zone. At the same time, the use of this information to aid in assuring stable kiln operation and satisfactory clinker quality will be treated, 2.4.1 Formation of NOx NO, one of the two oxides of nitrogen which together are termed NOx, is formed in the kiln flame. It is formed partially from the high-temperature fixation of atmospheric nitrogen (thermal NO,) and partially from oxidation of the N-containing compounds in the fuel (fuel NO,) The other nitrogen oxide of interest, NO», is not formed in measurable amounts until the temperature is reduced to below 1000°C; thereafter it is formed by the reaction of NO and 02 in the combustion gases. NO2 seldom represents more than 5 - 10 % of the total NO,. From thermodynamic considerations, it can be anticipated that the equilibrium concentra- tion of NO will increase very strongly (more strongly than proportional) with temperature, and will increase proportionately with the concentration of O2 (and nitrogen, which is es- sentially constant). The rate of reaction for NO formation, which will determine how closely the reaction comes to reaching equilibrium, increases very strongly with tempera- ture, since NO, formation (according to the generally-accepted Zel'dovich mechanism) de- pends on the presence of radicals such as O, N, H, OH, etc, (2, 3, 4). In a hydrogen flame with its high population of a wide variety of radicals to initiate and propagate rapid chain reactions, the rate of reaction is greater than in an otherwise comparable gas mixture at the same temperature. The frequent observation that NO, levels are higher in kilns fired with natural gas than in comparable coal-fired kilns is in agreement with this mechanism, Asocem Page 11 August 2006 489Giism DTH INSTITUTE Many fuels contain organic nitrogen compounds. If all this nitrogen were converted to NOs, the resulting NO, levels would be very high. However, no relationship has been found be- tween the fuel nitrogen content and the corresponding NO, level. This can be attributed in part to the fact that flames in cement kilns are very hot. In an "axial" flame typical of ce- ment kilns, the core is reducing, while the hotter flame envelope is under oxidising condi- tions. In order for the nitrogen in the fuel to influence the NO, level, it must "find" one of the relatively rare oxygen moieties in the air-poor core of the flame before thermal decom- position of the compound to Np takes place. Conditions do not become oxidising until the NO formed reaches the surface of the flame. At the same time, the reaction rate for NO formation increases as a result of the higher temperature in the flame envelope; this tem- perature is indeed sufficiently high to ensure that the equilibrium concentration of NO is achieved or nearly achieved (despite the relatively short residence time of the gases in the flame. Thus the combustion gas, as it leaves the hottest portion of the flame, will have ap- proached the equilibrium NO concentration regardless of the original source of the nitro- gen. Thus, no influence of fuel nitrogen on NO, from cement kilns is to be expected. Flames are very inhomogeneous. All combinations of temperature and oxygen concentra- tion can be found, but we can only see the resultant average values. As the relationship be- tween temperature and NO is non-linear, two flames, identical in all respects other than the temperature distribution within the various flame regions, may show different NO, levels. It is therefore impossible to predict NO, from an average temperature and oxygen concentra- tion, and equally impossible to deduce the temperature from known NO, and average Oz values. Furthermore, the actual O; concentration in the flame, and the manner and rate with which fuel and air mix, are of great importance for determining the temperature and the po- tential NO, level: this mixing is in turn strongly dependent on the type of fuel bumed and on its content of volatile matter. All cement kilns are therefore individual with respect to NO, generation, Nonetheless, as will be shown later on, changes in NO, readings, together with other parameters, can be used to deduce changes in the burning zone temperature with surprisingly good accuracy. 2.4.2 Kiln Torque and NO, An increase of the material temperature in the burning zone will normally result in an in- creased adherence of the material to the refractory, and in a certain accumulation or ag- glomeration of material. Consequently, the kiln's inertia will, on the average, be increased, with a resulting increase in the power required for kiln rotation. It is therefore not surprising that there is a good correlation between NO, and the kiln torque. It will of course require a Asocem Page 12 August 2006 490DTH INSTITUTE certain amount of time before sufficient material is accumulated to impact the kiln torque, and therefore one can expect a time delay between a change in NO, and the corresponding change in kiln amps. The length of this delay will depend in part on the sensitivity of the measurement of kiln amps. The results obtained to date appear to show that fluctuations in NO, of short duration can- not be found reflected in changes in kiln torque or in other parameters of significance. Only changes lasting at least 15 minutes can be expected to be manifested later in the kiln torque readout, Therefore, it is probably advisable to be certain that changes in the NO, level are Jong-enough lasting to be meaningful before modifying kiln conditions in reaction to them. This is a result of the fact that temperature changes indicated by small changes in the NOx level may have little or no significance in a heat sink as massive as a cement rotary kiln, particularly when such changes are of short duration. The expected relationship between NO, and kiln torque is quite generally realised in prac- tice, and is exemplified in Figure 6, which shows NO, and kiln torque plotted as a function of time for a long, wet-process kiln. In the interest of clarity, minor fluctuations of very short duration have been omitted. The time delay of about one hour can be clearly seen Torque as % of Full Seale Asocem Page 13, August 2006 491ism DTH INSTITUTE Figure 6. Relationship between NO, and kiln torque (long wet process kiln). Figure 7 shows the same two patameters plotted against time; this time the kiln is a one- stage preheater with a production of 1050 tons per day. In this case, the delay is somewhat shorter, perhaps about 30 minutes. In both cases, however, NO, data precede the change in torque by a sufficient time increment to permit adjustment of the fuel rate or air flow, so that the temperature remains within the desired range. Figure 7. Relationship between NO, and kiln torque (1 stage preheater kiln) In cases where the kiln torque does not change in the direction predicted by the NO, read- ing, there is usually a good, logical explanation. For example, Figure 8 shows a time period during which the NO, is decreasing steadily, but it is not reflected in a corresponding de- crease in kiln amps. Such a case often indicates that localised reducing conditions may be present in the burning zone. This can frequently be confirmed by the oxygen analyser read- out, especially when, as here, a subsequent increase in oxygen causes a dramatic increase in NO,. Occasionally, especially when the burning zone is hot, increasing NO, readings may not be followed by higher kiln torque. Assuming that the kiln teed composition is constant, Asocem Page 14 August 2006 492INSTITUTE this may be a danger signal indicating that a dangerous increase in melt content may be oc- curring in the charge. woxipem) Torque a % of sal 00] L \ _ Time (hours) Figure 8, Localised reducing conditions may be present in the burning zone. A further advantage of NO, readout relative to kiln torque is that it permits the operator to maintain a more stable kiln torque. The average daily variation of the kiln torque of one 2500 ton-per-day wet kiln, before and after installation of an NOx monitor, is given in Ta- ble 1. Clearly, a reduction in the variability of kiln torque should be advantageous with re- spect to operational stability and brick life. Without NO, | With NO, ana- analyser lyser Free Lime [%] Average 15 08 Average deviation* 1,0 03 Asocem Page 15 ‘August 2006 493fism DTH INSTITUTE Kiln Torque [scale units] Average 69 39 Average deviation* 43 21 “expressed as the average deviation of each hourly value from the daily average free lime (in %) ‘Table I. 2.4.3 Clinker Alkali ys. NO, Since most raw mixes contain considerably more potassium oxide than sodium oxide, the K,0 can be used to represent alkali for most kilns with very little sacrifice in precision. There is a very clear inverse relationship between clinker KO and burning zone tempera- ture in any long kiln. Thus one might anticipate a similar correlation between NO, and K,0, Such a relationship does exist, as shown in Figure 9. The delay between the NO value and its corresponding KO is 1’ - 3 hours. The significance of this relationship is ‘twofold. Application of NO, data, obtained under stable kiln operation, permits the kiln op- erator to predict the alkali level of the clinker under production. If, for example, low-alkali clinker is desired, it may be possible to increase the volatilisation, and to follow the process of temperature increase with the NO, monitor. In efficient dry-process kilns, on the other hand, the volatilisation of alkali takes on additional significance: it controls the level of al- kali in the riser pipe and 4th-stage cyclone. The NO, monitor may be very helpful in judg- ing whether the burning zone conditions are suitable for avoiding build-ups or flowability problems. Asocem Page 16 August 2006 494fZismio INSTITUTE EE Time (hours) Figure 9. Relationship between the content of NO, and the content of Ki0 in clinker. 2.4.4 Free Lime and Litre Weight vs. NO, Free lime and litre weight are two clinker parameters frequently used to judge whether the clinker has been adequately burned. Because both parameters are temperature-dependent, it is reasonable to expect that they should also show a correlation with the level of NO,. Fis ure 10 shows the relationship of free lime and NO, as a function of time for a long wet kiln; the same relationship is illustrated for a 3100 ton-per-day preheater kiln in Figure 11. Both kilns are equipped with planetary coolers. The delay between the NO, reading and the cor- responding change in free lime is about 2 hours in the case of the wet kiln, while for the preheater kiln it appears to be only about one hour. The difference in both cases is probably sufficient to permit burning zone adjustments in time to prevent the production of insuffi- ciently burnt clinker, containing unacceptably high free lime, or unburned clinker, which represents wasted fuel, and which may be difficult to grind. ‘Asocem Page 17 ‘August 2006 495Gsm DTH INSTITUTE Fre time A 4 0 “ine our) ‘igure 10, Relationship berween NO, and free lime (long wer kil). In the cases where free lime does not show no good correlation with the NO, level, itis of- ten true that there has been a change in composition of the clinker, cither as a result of feed variations or of abrupt changes in consumption of ash-rich fuel. As in all the correlation noted, itis essential to ensure a uniform rate of feed with minimal compositional variations if the full potential of the NO, monitor is to be realised Asocem Page 18 August 2006 496(gesmmiorn INSTITUTE Figure 11, Relationship between NO, and free lime (4 stage preheater kil). In a manner similar to the free lime, the litre weight follows the NOx by about 2 - 3 hours, depending on the time in the cooler. Figure 12 shows one good example of the dependence; the delay in this case is generally about two hours. ay es 7 sy - ee e SEATS ' [= q wr oe Figure 12. Relationship between NO, and the litre weight, Asocem Page 19 ‘August 2006 497fiism DTH INSTITUTE 2.4.8 Expansion of the Kiln Shell as a Function of NO; The investigations included a large kiln fitted with equipment for continuous measurement of the "migration" of the buming zone tire. The purpose of this measurement was to give wariing when the clearance between the kiln shell and the tire became too small. The pa- rameter actually measured is thus the expansion of the kiln shell, which is temperature de- pendent just as the kiln torque is. Because of the time delay associated with heat transfer through the refractories, it can be anticipated that the delay between NO, reading and corre- sponding value of the shell expansion would be at least equivalent to that associated with the kiln torque. A plot of the expansion of the shell, together with the NO,, as functions of time, is shown in Figure 13. The delay is clearly 1 - 3 hours. Live ing migration (% of sale) Live ing migration % Time (hours) Figure 13, Relationship bemween NO, and the burning zone live ring. Asocem Page 20 August 2006 498fis DTH. INSTITUTE 2.4.6 Further Investigations A certain wet-process kiln was investigated to ascertain reasons for unacceptably high dust carryout which was being experienced. Among the relationships noted was that, as a gener- alisation, the dust carryout was most severe at very low NO, readings, which themselves correlated with high temperature readings just below the chain section. While the cause- effect relationship cannot be demonstrated with certainty, it appears likely, other factors being equal, that the use of shorter, sharper flames, which favour higher NO, readings, may have improved high temperature heat transfer, so that any "flash-drying” effect in the cooler portions of the kiln was minimised. This in turn should lead to better retention of the mate- rial within the kiln. 25 Conclusion This module has dealt with the use of a NO, monitor as an aid to detection of temperature changes in the burning zones of cement kilns. The advantages of rapid response to chang- ing kiln conditions have been pointed out, together with evidence for the relationship be- tween other parameters and NO, level. Finally, suggestions are offered relative to util tion of the rapidity of NO, response as an aid to improving kiln stability and clinker uni- formity, Asocem Page 21 August 2006 499