“HOLDERBANK” Cement Seminar Process Technology Circulation Phenomena in the Clinkerization ProcessSUMMARY This paper describes the circulation phenomena of the volatile elements. in the kiln system. It indicates the tolerable inputs of circulating elements so that no excessive build-up and clogging problems arise. In particular it shall serve as guideline how an encrustation problem caused by volatile elements is systematically solved.TABLE OF CONTENTS 1 INTRODUCTION 2 MECHANISM OF THE CIRCULATION PHENOMENA 3 CIRCULATING ELEMENTS IN THE KILN SYSTEM 3.4 Input of Circulating Elements 3.1.1 Input by the Raw Material 3.1.2 Input by the Fuel(s) 3.2 Enrichment of Circulating Elements / Endangered Zones for Encrustation Formation 3.3. Output of Circulating Elements 3.3.1 Clinker 33.2 Kiln Gas Bypass 3.3.3 Kiln Dust 3.3.4 Emission by Exhaust Gas 3.4 Volatility of Circulating Elements 3.4.41 Definition 3.4.2 Affinity of the Circulating Elements 3.4.3 Volatility of the Circulating Element Compounds 3.4.4 — Parameters influencing the Volatility of the Sulfur Compounds 3.5 Condensation of Circulating Elements 4. TYPICAL APPEARANCE OF BUILD-UPS 35. KILN OPERATION PROBLEMS DUE TO CIRCULATING ELEMENTS 6. IDENTIFICATION OF PROBLEMS WITH ENCRUSTATIONS AND BUILD-UPS 61 Material Balance 62 Criteria and Indicators to evaluate the Build-up Problem 6.2.1 Process Variables 62.2 Material Balance 6.2, 3 Enrichment of the Circulating Elements in the Hot Meal 624 Total Sulfur Volatility Page aan ©oo0mmaarno 10 13 13 14 15 15 15 16 7 763 6.31 6.3.2 7a) 72 73 Example of a Circulating Phenomena Problem Material Balance and Hot Meal Analysis Analysis of the Example . MEASURES AGAINST BUILD-UP FORMATION General Measures Measures against Chloride Problems Measures against Sulfur Problems MATHEMATICAL MODEL TO SIMULATE THE CYCLES OF THE CIRCULATING ELEMENTS 17 7 18 20 20 22 23 24INTRODUCTION Alkali, sulfur and chlorine compounds (hereafter called circulating or volatile elements see Fig. 1) in raw materials and fuels utilized for the cement manufacture, when present in high concentrations often give rise to difficulties in kiln operation with build-up formation in the preheater and the kiln inlet section. The build-up formations cause cyclone blockages or restrictions of the Kiln inlet area so that the kiln has to be stopped for cleaning. In extreme cases more than 200 annual kiln stops due to blockages may occur, so that the impact on kiln availability and productivity can become a severe issue. Suspension preheaters armed with dozens of shock blowers (Fig. 2a, 2b) to prevent build-up formation illustrate the importance of this problem. MECHANISM OF THE CIRCULATION PHENOMENA Depending on the degree of volatility, the circulating elements evaporate in the sintering zone of the cement kiln and are carried by the gases to colder zones, where they mainly condense on the raw meal and partly also on the surrounding walls. Afterwards they return with the raw meal into the sintering zone where they partly reevaporate depending on the degree of volatiliy. This repeated process through the kiln leads to the establishment of intemal cycles. Finally the cycles reach an equilibrium so that the output of circulating elements is equal to their input by the raw materials and the fuels (see Fig. 3). Almost all the circulating elements leave the system finally with the clinker. However, this is only the case when beforehand sufficienctly high internal cycles of the volatile elements have been formed. The extent of these cycles depend on the degree of volatility of the circulating elements. As the latter recondense on the colder raw meal and the surrounding walls, the formed sticky molten salts are able to reduce the fluidability of the raw meal and, if present in sufficient quantities, to glue it finally on the walls. From time to time, especially during a change of the temperature profile, pieces of build-ups fall down and mainly block the cyclone outlets (see Fig. 4). If the amount of molten salts becomes too high, either because of an excessive input of volatile elements or due to a high degree of volatility, the installation of a kiln gas bypass becomes necessary in order to extract part of the circulating elements from the kiln system (see Fig. 5a, 5b, 5c) A small part of the circulating elements leave the kiln system with the main exhaust gas dust. The latter is efficiently precipitated in the dedusting unit and is normally reintroduced into the kiln system. This is called the external cycle of the circulating elements (Fig. 6). In normal cases a negligible amount of circulating elements is emitted by the stack into the atmosphere. However, the emission of SO, is not negligible any more, when the sulfur in the raw material is present in form of sulfide (FeS,, PbS, ZnS) or organic compounds. in this latter case the sulfides are volatilized in the temperature range of 400 - 600°C and leave the kiln system partly as gaseous SO, emission (Fig. 7)34 344 CIRCULATING ELEMENTS IN THE KILN SYSTEM Input of Circulating Elements (see also Fig. 31a, 3b) In the following the typical inputs of circulating elements by the raw materials and the fuel(s) are indicated. Itis differentiated between input ranges where usually no encrustation and build-up problems arise and input ranges that usually lead to severe clogging problems. However, alll figures may serve as rough guide lines only. The real limits for the build-up and clogging formation depend on a lot of individual parameters like the degree of volatilization, the temperature profile, the completeness of combustion and the excess air factor as well as the kiln system itself. The indicated values are guidelines for suspension preheater kiln only. ny etials (loss fre > Alkalis (K, Na) generally appear as interlayer cations in the clay minerals and the feldspars. > The sulfur is introduced in several mineralogical forms: + as sulfate: gypsum CaSo4 . 2H20 anhydrate CaSo4 * assulfide: pyrite Fe, organic compounds In the following only the sulfates are considered, > The chlorides are mainly introduced as NaCl (from sea water) or KCl. Please note that the “kiln feed” normally includes already the external cycle (see Fig. 3) so that its concentration on circulating elements is higher than the one of the pure raw mix. Note: The following limits are typical for 4 - 5 stage SP-kilns. The other kiln systems tolerate higher inputs. cl < 0,02 % normal case, no problem > 0,05 % heavy problems with encrustations depending on the sulfur cycle Note: Sometimes additional chlorides come from the applied fuel(s). SO, < 05 % normal case, no problem if sufficientalkalis available (sulfates) *) > 1,25 % heavy clogging problems, depending on total alkali input and the additional sulfur from the fuel *) Sulfur in form of sulfides behaves in a different way, see chap. 3.3 "Emission by Exhaust Gas”ko < 1,0 % normal case, no problem > 4,8 % problems with encrustations, however depending on the degree of sulfatisation (molar alkali/sulfur ratio) Na,O _As the sodium volatility is very low, there is no real encrustation problem due to recirculation of Na,O. 3.1.2 Input by the Fuel(s) Note: The following limits are typical for 4-5 stage SP-kilns. The other kiln systems tolerate higher inputs. Coal; $< 4,5% No clogging problems, depending on the Coke: S<2 % sulfur and alkali input by the raw materials Fuel oil S<25% and the completeness of combustion (corresponding to approx. 5 g SO,kg cli) Coal: = S>3 % Severe clogging problems to be expected, Coke: S>4 % depending on the alkali and sulfur input Fuel oi: S>5 % by the raw materials (corresponding to approx. > 10.g SOykg cli) Gas Sulfur content is normally zero! Enrichment of Circulating Elements / Endangered Zones for Encrustation Formation Depending on the individual circulating element and its compounds, the condensing point lies in the temperature range of 650°C to 1000°C. The condensation of chlorides and its compounds takes place mainly between 650 and 800°C whereas the condensation of the sulfates and its compounds is between 800 and 100°C. Therefore the endangered zones for the formation of build-ups by the condensed circulating elements depend on one hand on the circulating element and its compounds and on the other hand on the kiln system itself (see also Fig. 4). In the following the build-up zones for the various kiln systems are indicated. At the colder end usually the encrustations by the chlorides are found whereas at the hotter end the ones of the sulfates are met.Kiln System |Zones of Build-ups Precalcinerkiin/ {The two lowest cyclones stage and their riser ducts, kiln inlet area 4or5 stage SP kiln |(first section of rotary part) Lepol kiln [Second preheating chamber, kiin inlet (first section of rotary part) 3 stage SP kiln Lowest cyclone and its riser duct, kiln inlet, first section of rotary part 2 stage SP kiln Lowest riser duct, kiln inlet, first section of rotary part Long dry kiln / wet | Calcining zone of rotary part (transition zone) kiln Fig. 8 and Fig. 9 show some typical analyses of raw meal (kiln feed), hot meal (meal from lowest cyclone) and clinker. 3.3 Output of Circulating Elements 3.3.1 Clinker > The chlorides are so volatile that they hardly leave the kiln via clinker. In exceptional cases, when the sintering zone has largely cooled down or when enbeded in big material lumps, the chlorides may leave the kiln in major quantities. However, normally the chlorides form a large cycle within the kiln system and they need to be extracted by a kiln gas bypass. > The sulfur and the alkalis leave the kiln system normally via clinker (see Fig. 10) either as definite compounds: K,80,, KyNa(SO)),, Na,SO, Cak(SO,), Caso, (rare!) or in solid solution in clinker minerals: K with the Belite, Aluminate Na with the Aluminate SO, with the Belite The calciumanhydrate CaSO, is rather volatile (decomposes at temperatures > 1000°C) and forms therefore a large sulfur cycle in the kiln system. Therefore it is very important that there is sufficient alkalis to combine with the sulfur and to leave the kiln system as alkali/sulfur compound,3.3.2 Kiln Gas Bypass Kiln gas bypasses (Fig. 5) are mainly used to extract the very volatile chlorides from SP preheater kilns. Chloride bypasses withdraw typically 5 to 15 % of the kiln gases. The hot gases from the kiln inlet are quenched down by fresh air, sometimes supported by injection of water into the quench chamber, to a temperature below 600°C. The gaseous chlorides condense onto the withdrawn dust particles and are separated finally in a electrofilter or a bagfilter (see Fig. 5a, 5b, 5c). In rare cases kiln gas bypasses are also applied in case of too much CaSO, and not sufficient alkalis. ‘Also for the production of low alkali clinker large kiln gas bypasses are used (20-50 % of the kiln gases) in order to withdraw the alkalis from the kiln charge and to produce a clinker with an alkali content of < 0,6 %, i.e. Na,O + 0,66 K,O < 0,6 %. Thereby the alkalis are volatilized by hard burning and by injection of chlorides into the kiln (see also chap. 7.3) The amount of bypass dust (10 g/kg cli per 10 % bypass if the withdraw system is optimized) must be discarded e.g. into the quarry or partly reutiized as additive to the cement, or in rare cases may be sold as filler material. The heat loss due to the extraction of the bypass gases amounts to 20 ku/kg cli per one percent bypass in case of a normal SP kiln or half of it for a precalciner kiln. Typical chemical concentrations of bypass dusts are found in Fig. 11 and 12. 3.3.3 Kiln Dust Another possibility to withdraw circulating elements from the kiln system is via external cycle (Fig. 6) which is interrupted and partly discarded. The enrichment of this kiln dust by circulating elements depends on the kiln system. Whereas kiin dusts from long wet kilns are highly enriched, the ones from SP kilns show nearly the same chemical composition than the raw meal. Typical chemical concentrations of dusts from the different kiln systems are shown on Fig. 11 and 12. Thereby the following legend applies: WL = long wet kiln DL = long dry kiln DG = dry kiln with grate preheater (LEPOL) DS = SPkilns: F - Filter dust from kiln exhaust gas BP - Bypass dust 3.3.4 Emission by Exhaust Gas Normally there is no emission of circulating elements by the exhaust gas. The only gaseous component, the SO, which does not condense at low temperatures is effectively absorbed by the free lime at the lowest cyclone stage.However, a source of SO, emission is the raw material sulfur in form of sulfide (e.g. pyrite). The sulfides decompose at temperatures between 400 to 600°C, forming SO,. Approximately 70 % of the SO, immediately reacts with the CaCO, of the kiln feed to CaSO, and finally at higher temperatures to CaSO,. The residual 30 % of the SO, are partly absorbed on their way with the flue gases to the stack, mainly in the raw mill and in the conditioning tower. However, a certain portion of the SO, is finally emitted by the stack, depending on the kiln and raw mill system (see Fig. 7). 3.4 Volatility of Circulating Elements 3.4.4 Definition The total volatility of a circulating element or a compound of it is defined as shown in Fig. 3, Cc CeL = Concentration in the clinker e ete Chim CHM = Concentration in the *hot" meal on loss free basis The total volatility of a circulating element or of a compound of it indicates which portion of it is volatilized in the kiln and does not leave the kiln straight with the clinker. 3.4.2 Affinity of the Circulating Elements Circulating elements have a strong affinity to other elements and form chemical compounds. The following affinity order has been observed (see also Fig. 14) 1. The chlorine combines first with the alkalis, forming KCI, NaCl. The residuel chlorine, if any, combines with the calcium, forming CaCl. 2. The residual alkalis combine with the sulfur, forming K,SO,, Na,SO,. They form also @ double salts Ca,k, (SO,),, K,Na (SO,),. The residual alkalis, if any, combine with CaO, forming K,CO,, Na,CO;. 3. The residual sulfur (SOs or SO,) combines with CaO, forming CaSO,.10 3.4.3 Volatility of the Circulating Element Compounds General a) In the kiln the alkalis are liberated from the clay mineral lattice. They partly dissociate into the gas phase and recombine with other elements according to the affinity order as described in chap. 3.5.2. The rest recombines directly in the charge material with chlorine or sulfur or is integrated into the lattice of the clinker minerals (belite and aluminate, see chap. 3.3). Especially the sodium is little volatile and goes preferably direct into the clinker (see also Fig. 15). b) The chlorides liberated during heating of the material and combustion of the fuel react with the alkalis to form alkali chloride. This reaction takes place either in the charge material or, after vaporization, in the kiln gas (see also Fig. 16) ¢) Upon volatilization of sulfur at buming zone temperatures in the cement kiln, sulfur dioxide is the predominant component. The gaseous SO2 origines either from the dissociated sulfur. of the combustibles or the decomposed CaSO4 and the partly volatilized Alk2S04 from the charge material ‘Subsequently if there is an excess of alkalis, the intemal sulfur cycle is caused primarily by the reaction with these, which takes place almost entirely in the rotary kiln, The alkali sulfates formed in this reaction are, in so far as they are present in vapour form, precipitated on the material. This occurs mainly in the rotary kiln itself, but partly also in the preheater. The precipitated alkali sulfates thus travel through the kiln again, pass through the sintering zone, and are partly discharged from the kiln with the clinker, while some of the alkali sulfates remain in the cycle. The calcium sulfate (CaSO4) is formed as a result of the reaction between SO2 and CaO. It is partly present already in the raw materials or is formed preferably in the temperature range of 800-900°C as illustrated in Fig. 17. Above a temperature level of 1000°C the calcium sulfate starts decomposing, first rather slowly and beyond a temperature of 1300°C rapidly. Sulfur dioxide again is formed. if the alkali input is not high enough to combine the whole incoming sulfur as alkali sulfate, high sulfur dioxide concentrations in the kiln gas arise. In such circumstances calcium sulfate may pass un-decomposed through the sintering zone leaving the kiln enbeded in the belite mineral or even as CaSO4. The sulfur cycle is illustrated in Fig. 18. Volatiliy of the Compounds of Circulating Elements Fig. 19 indicates the relation between vapour pressure of various alkali compounds at different temperatures. This demonstrates that the volatilization mechanism is dependant upon the form of combination of the particular volatile element.1 Chlorides: KCI, NaCl, CaCl, At a temperature level of 1200 - 1300°C the chlorides are already volatilized to a great extent. At sintering zone temperatures they are almost entirely volatilized so that the total volatility factor is approx. 0,97 to 1. Sulfates: Alk,SO,, CaSO, Basically the Alk,SO, is little volatile, whereas the CaSO, is highly volatile. Therefore the most important criteria for the total sulfur volatility is the molar ratio between the alkalis and the sulfur itself, corrected by the chlorine (see Fig. 20): Molar Alk / SO, rat Ak- Cl 9 = KO + NaO - Cl SO, 94 62 ra 80 The desirable value for the molar ratio: Alk. SO, = 12 If there are sufficient alkalis available to combine with the total sulfur input (from raw materials as well as from the fuel), the total volatility for the sulfur is @ = 0,3 to 0,5. However, i there is a surplus of sulfur over the alkalis, the highly volatile CaSO, is formed. @ Its volatility is approximately = 0,9, but can increase up to = 1, depending on the operating conditions of the burning process. in general the sulfur volatility is very much depending on the operating conditions of the burning process, such as > the maximum temperature in the sintering zone the retention time of the kiln charge material at high sinter zone temperatures the granulometry of the kiln charge material (diffusion to the surface of the granules) the partial pressure of O, in the kiln atmosphere vvvy the partial pressure of SO, in the kiln atmosphere For more details see next chap. 3.5.4,12 3.4.4 Parameters Influencing the Volatility of the Sulfur Compounds Maximum Temperature in the Sintering Zone The essential feature of the volatility - temperature curve is that above a certain critical temperature the volatility increases first exponentially and then slowly reaches a maximum (see Fig. 21). For sulfur this critical temperature is in the order of the burning temperature. Consequently hard burnable raw mixes or overheating of the kiln charge material (low free limes in the clinker) have a very important bearing on sulfur volatility. Retention Time of the Kiln Charge Material at High Burning Temperatures Volatilization of the sulfur compounds is a dynamic process. The longer the kiln charge material is exposed to the high burning temperatures, the higher the total amount of volatilized sulfur. Granulometry of the Kiln Charge Material If the kiln charge material is well granulated, the sulfur takes more time to diffuse to the surface of the granule. Consequently less sulfur volatilizes. Kiln Atmosphere The composition of the kiln atmosphere is an essential factor for the sulfur volatility: Me, (SO,), <> n «MeO +m-+SO,+ m 0, 2 ‘The equilibrium of the dissociation is shifted with increasing ©, partial pressure and SO, Partial pressure in favour of the sulfates Too little excess air or also local reducing kiln atmosphere increases the volatility of the sulfur. This behaviour is illustrated in Fig. 22 for the K,SO,. Laboratory tests have been executed for the primary volatility , in function of the oxygen content of the kiln atmosphere and the temperature (see Fig. 23). In a laboratory test the total volatility @ cannot be simulated, but only the primary volatility c,, i.e. the volatility of the sulfur when exposed the first time to high temperatures. It is remarkable that already at a temperature level of 1000°C, the sulfur volatility goes up to 1 (100 % volatility) if there is no oxygen in the kiln atmosphere. This is the case if the combustible produces a local reducing atmosphere in the kiln charge material e.g. when burning whole tyres at the kiln inlet. From these tests it can be derived that the main influence of the oxygen content on an increase of the sulfur volatility is produced between 0 to 2 % O2. Beyond 2 % O2 the influence is negligible.35 13 inlet. From these tests it can be derived that the main influence of the oxygen content on an increase of the sulfur volatility is produced between 0 to 2 % O2. Beyond 2 % O2 the influence is negligible, Also the partial pressure of the sulfur dioxide (SO,) decreases the sulfur volatility. That means that if the sulfur cycle in the kiln is large enough, the dissociation of the sulfates decreases and the sulfates can gradually leave the kiln with the clinker. However, this is not much of a help, as the required high sulfur cycles already cause encrustation problems! Condensation of Circulating Elements As previously stated, the circulating elements volatilize in the hot zones of the kiln and condensate at the colder areas of the kiln system. In Fig, 24 some melting points of the chlorides and the sulfates are indicated. Generally speaking it can be stated that the chlorides condense at lower temperatures than the sulfates. In the melting phase secondary compounds are formed which are more complex than the original volatile elements and compounds (see Fig. 25). Furthermore, investigations have revealed that calcium sulfate, calcium oxide and alkali sulfate form eutectic melts which can have much lower melting temperatures than the single compounds (Fig. 26). Under presence of chlorides these melting temperatures are even more lowered to temperatures until < 700°C. Very low melting temperatures show also the alkali carbonates. However, in such a case the alkalis can be sulfatizated by the addition of gypsum so that it presents normally not a major problem. All these melts, when present in sufficient quantities, lead to severe encrustations and build-up formation in the preheater and kiln inlet area. A further problem is given by the fact, that the volatilization process goes along with an endothermic reaction whereas the condensation is exothermic. By this way an important amount of heat is drawn from the sintering zone to the kiln inlet so that the area of condensation is shifted even more towards the cold end of the kiln system. TYPICAL APPEARANCE OF BUILD-UPS ‘Typical appearance of build-ups and deposits are shown in the figures 27, 28 and 29.14 KILN OPERATION PROBLEMS DUE TO CIRCULATING ELEMENTS The consequences due to high internal cycles of the circulating elements are rather severe. First it starts by an increased encrustation and build-up formation at the kiln inlet area and the lower part of the preheater. As a consequence the pressure loss across the system increases and at the same time also the inbleeding false air quantity. This reduces the maximum kiln draft and thus the maximum clinker production. When the kiln operator tries to compensate the lower available kiln draft by a lower excess air rate, the situation becomes even worse as the sulfur cycle further increases. Studies have revealed that a high chloride cycle impedes also complete combustion. This in turn further increases the sulfur cycle. High sulfur cycles lead to a poorly granulated clinker and therefore to dust formation. The dust entrains the heat from the buming zone to the kiln inlet, so that the cycles of the volatile elements further increase due to a longer residence time at high temperatures. Furthermore, the high cycles of volatile elements transport the heat of the sintering zone to the area of condensation by the endothermic - exothermic reactions, causing the same effect as the dust cycles described above, The result of these mechanisms is always the same: ~ Frequent kiln stops due to encrustation and clogging problems, i.e. reduced kiln utilization factor - Reduction of the maximum kiln production ~ Higher heat consumption - Formation of instable coating at the transition zone and thus high refractory consumption IDENTIFICATION OF PROBLEMS WITH ENCRUSTATIONS AND BUILD-UPS Encrustation and build-up problems can be caused by chlorides, sulfates, alkalis or any combination of them. Therefore a detailed analysis is a prerequisite to find an appropriate solution. The first step of the analysis consists always in performing a material balance with the inputs and outputs of circulating elements (see chap. 6.1). In @ second step the problem is evaluated according to the most important criteria and indicators for build-up formation (see chap. 6.2). In a third step specific measures against build-up formation are taken (see chap. 7).15 6.1 Material Balance Definition of the balance boundary (see Fig. 30a) - Shall the external cycle be included or excluded? = Please note that the kiln feed includes the extemal cycle so that the concentration n volatile elements is higher than the real inputs by the raw material. In this case the kiln dust must be taken into account as further output! ‘Taking material samples over a sufficiently large period (Fig. 30) - The sampling period should be at least 8 hours of representative kiln operation. - From every input and output an hourly spot sample shall be taken. The spot samples of the individual inputs and outputs are finally combined to one integrated sample. - The following quantities for the individual spot samples shall be taken: ~ raw mix (before grinding) ~20 kg ~ meal or dust ~ 0,5kg ~ clinker ~5 kg - fuel ~ 05kg Besides the samples for the material balance also samples of the hot meal at kiln inlet (outlet of the lower most cyclone stage) shall be taken, observing the same frequency and sample quantity as stated on point 2. 6.2 Criteria and Indicators to evaluate the Build-up Problem 6.2.1 Process Variables > Position of the build-ups * Ifthe build-ups are found up to the second lowest cyclone stage or even to the third lowest cyclone stage the problems could origine from excessive chloride cycles or in rare cases from too high alkali cycles. * If the build-ups are found mainly at the lowest cyclone stage, the lowest riser dust and the kiln inlet, the problems normally are caused by excessive sulfur cycles16 > Completeness of combustion . + CO at kiln inlet > 0,1 % and/or O2 < 1,5 - 2 % cause high sulfur cycles. If no secondary firing or precalcination is applied also the CO and O2 concentrations after preheater can be taken to judge the completeness of combustion (CO must be < 0,1 % and O2 usually 3 - 4 %, depending on the inbleeding amount of false air). > Temperature profile ° ° Excessive temperatures within and after the preheater indicate a disturbed temperature profile in the rotary kiln and thus a too high sulfur volatilization. A disturbed temperature profile in the rotary kiln can also be seen from the surface temperatures of the kiln shell > Pressure profile . The pressure profile over the preheater indicates where the build-ups are located. 6.2.2 Material Balance First a material balance must be performed as described in chap. 6.1. Afterwards, the following evaluation shall be done: > Input of circulating elements . It has to be determined in which form the sulfur is present in the raw materials, as sulfate or sulfide. When present as sulfide, part of it will leave the kiln system as emission via exhaust gas stack! Therefore the sulfur emission by the stack has to be deducted from the overall sulfur when judging a potential sulfur problem in the kiln. The inputs of circulating elements (without emitted sulfur through the stack!) should be compared to the ones given in chap. 3.1 (see also Fig. 31a, 31b) in order to check whether they are in a normal range where usually no build-ups are formed or whether they are too high. This, of course, is only a rough guideline, > Alkali / sulfur ratio (A/S) . The AJS ratio should be preferably at 1,2 or in a range between 0,8 to 1,5. ‘Compare it to the A/S ratio of the investigated case, deducting first the emitted sulfur from the total sulfur input by the raw mix and the fuel.7 62.3 \ent of the Circulating Elements in the Hot Mé > Fig. 32 illustrates the tolerable concentrations of circulating elements in the “hot meal, i.e. in the meal ex lowest cyclone stage. "Normal limit" means that beyond this concentration the build-up formation normally starts. "Maximum limit" means that beyond this concentration the build-ups become normally so severe that a continuous operation is almost impossible. The measured hot meal concentrations shall be compared with these guide values. > Fig. 33 considers the fact that normally both chlorides and sulfates are present in the hot meal and that both together determine the tolerable limits of concentrations. The actual case shall also be compared with this diagram. 6.2.4 Total Sulfur Volatility > With the formula for the total volatility (see Fig. 13) the individual total volatilities of the sulfates shall be calculated * If @ ofthe sulfur is > 0,7 and if at the same time the A/S_ ratio is within the range of 0,8 - 1,2, the sulfur cycle is definitely too high and needs improvements by measures as stated in chap. 7. 6.3 Example of a Circulation Phenomena Problem (Fig. 34a) 6.3.1 Material Balance and Hot Meal Analysis inputs Raw mi SO3 0,5 % (loss free basis) Ko 05 % NAO = 02% ci = 0,05 % Coal: s = 2%, SO3=5% Hu = 26'800 ki/kg, 6'400 kcal/kg Spec. heat consumption: q = 3'380 kJ/kg, 800 kcal/kg18 Outputs: Clinker: SOs = 085% KO = 05% NaO = 0.2% a = 003% SO,-emission: SO, = 400 mgiNm? (= 0,1 % SOs) Hot meal (loss free basis) S03 = 45% KO = 4% NaO = 03% a = 2% 6.3.2 Analysis of the Exampl 4. Material Balance % SO3 % KO [% Na,O [% Cr input raw mix 0,5 0.5 2 0,05 coal 0.6. total 14 0.5 0,2 0,05; Output clinker 0,85 os 0.2 0,03, 'SO,-emission_|0,4 — {totat 0,95) os 2 __—(0,03 > The total sulfur output is smaller than the total input. This is often the case when performing a material balance. There are two possible explanations: 1) The samples are not representative. 2) The process was not in.a steady state. Sulfur was kept back in the system, forming encrustations. During cleaning, the sulfur containing deposits left the kiln with the clinker but were not catched representatively by the sampling procedure.19 > The total chloride output is smaller than the total input. Here the same problems arise as described above. Normally the clinker does not contain more than 0,01 % Cl due to the high chloride volatility. However, if the chloride cycle becomes very large, values up to 0,05 % Cl in the clinker have already been measured. 2. Form of Sulfur in the Raw Materials Note that the raw material contains sulfidic sulfur (FeS2) due to the SO2 emission. The real sulfate input to the kiln is therefore: from raw mix to kiln 0,5-0,1 = 0,4 % SOs coal + 0.6 % SOs total input to the kiln 1,0 % SO3 3. Comparison with Typical Inputs of Circulating Elements (see Fig. 31a and 31b) > Inputs by the raw materials: - S03 = 0,4 % (sulfates only!) ok. ~ K,O and Na,0 0.k - C1=0,05 % very high, bypass required! > Sulfur inputs by the coal: - S=2% high, but within the normal range 4. Alkali / Sulfur Ratio os 4 02 _ ons ate: F AS = = 0,63 ry a *) total input to the kiln (see point 2) The A/S ratio is outside of the desirable range of 0,8 to 1,5.7. 7A 20 5. Enrichment of Circulating Elements in the Hot Meal > Comparison with tolerable concentrations of circulating elements (Fig. 32) ¢ SO3= 5%: high, far beyond normal limit, problems with encrustation + Alkalis: 0,86. 4+0,3=2,9%: slightly above normal, but highly desirable due to the large sulfur input! © Cl=2%: high, far beyond normal limit, problems with encrustations > Comparison with diagram for maximum concentrations (Fig. 33) S03 = 4,5 %) Cl =2 %) frequent blockages to be expected 6. Total Sulfur Volatility oF1- Gy (Fig. 13) Cou @ = 1- 085 = 081 45 @ > 0,7: — Because of the low A/S ratio, a substantial portion of the sulfur is in form of CaSO, which leads to the high volatility of > 0,7. MEASURES AGAINST BUILD-UP FORMATION General Measures Reduction of the Inputs of Circulating Elements > The most obvious measure against build-up formation is to reduce the input of circulating elements. It is normally not possible to change the main raw materials. However, sometimes a minor component that contains a substantial amount of circulating elements can be repla-ced. In most cases the sulfur content of the fuel is more easy to change. Please note that the fuel may also contain considerable amounts of chlorides. > The circulating elements of the raw materials in the quarry deposits are often not homogeniously distributed. In such cases prehomogenization of the raw materials combined with selective quarrying helps to reduce peak inputs of circulating elements into the kiln system.24 “Intelligent” Cleaning > Cleaning of the preheater and the kiln inlet will always be necessary. It can be more or less facilitated when observing some rules: > The riser ducts shall be protected by introducing the raw meal from the upper stage as low as possible (Fig. 35). Also adequate meal distribution boxes shall be installed, which distribute the raw meal over the whole cross section. An example is given in Fig. 36. > The meal ducts should be equipped with pendulum flaps in order to avoid a hot gas bypass through the ducts into the cyclones (Fig. 37). > Meal ducts with insufficient inclination (> 55°) and sharp bents should be avoided. > The cyclone outlets for the hot meal should be sufficiently large. If frequent bridging of the outflowing raw meal occurs, the outlet section shall be first equipped with air blasters and, if this measure does not help, it must be enlarged. > Dead corners in riser ducts, cyclones and the transition chamber shall be avoided. > Critical locations where always material deposits are built shall be armed with air blasters. Please note that mostly several blasters for one location must be installed since their cleaning radius is rader small (< 0,5 m). The blasters should always shoot in the direction of material flow (see also Fig. 38). > Foran efficient cleaning a special high pressure water pump (e.g. type WOMA) shall be applied. The application of this pump is dangerous and need special training of the operators. There is also a danger of destroying the refractory lining! > Cleaning should only be done if the pressure profile or a quick inspection indicate a need for. Opening of the big access doors disturbs kiln operation and let enter cold air which favours build-up formation. > Any false air entrance at the kiln inlet area and the lower preheater part must be avoided by continuous supervision and maintenance. > The installation of coating neutral refractory at the transition chamber and the lowest riser duct has produced good results in many applications72 Smooth Kiln Operation In many cases the cycles of circulating elements are frequently increased by an inadequate kiln operation applying to drastic changes in fuel feed and draft. Also the best kiln operator cannot apply during his daily work of 8 h such a super constant kiln operation. Therefore the author is of the strong opinion that only a fully automatic kiln control will provide optimal results, Measures against Chloride Problems > Reduction of the Volatility There is little chance to decrease the chlorine and chloride volatility as evaporation takes place at a low temperature range (800 - 100°C). > Discarding of Dust (external cycle) For long dry and wet kilns as well as for Lepol kilns the chlorides are effectively withdrawn from the kiln by discarding the finest fraction or the total of the kiln dust. For preheater Kilns dust discarding is normally not very efficient as the accumulation of chlorides in the dust is small. However, in case of a large internal chloride cycle this measure could help to keep it at a lower level. The effect of the measure can be calculated by a material balance. > Reduction of the Sulfur Cycle Build-up formation is provoked by all circulating elements together. As the chloride cycle cannot be effectively influenced, all possible measures should be taken to reduce the sulfur cycle. > Installation of a Kiln Gas Bypass If the chloride input of a SP kiln is larger than 0,02 to 0,03 % (loss free basis) a chloride bypass must be installed. Whether the higher limit of 0,03 % can be tolerated depends on the expected sulfur cycle. A.rule of thumb to calculate the quantity of required bypass gases is: % Bypass = % Cl of the raw materials (loss free) x 100 Example: % Cl of the raw materials = 0,05 % Required bypass size =5 %73 23 Measures against Sulfur Problems > Reduction of the Sulfur Volatility The sulfur volatility can be influenced to a great extent. . First of all, if there are possibilities, the A/S ratio should be adjusted to the ideal value of 1,2. ‘The second measure is to control the excess air rate to 2 % O2 at kiln inlet. Please note that the measurement of O2 at kiln inlet is a spot sample and does not necessarily represent the whole inlet cross section. The 2 % O2 can therefore be a guide value only. The third measure is to ensure an adequate fuel preparation in order to have a complete combustion with a CO content at Kiln inlet of 0 to maximum 0,05 %. That means the correct fineness of the coal and correct fuel oil temperatures (e.g. 150°C). Very important is also a stable dosification of the coal and no pulsation of the coal dust in the feed pipe (velocity 35 m/s, corner pots). The burner itself should be of the latest design, which produces a short and stable flame in order to have the shortest possible retention time of the kiln charge in the high temperature zone. It should be directed parallel to the kiln axis and should not point to the kiln charge in order to avoid local reducing burning conditions. The thermal load in the sintering zone should be as small as possible. For that purpose a secondary firing or precalcination shall be applied Avoid overburning of the clinker, Fig. 38 demonstrates the strong influence of burning zone temperature (indicated by the concentration of NOx) on the accumulation of SO3 and especially CaSO, in the hot meal. Furthermore also the influence of the excess air is shown. If solid fuels (e.g. used tyres) are burnt at the kiln inlet, lifters shall be installed in order to keep the fuel pieces at the surface of the kiln charge and to avoid local reducing burning conditions. ‘Sometimes there is a possibility to improve the burnability or the granulation of the clinker by modifying the raw mix. These measures help to reduce the required maximum temperature in the burning zone and to reduce the sulfur volatilization from the clinker granules. Shifting of the condensation area of the sulfur towards the kiln inlet and the first zone of the rotary part This effect is achieved by increasing the A/S ratio and by avoiding high kiln inlet temperatures,74 24 > Discarding of Dust Especially for long dry and wet kilns discarding of dust is a very effective measure to withdraw the sulfur from the kiln. This does not hold true for SP kilns as the accumulation of sulfur in the external cycle is small. > For SP kilns the installation of a kiln gas bypass may become necessary if there are almost no alkalis to extract the sulfur from the kiln, > Automatic Kiln Control Automatic kiln control helps very much to keep the sulfur cycle low as no overheating takes place and the kiln draft is always correct. Measures against Alkali Problems > Alkali Volatility In absence of sulfur the alkali volatility is very high and creates problems in the preheater. In such a case the raw mix can be sulfatizated by addition of gypsum. > Low Alkali Clinker If low alkali clinker must be produced, all measures must be taken to increase the alkali volatility, such as reducing the sulfur input * producing a long and stable flame + applying hard burning (CaOtree < 1), if possible reducing the bumability by increasing the silica ratio * applying a minimum of excess air * chlorination of the raw mix either by burning chloride * containing solvents or adding CaCl, > In case of long dry or wet kilns the alkalis are withdrawn by discarding a fraction or the total dust of the external cycle. in case of a SP kiln a (large) kiln gas bypass is, required. MATHEMATICAL MODEL TO SIMULATE THE CYCLES OF THE CIRCULATING ELEMENTS The cycles of the circulating elements in the kiln system can be simulated by a mathematical model (see Fig. 40). This model is used for bypass calculations and for simulating special effects on the behaviour of the volatile cycles.VOLATILE ELEMENTS - Sulfur $03 - Potassium Ko0 pfelicles ahs Nar - Sodium Na sO - Chlorine Cl (uapere tien ee He & Ln conslunrcrbeon on Ya Ped me walls nd Chuae fault ups el wad. Hee, Ly ilines - Pipe Fig. 1Fig. 2b£ ‘Sid XIN MD pees UID FOxUND FSP UL ajoko, Jouse}u| PeZIIRDIOA ~~ apkg | |pusa}xQ | euoZ Buezuis peer KP] sod Ag 77970004 WALSAS NTI 3HL NIHLIM SLNAN313 STLVIOA JO NOLLYINOYIOSP—Preheater/ Precalciner Kiln Lepol Kiln Long Dry Kiln with Crosses ‘Slurry Ring BUILD—UPS DUE TO CIRCULATING ELEMENTS IN THE VARIOUS KILN SYSTEMS Ring in the calcining zone FIG.Va-E62) Tox nna ia anvil] oseoee siva] nave NOLLOSPNI YaLVM @ SSVdA@ TWNOLLNSANOD ‘TO “SL uoIsiAig ABojouyoe|, e6ad0q wt OL 4/ MIN 000,91 wt se o— uf Z-L yaLid OVE U/QWIN 00,2 uw wie 4/,4N 000,521 P/} 002.2 be 9,001,1 OW TW MWe 2, See Fig. 5aNOLLOIPNI YALVM LNOHLIM SSvdAd SVD LOH To xSL 4/,WN 000,521 P/3 002,2 > “Ss 4/,4N 002.9 9, 0O1,L MO 4/,WN 000,z¢ Fig. 5b4/,4N 000,SL JoKBAUCD MO19S p9|009 4930" 4/ 4IN 000,Sz yQBsaaa4 svo Hum ssvare Y/4N 000,921 P/+ 002.2 %L = Y/,4N 008,8 TO “SL Fig. 5¢Circulation Phenomena Fig. 6$02-Emission in case of Sulfides £ a 3]S0, Fig. 719 RAW MEAL HOT MEAL a CLINKER RAW MEAL HOT MEAL CLINKER L.o.i. 34.8 7.9 0.82 L.o.i. free: SiO2 21.3 19.8 22.8 Al203 5.1 4.6 5.7 Fe203 3.4 2.7 3.5 cao 66.0 57.0 63.7 MgO 2.0 1.6 1.8 $03 0.2 1.6 0.55 K20 0.78 6.4 0.62 NagO 0.57 1.3 0.73 TiO2 0.23 0.18 0.25 cl 0.25 5.5 0.11 Fig. 8RAW MEAL HOT MEAL CLINK®? RAW MEAL HOT MEAL CLINKER L.o.i. 35.2 5.6 0.84 Lo.i. free: Si02 23.5 22.3 23.8 Al203 43 41 46 Fe203 2.0 19 20 @ cao 65.6 60.0 65.0 MgO 25 2.2 2.2 $03 0.12 4.2 1.2 K20 1.06 3.3 0.96 Na2O 0.26 0.32 0.38 Ti02 0.23 0.21 0.21 Mn203 0.12 0.07 0.09 P205 0.08 0.06 0.07 cl 0.06 1.56 0.01 120 Fig. 9Volatile elements in clinker as definite compounds K2S0q, K3Na (SOq)9; Na2SO4 Cagk2 (SO4)3 CaSO, (rare) in solid solution in clinker minerals (see chapter 13) K : Belite, Aluminate Na 5 Aluminate $03 : Belite Fig. 10desis Fig. 7a KILN DUST ANALYSES. d — Wot loTavd aimee fo (fou? é yPese perloh ——‘\_|CHLORIDE POTASSIUM fn splice 40 —— jupacle eur 36 4 : coher! [les high co ) 325 in ae ola} J w | hype 4 28 vid Whe do lenil » & 24 InniBowed = 4 wile GB a0 J . ur | ; byre® ") w , 6 4 e ak oy & ‘ 5 a 7 “e 124 el. a Pee ae 4 . . . ° eje 2 44]. . els et : 3 . wl t|. 4 | Bg hae lal & . FP jap |PGOL WL PS, |oa]ou jw. — epee» 4 Cy, pass . Pepe ee bln piuliall j x -Cosked io ol & fet eon Fig. 11KILN DUST ANALYSES LOSS ON IGNITION SULFUR (SO3) 40 . BBEL DSc cfe ame 00 © oe . s . . a . occ e 3 e ~o ee oo 09.00 Wekeo BH e oy . e % U ccedeteptetybe | S : : a ee Be ce oe 8 . g a © 880 oo ee on T cee T T T T T T T T T T © Q o + ° gs 8 8 & & & 8 ALHOIAM AG LNSOYAd Fig. 12THE VOLATILITY OF A CIRCULATING ELEMENT Hot meal Cum Volatility : Fuel Clinker fcan oO Concentration of the circulating element in the hot meal at kiln inlet on loss free basi f- Cune Cel Chn Cot @=1- Cum @ = Factor for Total Volatility CoM = Co. = Concentration of the circulating element in the clinker FIG. 13Sosa no *os n> Fon tay tomy Diw]-*os (fos!) = Iv vos™v (D1-71v [(es44d)$] -"os 1D>1v MS Ppa 3b > wren Ayyornct-a NEW e e Fig. 14Circulation of alkalis + Alkalis in dust AlkgS0q! (Alko0 ; Alk Cl) in solid solution or in clinker minerals Fig. 15SS Circulation of chlorine f 2% Chlorine in finest dust i i ee (Alk CI) AlkCl AlkCl (CaCl) Fig. 16—— SO. ABSORPTION BY CaO resp. CaCO3 SO Absorption a Decompostion of CaSO, \ ‘aS04 | fooo +80, =caso, @ CaS05+ 1/2 Op = CaSO, a CaCO; + SO, = CaSO,+ CO, T T T T T > 600 700 800 900 1000 °6 Reaction Temperature FIG. 17Circulation of sulfur 802+ CaO (&.Ca CO3) Decomposition of Ca SOg (AlkgS04 ) 500-1000°C (opt. 800°C) Ca S04] --4-- s eantt 7 ae == ‘Ca S04 oa Met TV V {02 KT L (ak 2804 = ar Ye Alkz S04 Alk2S04 (Ca S04) Fig. 18VAPOUR PRESSURE mm Hg 760 700) 600 500 400) 300) j% 200) K2504 100) 700 800 900 1000 1100 1200 1300 1400 1500°C Temperatures Fig. 19Important criteria Molar alk/SO3 ratio ( nit % Tut mi) KO, Naz0 yuh perc Alk - cl = 94 62 TE ahr y(t S03 S03 80 Caliah oy pohl-oipal Cha ¢ tab adx ) Desirable value: Alk - Cl = 12 $03 Fig. 20VOLATILITY-TEMPERATURE CURVE Volatility Critical range Temperature °C 4 200°C Fig. 21O2 in kiln gas K2S04 > K20 + $02 + 1/2 O02 @ Oxygen excess in burning zone K2SO4 <== K,0 + 502+ 1/2 OF > Oxygen deficiency in burning zone K28O0q4 < K20 + S02 + 1/2 O02 > e@ Fig. 22SO, €1 1,0, 1400°C 08 0,6 04 e 0,2 1200°C 7 1000°C 0 1 25 50 %O, 70% N, ,a.30% CO, Fig. 23Chlorides Nach Kel Cally Sulfates Na2SO4 K2S04 CaSO Melting points 801°C 776°C 772°C 884°C 1069°C 1280°C (decomposed) Fig. 24Secondary compounds Chlorides KCl (NaCl) Sulfates K2S0q4 K3Na (SOq)2 Na2SOq CagK2 (SO4)3 CaSOq4 Carbonates K2C03, (Na2CO3) e Spurrites 2 C95 - CaCO3 2 CoS - CaSO4 Fig. 25MELT INTERVALS IN THE SYSTEM CaSO, - KySO,4-Na2SO, Na2SO,4 fo-m A MELTTEMPERATURE °C <800 800-850 cae Es 250-200 900-950 / B& {OO > 250 é WA + 700-800 > 800 CaSO, K2S04 Fig. 26sake, ueynbaay (pL saake| 312s pasuapuoy (9 1 n N 2 at) yeluy uLD S : uo 242 Way aH : = oe vSl/e8 Lbv/ts8 apejuns ydomspuim (2 L auoloh> pag aH O91 /¥8 S3dA1 LTSOda0 40 SHdvUDOUIVH TP FI@VLOLOHd. <=S.E.M. MICROGRAPHS OF DEPOSITS PHOTOTABLE, i | i REM 84/506 REM 84/525 3.a)|cHD - Ist cyclone — 20 um \pfine matrix’ \ 1 KCI blocks embedded. REM 84/502"oe Tut Riser pipe — ZUM in! \ibordehMaterial Balance Boundaries T pe L_/ L Raw Mix) \o —K, e b PL al Clinker Fig. 30aMaterial Balance of Circulating Elements Definition of balance boundary line Material sampling .» raw mix ~ 20 kg/sample + meal dust ~ 0,5 kg/sample e@ . linker ~ 5 kg/sample . fuel z 0,5 kg/sample Sampling period: During 8 h every hour one spot sample. The 8 spot samples are combined to one integrated sample. Similar sampling of the "hot meal" 0 uabe Wey Aang pop l Cratdlabl y wpeiol nlabcimabier Fig. 30bTypical Input Limits for Circulating Elements by the Raw Materials (For 4-6 stage SP kilns only) (loss free basis) a < 0,02 % > 0,05 % S03 << 0,5 % > 1,25 % K20 << 1,0% > 1,5 % normal case, no problems heavy clogging problems, depending on the sulfur cycle normal case, no problems heavy clogging problems normal case, no problems problems with encrustations, depending on degree of sulfatization NaQO Little volatile, thus no problems Fig. 31aTypical Input Limits for. Circulating Elements by the Fuel(s) (For 4-6 stage SP kilns only) Coal $< 15% No clogging problems, Coke s<2 % depending on sulfur and alkalis Fueloil S < 2,5 % input by the raw materials and the completeness of combustion (corresponding to appr. < 5 g SO3/kg cli) Coal S>3% Severe clogging problems Coke S>4% depending on the alkalis and Fueloil S > 5% sulfur input by the raw materiak@ and the completeness of combustion (corresponding to appr. > 10 g SO3/kg cli) Fig. 31b80 z (6-72) INIMOTHD sz v («P20%N) — SLTWTW ¢Z ¢° (%-f0s) YNHdINS Hwy |OULION sup WunwWixDyw (siswa uDINIID NO) 7W3AW LOH NI SNOILVALNIONOOD Fig. 32Maximum tolerable concentrations in the "Hot Meal" (All concentrations on loss free basis) Sulfur: 5% $O3 Alkalis: 4% Na2O0-equivalent Chlorine: 2% Cl Combination of Sulfur and Chlorine 0 1,0 20 !' 30 4,0 5,0 25 3,75 % 803 TS/VA ““HOLDERBANK™ Datum: 13.04.89 | Zchng.Nr. 47766-E Fig. 33Example of a Circulation Phenomena Problem Material Balance Raw mix: $03 = 05 % (loss free basis) cl = 0,05% K20 = 05 % NagO = 0,2 % Coal: s = 2%,$03=5% Hy = 26800 kJ/kg, 6400 kcal/kg Specific heat consumption: q = 3/350 kJ/kg, 800 kcal/kg Clinker: S03 = 0,85% K2g0 = 05 % NagO = 0,2 % cl = 0,03 % $O9-emission: $O2 = 400 mg/Nm? (= 0,1 % $03) Hot Meal Analysis (loss free bases) SO3 = 45% Kg0 = 4 % Na20 = 03% cl = 2% Vewl, : M,, hy ol Fig. 34aExample of a Circulation Phenomena Problem Material Balance %SO3 | %K2O | %NaQ0} % Cl Input raw-mix 0,5 0,5 0,2 0,05 coal 0,6 e@ total 1,1 0,5 0,2 0,05 Output clinker 0,85 0,5 0,2 0,03 $02-emission 0,1 total 0,95 0,5 0,2 0,03 ® 1) Analysis of material balance 2) Form of sulfur 3) Comparison with typical inputs 4) A/S 5) Comparison with hot meal limits 6) Sulfur volatily Fig. 34b‘Cement Seminar 1995 Circulation Phenomena Examplé: 4. Auxiliary Catculations Coal Consumption = 3350 kuikg = 0,228 kgcoall kg ol LEO ki/kg coal Sulfur from‘Coal = S %803 x 8.7L = O. 625 %ciS03 42432.7 _ 803 = Sefae Molesikg = ZS s 32.7 Moles kg 802 via Exhaust Gas = 2 Nmsikgex 40 mgim3 = £29 © mgSo2ngali $03 = 4 Moles/kg_ = 7 27 ‘S02 4,0 Moles kg $03 Equiv. via ExhaustGas = 7 29 x GAP mg so2ikgci= ACEO mg SO3Kkg ali 2 mea L een | input [Raw Mix 6,05 Coal = Total OOF Output [Clinker 0.03 Stack - up ~Oef 4Balance Error ©, b2 [Total OOS 3. |EATCnimentaRa VoraTIy ay] His geese ao Conc. in raw mix C feed OCS C2 IConc. in Hot Meal CHM O2 Enrichment C HM / C raw mix ¢ ,, in HM. 4 10 AS [Volatility 1-Cci/CHM 6 | 7-c.85~ G~ 20 Ze 14-6203 = Bro gay 6 e 4. Molar Alkali / Sulfur Ratio = K20 / 94 + Na20 /62-Cl/71 ; Fi i aelaheot te redone OS gy 4 O60 <<42 25 (80 5. (Comparizon with Limits’ a ee. 2 ee Enea ee | ual Total Input ABCC HIE! | ei OS" 0164 462. = OF input limits Oe 8 22 \7 : [Actual Concentration in HMI FinS Zo 4-046 30,3 =234 [Concentration Limits forHM___|25" | SD lon€. 22) 25 . * Na20/K20 = 62 / 94.2 = 0.66 6. Conclusion 4. 0 la - Uv. 4 a CL maha ¥ HMC TCIVA Ga & a & O10 “ae bic Fecty Be bcd pipeMoles Ca + CL lhe G4 47 36,5 » Mb » 34.7Cement Course 1995 Circulation Phenomena —_ Example: 1. Auxiliary Calculations Coal Consumption = 3350 kkgcli_ = 0.125 kg coal /kg cli 26800 kJikg coal S03 = 80.1 Moles /kg__= 2.50 s 32.1 Moles kg Sulfur from Coal = 5% S03 0.125 = 0.625 % cli SO3 ‘S02 via Exhaust Gas = 2Nmsikgex 400 mgiNm3 = 800 mg SO2/kg oli $03 = 80.1 Moles /kg__ = 1.25 S02 64.1 Moles kg S03 Equiv via ExhaustGas = 4.25 9 x 800 mg SO2/kg cli= 1000 mg SO3/Kg cli el oS ate ae Ee eee ne. input Raw Mix ICoat [Total O2 [Output [Clinker 02 Stack Balance Error 0.00 [Total 0.200 3, a Tate lat To S08 oe ICone. in raw mix Craw mix 0.50 ICone. in Hot Meal_C HM 4.50 Enrichment CHM/Cteed «| 45/05= in HM 9 jvolatiity 1-Cci/CHM $ | 1-085/45= 0.81 Molar Alkali / Sulfur Ratio K20 1.94 + Na20/62 - CI/74 '$03780, = 05/94+0.2/62-0.05/71_ = 061 <<<4.2! (1-125 - 0.1) 780 ech with Lim Be S03 c squiv]® Cee ae aoe a : fe mane: Ss | [Actual Total Input 7 ADEE 0.05 J05x066+02= 0.53 Input tits 05 1.25| 0.02 0.05|1.0 15 [Actual Concentration in FM 45 ZO |a0x080+ 03> aor [Concentration Limits for HM [2.5 solos 2.0|2.5 40 *NaZOIK20 = 62/942 = 0.65 6. Conclusion ‘The buildups are caused by high input of SO3 and Cl. HMC TCWVA GaProtection of the Riser Duct Walls against Condensation of Circulating Elements worse betterMEAL DISTRIBUTION BOXES BY POLYSIUS CORRECT Fig. 36 WRONGExample of a Pendulum Flape for the hot meal duct of the lowest cyclone in a suspension preheater (Polysius) Material quality of flap DIN G-X 40 CrNiSi 27 4 Fig. 37truakloe Creu Typical clogging areas of SP kiln : ~ inlet chamber ~ riser duct — cyclone inlet ~ cyclone meal duct Application of Air Cannons inns Fig. 38ENRICHMENT OF SO3 IN THE HOT MEAL OF THE LOWEST CYCLONE STAGE % SOz hot meal ppm NOx Kiln inlet mad T 1400 © 0p at transition chamber normal X Op at transition chamber moderate ® 0p at transition chamber very low FIG. 39Mathematical Model to Simulate the Cycles of the Circulating Elements in the KILN SYSTEM : : ; PREVIOUS “EMISSION a RAW MIX EXTERN CIRCULATION OUST DISCARDED ! " fi : ca | 1 | SYSTEM | i e ATP i a s Meo. 4 PRECALCINATOR ! }e—K} _ | Ay ee ‘=> BYPASS | Tate =| e ‘STATIC PART] : a © ROTARY ns KILN | SYSTEM ! Amex B | e Akt | + KILN BURNER Fig. 40“HOLDERBANK” Cement Seminar Materials Technology Rings, Balls and Build-Upss es wma aeeE Table of Contents INTRODUCTION LOCATION OF RINGS Classification ‘THEORETICAL ASPECTS OF RING AND DEPOSIT FORMATION CHARACTERISTICS OF VARIOUS RING AND DEPOSIT TYPES Exhaust Fan Deposits Slurry Rings Cyclone and Grate Preheater Deposits Meal Ring (Calcining Ring) in Long Kilns Middle Rings in Large Preheater Kilns Sinter Rings (excl. coal-ash rings) Coal Ash Sinter Rings Clinker Rings / Cooler Inlet Deposit Kiln Charge Balls METHODS OF REMOVAL/ELIMINATION TABLES 1 - 7 APPENDICES I - III w Hee NBOOom v8H 13RINGS, BALLS AND BUILD-UPS INTRODUCTION Rings and deposits are accumulations of solid materials (from the powdery kiln charge) in the rotary or static sections of clinker production lines. They have been encountered since the earliest days of rotary kiln production, with each develop- ment in process technology, e.g. grate and cyclone preheaters, grate cooler, bringing with them their own specific type of deposit. Rather than being of academic interest, ring and deposit formation has an appreciable influence on plant operations, frustrating operations personnel by their impairing or even impeding production, and annoying the company management by lowering produc- tion (and sales) and increasing production costs. As a direct consequence of rings and deposits, the gas and material flow through the kiln is restricted, resulting in a reduced kiln output. Especially in the sinter zone, the presence of rings can interfere with combustion of the fuel and can result in improper combustion. From time to time unstable rings and deposits can break away leading to blockage or mechanical damage in the cooler, or in cyclone blockages. The partial shedding of coating from the exhaust fan blades results in severe vibra- tion which mostly requires a short shutdown for complete removal. The breaking of a ring almost always causes a flush of material into the burning zone and a temporary loss of stable kiln operations. The formation of deposits in cyclones results in extra costs for the labour needed to remove the deposits by poking. The introduction of air canons (big blasters) provides a method for their regular automatic removal and has been installed in Group plants with persistant preheater blockages. High pressure water jets may also be employed. In the worst cases, a complete shutdown is necessary to allow entrance to the affected area and mechani- cal removal of the blockage with compressed air drills. This shutdown invariably weakens the sinter zone refractories, and accelerates the next shutdown for rebricking.2. LOCATION OF RINGS Classification Unwanted build-ups may be classified with regard to the type of material from which they are formed, either sintered or unsintered. Within these two groups the various types can be classified as follow unsintered . exhaust fan deposits + cyclone and grate preheater deposits + slurry or mud rings + meal rings sintered + middle ring + sinter ring + clinker ring + "snowman" in grate cooler + kiln charge ball Process technological characteristics of such build-ups e.g. kiln type, location, temperature of gas and kiln charge can be seen in Table 1. Material technological characteristics e.g. state of kiln charge, enrichment in various elements, and type of texture are summarized in Table 2. The location of the various types of the above rings and deposits can be seen in Fig. 1.Fig.1 z-o=a/1 SONY YAYINITO 2-t=a/7 SONY USLNIS e-2=a/7 SONY WSN | SONI STGGIN 431009 i-sea/t O41 1a SONY HSV NO ONILVOO SINALSAS NIM LN3YSS4I0 NI SdN-a1na GNV SONI ONIN ANYMIS sTiva Gnw NU LAM Nm ua.LW3Hadd aivyd NUM YALWSHaudd ANOTOADTHEORETICAL ASPECTS OF RING AND DEPOSIT FORMATION Although of much practical significance, little quantitatively based, fundamental knowledge is available on the formation of deposits from solids suspended in gas streams. In a qualitative way, however, the more important features of such pro~ cesses are known. The formation of a deposit is always a dynamic pro- cess in which the factors responsible for formation outweigh the forces of degradation. In general, the stronger the forces of destruction, the more unli-~ kely the chance of deposit formation, but when this does occur, a strong, hard to remove agglomeration is the result. After the transport of material to the area of depo- sition, a definite force is required to make it adhere to the wall. This can range in magnitude from that caused by turbulence within the gas stream, increasing to centrifugal forces when the stream changes direction, to that due to mechanical pressure. Whereas preheater deposits involve the first two, mechanical pressure certainly plays a part in ring formation within the rotating kiln. The forces according to Rumpf considered to cause deposit formation can be grouped as follows: A - melting or softening of surface due to friction or collision B - melting or freezing due to addition or removal of heat © - interlocking of aggregates built up of finer particles held together by surface forces D - interlocking of long fibrous particles E - electrostatic attraction The mechanisms B, C and D are the ones encountered in kiln operations. In general, the finer the powder, the greater the tendency towards agglomera~ tion, and in many cases the absence of particles under a critical size (e.g. 5 um) ensures freedom from deposition.CHARACTERISTICS OF VARIOUS RING AND DEPOSIT TYPES Tables 3 and 4 contain a list of typical proper- ties of rings and build-ups encountered within the “Holderbank" Group plants (with full chemical analy- sis being provided in Appendices I, II and III). Included are such factors as volatile element con- centrations and moduli of the deposited materials. As an indication of the texture, the size of the pores and the particles or aggregates of particles, from which the materials were built up, is given. In many cases the mineralogical composition is also given. Exhaust Fan Deposits In the case of kilns with pressure filter systems, in which unfiltered dust-laden gas passes through the exhaust gas fan, deposit formation causes problems. These arise when the deposit falls off one blade, and brings the rotating fan out of balance. Deposits of up to 3.5 kg/blade are known to occur. Characteristic propertie Exhaust fan deposits, composed of the finest raw meal particles are usually red-brown, hard and quite brittle. They exhibit a compact layered structure and have a very low porosity of 8%. Their chemical and mineralogical composition is basically that of the raw meal but often the plate-shaped clay particles are preferentially deposited parallel to the blade surfaces. Due to their long stay in the system, fan deposits are enriched in the volatile components K20, Na20, 803. Typical values include the following: LSF 20. - 100 SR 1.0 - 1.5 K20 + Naz0 2.1 - 3.08 803 4.7 - 6.0% The S03 is usually present as anhydrite (CaS04).Binding mechanism: In this case, the temperature is such that liquid phase involvement - aqueous or molten salts - can be ruled out. The dust particles, because of the fan rotation, strike the blade surfaces with a high velocity and are so compacted. As the texture of the surface, after even a short time in operation, possesses undulations in the order 0.5 - 20 um, the smaller dust particles can be mechanically "locked-on". Subsequent development of the deposit follows by an identical mechanism. Slurry Rings (including mud balls) Characteristic properties: These occur in long wet kilns and are composed of the partially dried kiln charge somewhat enriched in alkalis and S03. They are soft and can usually be broken - and hence prevented - by heavier chains. The 20 content lies between 20 and 30%, a range in which clay materials exhibit a sticky, plastic consistency. The content of the alkalis which greatly increases the tendency to adhesion (influence on rheological properties) can be up to 10% K20 + Naz0, and about the same level of S03. In many cases, balls form (in addition) on the chain links by the same mechanism. A typical example of a mud ball is plant I in Table 4. Binding mechanism: The binding mechanism is the well-known ability of clays to form a sticky, plastic mass when con- taining the correct quantity of H20, and to harden on the further water loss. To this mechanism must also be added the crystallization of K2S04 solu- tion and the further strengthening of the struc- ture by formation of CaS04. Photo la gives an example of such a ring.Cyclone and Grate Preheater Deposits Characteristics: These deposits form on the roofs, walls, outlet and riser pipes of cyclone preheaters, in the hot chamber of grate preheaters, and vary considerably in appearance and homogeneity. In general, they have a light colour varying from cream to brown to pink, indicating that the component particles had not been heated higher than 1200°C. In some cases, darker zones of harder burnt material can be observed. Depending on their place of deposition, they range from a dense, compact, definitely layered structure, hard to break to a porous (30%) material with only moderate strength with less obvious layering. The former type is typical of cyclone cones and discharge pipes while the latter is to be found in the transition and swirl cham- bers. Soft deposits can, however, also be found in the cyclones. From a chemical viewpoint, this deposit type usually is characterized by a concentration of the volatile elements in the following range: K20 = 1 - 308 Nago = 0- 28 In some cases, therefore, deposits can occur with no appreciable increase in concentration. Typical analyses found for deposits are given in Table 3 and Appendix I. The mineralogical composition of preheater depo- sits differs as would be expected from that of the raw meal in that the clays are essentially decom posed, and a reaction to form intermediate minerals has taken place. Minerals containing only the volatile elements can also be found. Amongst the minerals found in preheater deposits are the following: raw meal calcite caco3 quartz Si09 normal intermediate phases free lime cade periclase Mgo’ mayenite C12A7 elite ordtypical deposit phases with low melting point: sylvite KCL halite NaCl langbeinite 2CaS0q . K2S04 arcanite K 2804 typical deposit phases without melt involvement: carbonate spurrite 2C28 . Caco3 sulfate spurrite 228 . CaSO4 anhydrite caso4 Formation mechanism: The binding substance in this deposit type is the low melting point Nag0, K20, 803, Cl based com- pounds. These are molten in the kiln gas and are deposited on the cyclone walls and pipes, or first on dust particles which then themselves are depo- sited out of the gas stream in these areas. Cooling on contact or with increasing thickness results in an appreciable strengthening of the originally sticky deposit. Because of the exten- sive duration of stay in the kiln system, a reac tion takes place with gaseous C02 and S03, resulting in the formation of lath shaped spurrite and sulfate spurrite which additionally strengthen the texture. Typical textures for unsintered, pre- heater and kiln inlet deposits can be seen in photos lb - 1d. Meal Ring (Calcining Ring) in Long Kilns Characteristics and formation The meal rings, often called "calcining rings” in long kilns, are in their properties and mechanism of formation very similar to those of preheater deposits in heat exchanger kilns. This is perhaps not surprising in that both build-ups occur in the same temperature zone. Meal rings are mostly less troublesome than preheater deposits because often, due to their relatively poor strength, thermal fluctuations, kiln deformation and the action of the material stream, they fall off periodically under their own weight. A typical example of a calcining ring is plant J in Table 4.Middle Rings in Large Preheater Kilns Characteristics: Unlike meal rings, middle "rings" are dense (fine grained) of low porosity, very hard and seldom fall off during operations. Although termed as a ring they are rather more elongated, like a band, being often some 15 - 20 m long extending from 7 to 11 diameters from the outlet, e.g. 35 - 55m for a 5 m@ kiln. Unlike previous types, this deposit is clinker-like in colour indicating it being composed of well burnt kiln charge. Perpen- dicular to the direction of deposition, the fine layered structure can be seen showing the cur- vature of the kiln shell. The chemical composition of middle rings is very similar to that of clinker. This is surprising because considering the long duration of the stay in the kiln, no increase in concentration of the alkalis or S03 takes place, and often the ring shows lower volatile element values than for clinker. Typical analyses of a middle ring are given in Table 5. The minerals found in middle rings are the clinker minerals alite, belite, aluminate, ferrite and free CaO, the alite having often decomposed into microscopically mixed belite and free CaO, resulting from the temperature at the site of the ring being under the lower stability temperature of alite (i.e. 1260°C). Formation Mechanism: The mechanism of bonding is the freezing of the clinker alumino-ferrite melt. Due to a long cool flame, the clinker has a tendency to be fine, and the smallest clinker particles of 150 - 450 um are carried back by the flame and deposited onto the kiln wall in a zone where temperatures of below 1250°C exist. The particles immediately freeze in place, and because the kiln charge is still fine, it does not possess sufficient abrasive action to remove the growing ring. The typical compact structure of a middle ring can be seen in photo le.4.7 -10- Sinter Rings (excluding coal-ash rings) Characteristics: These occur at the beginning of the sinter zone some 4 - 5 D from the kiln outlet. They are greyish-black in colour, strong and are (usually) agglomerations of small clinker pellets and clinker dust. No layer structure is obvious because of the presence of large pores and voids. In general, the chemical composition is that of the clinker with no appreciable concentration of volatile elements, From a mineralogical viewpoint, the normal clinker minerals alite, belite, aluminate, ferrite and free CaO are observed, with reactions to form belite and CaOgree, spurrite and belite being found with increasing depth in the ring, i.e. decreasing temperature, similar to the case of middle rings. Bonding mechanism: The bonding is created by the freezing of the alu- mino ferrite clinker liquid in the case of pure sinter rings. This phenomenon occurs especially at the beginning of the sinter zone, where the liquid phase is just starting to form (approx. 1280°C). Due to the rotation of the kiln, the charge in this zone freezes with each kiln revolution; a new wet layer sticks on, and with time a thick deposit builds up consisting of particles of less than 1 mn. Coal Ash Sinter Rings Characteristics: In kilns fired with a high ash content coal, sinter/coal ash rings can form at 7 - 8.5 D from the kiln outlet. They are dense, often layered and sometimes glassy in appearance and built up from particles some 150 - 250 um in size. They are rather less dense and have larger pores and voids than middle rings. Photo 1f gives an example of the microstructure of such material, showing the coal ash layers.-.1- From the viewpoint of their chemical and minera- logical composition they are essentially similar to clinker, exhibiting the minerals alite, belite, aluminate, ferrite and free CaO. With decreasing temperature (increasing ring depth) reactions to form spurrite and calcite take place, and also the transformation of alite —> belite + CaOf and p- belite—>y belite. Details of the chemistry and mineralogy are given in Table ¢ . No enrichment of the volatile phases can be observed. Because of the enrichment in coal ash, the belite content is higher than that of the clinker, and tends to be found in layers. Formation mechanis! The bonding medium here is the sticky molten coal ash particles and perhaps to a slight extent, the alumino ferrite clinker liquid phase occurring by a mechanism such as in Fig. 2 showing the typical build up during kiln rotation. Fig. 2: Mechanism for ring formation ash layer ash layer ash layer / (sticky) + sticking kiln kiln charge / ash layer “ = = TZ kiln charge kiln charge kiln charge a) b) ce) The molten coal ash droplets adhere to the exposed kiln lining at a point and temperature at which they are still partially fluid and sticky. When this sticky layer passes under the kiln charge on each rotation, it is assumed that a single layer of the still very fine kiln charge adheres to it. Because of the presence of fine crystalline alite and the overall occurrence of liquid phase, it must be assumed that the material temperature at the position of the ring lies above 1260°C.ela The alite crystals are very small and certainly much smaller than those of the clinker. Because of this, it can definitely be said that the ring is not formed from clinker dust blown back down the kiln. Clinker Rings / Cooler Inlet Deposit (snowman) Such rings and deposits are formed from normal size clinker granules and have a high porosity containing many voids. They are usually not troublesome to kiln operations as they can easily be removed. Their composition and mineralogy is identical to clinker, but in some cases, rings of up to 3.5% K20 and 3.0% S03 have been observed. The mechanism of bonding is the freezing of the clinker liquid phase as the clinker passes through the cooling zone (ring) or on falling down the chute into a grate cooler, grate kilns being usually operated so as to have no cooling zone within the kiln itself. Kiln Charge Balls Kiln balls occur in cases where a tendency to meal or sinter ring already exists and can be up to lm in diameter. The chemical composition is, thus, an important factor. They are usually found upstream of meal or sinter rings. They are usually made up of already calcined material and can have a porosity of up to 558, consisting of many fine pores. Often they consist of a hard dense porous core, surrounded by the majority of porous material. The core usually is a piece of coating from say the lower heat exchangers or the transition chamber, and often has a com- position different from the kiln charge in the area of formation. Differences in composition can be seen in Table 7.~13- The mechanism of meal ball formation can be due to either, or a combination of the following factors: - stripping and subsequent "balling" of old, excess coating - agglomeration enhanced by available clinker and/or salt melt - ring section acts as a dam, retaining “piece: of material for long periods. Radial growth of the pieces occurs by compaction and adherence of fresh surface due to continual rolling action of the pieces/balls over the charge. In most cases, no liquid phase participation in sufficient quantities is possible so that the balls behave like a snowball and by their own pressure material sticks to the surface. This mechanism is similar to that of deposition on the exhaust fan blades. METHODS OF REMOVAL/ELIMINATION An important prerequisite for minimizing the ten- dency to form objectionable coatings and rings, is stable kiln operation. This applies to the com position, fineness and feed rate of the raw material and fuel, and burning zone heat control. The tendency to form coatings in the kiln is reduced by lowering the dust load of the kiln gas. Objectionable coatings and rings which are formed as a consequence of high concentrations of various cir- culating elements can be obviated by appropriate reduction of the cycles in question. This can be achieved by: - Employing different raw materials and/or fuel with lower concentration of the offending element. This is generally not practicable. - Control of the raw meal milling so as to reduce the concentration of the very fine particles of sizes under 20 pm.Disk.8/m1 Ring -14- - Intervention into cyclic process by either discarding dust in which the circulating elements have become concentrated, or by means of a bypass installation which extracts a portion of the kiln gas. The penetration of false air into the preheater and kiln inlet chambers should be avoided, as such cold areas will act as sites for preferential build-up. In order to reduce the tendency to form sinter rings, it is in the first place necessary to reduce the proportion of fusible matter in the clinker, ive. the lime standard and silica modulus should be increased. "Coating-inactive" bricks have also proved successful in certain cases, in reducing the tendency toward sinter ring formation. In coal-fired kilns a coal with a normal ash content should be employed as coals having ash contents of 408 are characterized by a very high tendency to xing formation. No general approach can be given to the effectiveness of other measures, e.g. alteration to firing conditions, as these represent variables which are peculiar to the particular installation. Clinker rings can be avoided by shifting the flame further back, thus increasing the clinker tem- perature at the kiln outlet. As a result of this, however, the "stickiness" range of the clinker is shifted towards the cooler inlet. Coatings can then be formed on the cooler inlet chute. This is par- ticularly problematic with satellite coolers. In instances where this occurs with grate coolers, these coatings can be eliminated by the use of water cooled plates on the inlet chute.Sie oovt/oozt | 009t/008 OSbI/OSET | O08T/o09T OSET/OS2T | O09T/O0rT 002T> O0bT > 002T> OObT> 002T/008 OOvT/OOrT OOTT/000T 00TT/000T 008/002 OOTT/00L ‘auoz 4aquys jo pua auoz saquys auoz 4ayujs 30 Buyuu}6aq auoz Bupupoyes auoz Bujujapeo saquey2 33 [Up daquey> 304 30 4004/51 Lem 8 ¢ obeys aoueuqua 4a[009 7246 76 ‘Aap 6u01 saqrayasd ‘Aap 6u0| ayeu6 [oday (wazeayaud) ‘Aap 6u}3209 Bupa sayqup > 6uy3%02 auoz 433u}s Bua saquys tLeq abueyo ULL Buy. atppyu Bupa yea 6u}e09 6u43¢09 6uy3209 00> ooe/ost auoz Buy kup Buja Aaan[s ogst/e2t sapeiq uey ysneyxa ie Suyqe09 abueyo se6 (2,) unzeveduaa uo}3e20, (s)aday utpy (p261 ‘z34¢d0 03 Buypacoae) @Nt1v09 aww sonra 40 worsv907 any eo a adaz0qu92 Buy3e09 , = [mT] ~| = { i : wa met t 4 30 Buyuuy6og | Tv} Guys xeqwTs | ours snozod + + + roo) + yo Joos/stten | /od Bupye0D (aenp) wn | on fe oe - = Zoo | 19} Fos | ween u S94Ki DNTY SqOTUVA gO SOTESTUSLOMIVIO TWIUSLYN TERMED —1Z OTPLTABLE 3 maa a a - 7 wou PmoLLok went vi ze} 690 60} we wn ow = 7 bl - ast | 6s"1 | 19't | g0°o B60 | OE sesiu| oo 5-0 a6s0y> PaLits wxoaq 02 19y ‘sasod auow oun Suess} 69 | ge°z | z9°2 | 9o'e ceo | sie) 4 Ee a Patt - waeb/e3}ya) unoig anypaa} cor | e2°2 | 10'e ot | ovez a - ouow junoug/paa | Buos3s | opt | oc"T EO 60°0 a mt = . - ‘uou moLLek wen! g2t | bee [sz'z | seo | 9s'z | et | 60°0 v sownmee TABLE 4 403 vez | sso usar 00€ = ost }oos - ooz f'avba ‘vey ‘s2a *st9 ayssands we | wee a srze ‘002 0ST - oot sora ‘ves *s¢y ‘sty gona ase use 002 - oot 002 ‘avly “vey 5% “S09. wrouy oor - os | os - dnosa) coz | wo we jor | uroag ‘OSb - ast | osz - ost a ‘sta *sta | /morsak ‘seqeudins. Ssnopsten ‘ag ,tands, oor - os } oor AV) S29 = sOUTK aS oor - os | oor Guoays fuoaas ‘Abo 1249444 aanprat sabuasas onary anys souesvadde ye19099 Hen squauata auyaeten 0438207 aun sonty 0 sativsdoud-~19- TABLE 5 Typical analyses of a middle ring at various depths sample ring ring ring clinker internal | middle external Loss on ign. 0.47 1.82 0.94 0.37 Siog 23.0 17.8 21.9 21.9 1203 4.9 5.1 5.5 5.6 Fe203 3.0 2.9 3.1 3.2 cao 66.4 70.7 66.8 66.1 Mgo lel 1.0 0.95 0.95 803 0.13 0.07 0.27 0.48 K20 0.16 0.09 0.30 0.35 Na20 0.06 0.06 0.12 0.14 Tio, 0.25 0.23 0.25 0.25 M203 0.02 0.02 0.02 0.02 P205 0.24 0.21 0.20 0.20 ci- 0.01 0.01 0.01 0.02 Ee Total 99.74 100.36 | 100.01 99.57 Ls 92 122 96 93 SR 2.91 2.23 2.55 2.49 AR 1.63 1.76 1.77 1.75TABLE 6: Chemistry and Mineralogy of a (coal ash) ring kiln point 29.5 32.5 33.5 depth in ring| under hot middle near shell surface | | 1 chemical Snalysis: siog 24.65 24.61 21.77 1203 5.68 5.70 5.48 Fe203 4.23 4.29 3.53 cad 61.27 61.92 65.31 | Mgo 0.49 0.79 0.64 K20 0.58 0.34 0.17 | Na20 0.36 0.03 0.20 | S03 0.15 0.27 0.34 Loss on ign. 2.61 1.63 2.48 | Total 100.0 99.68 100.0 Ls 78.1 79.0 93.7 SR 2.49 2.46 2.42 AR 1.34 1.33 1.55 free lime 1.0 4.0 2.7 minerals det we. & alite ~ 30 vis ~ 40 & and Abelit 35 - 40 | w 55 - 60 ~ 30 liquid phase (aluminate + ferrite) nis vis vis carbonate spurrite+caoft nis ~ 10 { wis ( Abelite <5 <5 texture | average pore size (esti- mated) pm 400 - 800 400 - 800} 100 - 300 1 —_t-21- TABLE 7: Chemical composition of core and rim of meal ball and the kiln charge composition at the corresponding zone sR 2.4 kiln ball kiln charge rim | core calcining zone | Loss on ign. 3.9 4.3 | 1.9 | siog 20.9 | 17.2 | 21.2 A1203 5.6 | 8.0 5.7 Fe203 2.8 4.4 2.7 cao 63.0 62.5 62.1 S03 1.9 1.7 2.2 | K20 2.1 1.5 2.3 | cls oO. | on | i | glAPPENDIX I ——~ 69 Ot £01 ost | cece | ort | ezt | 99 29 4s} gerz v8°2 2°2 |sp'T Jost foot jeste |szrz jeez | cccz Ww 29'2 oe cee Jape joee |e |soz fost us — (v9"got) | (€8°91T) 2°10T | 2b"tot | 96°86 | zeveoT | 15°86 | GT*tOT texo, vez evel Be°0 et far | ot -19 a 60°0 vi = soo | 4070 | c0°0 Seq 20°0 £0°0 f ¥0"0 Too | to°0 -|20°0 Egeun - 110 9 91°0 Tro “to | 2270 eon ££70 at 60" 6070 | 9t'o | et-o ocen Sr1e gr£z ey | ptt | oe 024 9t"0 €£°0 je | 95°2 Ove | L762 Eos 28°0 6b"0 et vt st 6H gle orse e | stts | etpe | stor 9e9 Ut 88°0 at fer | az Eoga4 92 sre “2 | ay | 9 forty 4°6 8°01 pret | erat | oot Zors 9° ut grez | 6°9 | 6°9 | ‘uBy uo ss07 auolaky *¢ 0432907 4 a v qeid 98,25 | O2T,yS | 222,95 | L6€,05 | S0s,cb | vos. cr | 6TT,HS | Z2b1,¥5 | OPT. PS | BETS | “AN “9eN-VH SLISOd30 3NOTOAD UALVSHIYd 40 SISATYNY TWOIN3HO 31 XION3dd¥= 23- APPENDIX IT 4s7 WwW us vIT 961 dst ere TET 6S°T ae Lee 19 28°201 1°66 $9°00T (90) 30LuT *uBy uo $80} te90, ope Egeuy 2a o-gh 9 fos bn told Eg2ty

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  The Outsider: A Novel

  Stephen King

  Rating: 4 out of 5 stars

  4/5 (1839)
• The Light Between Oceans: A Novel

  

  From Everand

  The Light Between Oceans: A Novel

  M.L. Stedman

  Rating: 4.5 out of 5 stars

  4.5/5 (789)
• The Sympathizer: A Novel (Pulitzer Prize for Fiction)

  

  From Everand

  The Sympathizer: A Novel (Pulitzer Prize for Fiction)

  Viet Thanh Nguyen

  Rating: 4.5 out of 5 stars

  4.5/5 (119)
• Manhattan Beach: A Novel

  

  From Everand

  Manhattan Beach: A Novel

  Jennifer Egan

  Rating: 3.5 out of 5 stars

  3.5/5 (792)
• The Woman in Cabin 10

  

  From Everand

  The Woman in Cabin 10

  Ruth Ware

  Rating: 3.5 out of 5 stars

  3.5/5 (2322)
• Brooklyn: A Novel

  

  From Everand

  Brooklyn: A Novel

  Colm Toibin

  Rating: 3.5 out of 5 stars

  3.5/5 (1937)
• A Man Called Ove: A Novel

  

  From Everand

  A Man Called Ove: A Novel

  Fredrik Backman

  Rating: 4.5 out of 5 stars

  4.5/5 (4609)
• Wolf Hall: A Novel

  

  From Everand

  Wolf Hall: A Novel

  Hilary Mantel

  Rating: 4 out of 5 stars

  4/5 (3811)
• The Perks of Being a Wallflower

  

  From Everand

  The Perks of Being a Wallflower

  Stephen Chbosky

  Rating: 4.5 out of 5 stars

  4.5/5 (2099)
• The Art of Racing in the Rain: A Novel

  

  From Everand

  The Art of Racing in the Rain: A Novel

  Garth Stein

  Rating: 4 out of 5 stars

  4/5 (4200)
• Little Women

  

  From Everand

  Little Women

  Louisa May Alcott

  Rating: 4 out of 5 stars

  4/5 (104)
• A Tree Grows in Brooklyn

  

  From Everand

  A Tree Grows in Brooklyn

  Betty Smith

  Rating: 4.5 out of 5 stars

  4.5/5 (1929)
• Sing, Unburied, Sing: A Novel

  

  From Everand

  Sing, Unburied, Sing: A Novel

  Jesmyn Ward

  Rating: 4 out of 5 stars

  4/5 (1103)
• The Constant Gardener: A Novel

  

  From Everand

  The Constant Gardener: A Novel

  John le Carré

  Rating: 3.5 out of 5 stars

  3.5/5 (104)
• Her Body and Other Parties: Stories

  

  From Everand

  Her Body and Other Parties: Stories

  Carmen Maria Machado

  Rating: 4 out of 5 stars

  4/5 (821)