Granulometry of Clinker

Presenter : Eng. Ali Nadeem Mohd. Nadeem Production Engineer Qatar National cement company

Clinker burning is a very complex procedure. Although clinker is produced for more than 150 years; there is still no full clear picture about the multitude of physical & chemical reactions occurring in the rotary kiln. Clinker liquid phase or clinker melt, is the fraction of kiln feed that melts between the transition and burning zones, which occurs at a temp. between about 1260 ºC and 1310 ºC with further rise in temp. the proportion of liquid face increases to around 20 – 30% (by weight) at 1450 ºC. The liquid phase practically corresponding to 23 28% of clinker mass is mainly composed of calcium ferrites and aluminates, and in a smaller extension of silicates.

When the kiln load / charge arrives to the upper transition zone, small part of it melts into liquid when kiln feed moves in sintering zone, it’s temperature increases & so does the amount of liquid phase. The amount of liquid at any given temp. can be estimated with the help of formulas. Too much liquid is harmful to the brick lining and to clinker grindability. Too little liquid severely impairs alite C3S formation and requires more fuel to reduce the free lime content in the clinker. For a given temperature, the amount of liquid increases with iron, alumina, magnesium, sodium, potassium and sulfur. The insufflation of calcium chloride in the burning zone has a similar effect. The liquid phase has an important role in clinker granulation and also in clinker mineral development and its properties.

The influence of the liquid phase upon clinker properties and refractory performance is so important that it deserves further consideration. The LP has an important role on clinker nodulization and also on clinker mineral development and properties. if the raw mix consisted only of C-S-A-F it would start melting at 1338 ºC , the so-called eutectic point for the system C-S-A-F . at the eutectic temperature, the liquid composition would be 55 % C, 6% S,23% A, and 16% Iron. Such composition is saturated in lime and un saturated in silica. Therefore it’s very aggressive to refractory products containing silica or silicates in their compositions. This explains why high alumina bricks exhibit Duck nesting.

The actual proportions being dependent on the chemical composition of the material. For example: the proportion of liquid formed is less accordingly as the silica modulus is higher. As shown in the following graph:

Liquid phase at 1450oC in % by weight

Alumina modulus Al2O3 =2.2 TM Fe2O3 lime standard = 96 KSt
35 30 25 20 15
1.50 2.00 2.50 3.00 3.50 4.00

Silica modulus SiO2 Al2O3 + Fe2O3

Dissolved in the liquid phase also appear chlorides and alkaline solutions that modify the rheological properties of fused phase (viscosity and surface tension), thus increasing the reactivity and aggressiveness of the liquid. The effect of such oxides on the rhelogical properties of liquid phase may be resumed like this:

K2O + Na2O + MgO

Viscosity Surface decreases tension increases insignificantly

Clinker formation rate increases

K2O + Na2O SO3
Surface tension decreases. Viscosity increases. Clinker formation rate reduces.

Surface tension and viscosity decrease

Clinker formation rate increases

It is also seen that the viscosity of liquid phase increases with temperature reduction or alumina ratio increase. The viscosity of liquid phase exercises great influence on:       Clinker nodulisation. Ring formation. Clinker formation rate. Thickness coating. and stability of

In order to improve the burn-ability and increase the clinker formation rate , we can:  Reduce the liquid phase viscosity.    Increase tension. the surface

Increase the liquid phase quantity. Grind calcite and quartz more finely.

Clinker liquid phase penetration in the refractory. Specific consumption cement grinding. in

High alumina ratio (AL2O3 / Fe2O3) & low alkalis Equivalent (% Na2O+0.659 % K2O) increase surface tension of the melt while a low burning zone temperature will result in increased liquid viscosity which is lower with decreasing alumina ratio (Al2O3 / Fe2O3).

When Iron Ore (Fe2O3) increases, the surface tension decreases, due to less viscosity & more mutability then Iron Ore is a “surfactant”- which is a substance that lowers surface tension.Temperature has the most pronounced effect on liquid phase viscosity. Increasing the burning temperature by 93 ºC reduces liquid viscosity by 70%, for Ordinary Portland Cement. This simple fact explains why hotter-thannormal temperature are so beneficial to clinkering & so harmful to the refractory lining. MgO, alkali sulfates, fluorides &chlorides also reduce liquid phase viscosity. Extreme caution should be exerted when insufflating** calcium chloride into the burning zone to reduce alkali in the clinker. The injection of sodium carbonate in the burning zone is also detrimental to the refractory lining.

Free alkali and phosphorus increase liquid phase viscosity, but this effect is compensated by MgO and SO3. Only clinkers with a sulfate/alkali ratio lower than 0.83 and which are low in MgO would experience the negative effects of high liquid viscosity. Another important property of the liquid phase is its surface tension. The surface tension has a direct impact on clinker fineness, coating adherence to the lining & clinker quality. High surface tension values favor nodule formation (granulometry) and liquid penetration through the nodules.

The resulting clinker contains less dust (fraction below 32 mesh) and lower free lime content. A liquid phase with high surface tension has less tendency to ‘wet’ the brick surface, therefore reducing clinker coat-ability or adherence to the lining. Alkali, MgO and SO3 reduce liquid surface tension. So does temperature. Sulfur and potassium have the strongest effects, followed by Na2O and MgO. Therefore, MgO, SO3 and K are good coating promoters. The mineralogical nature of the raw material conditions the raw meal granulometric behavior. For example limestone of sedimentary origin shows better grinding capacity than metamorphic limestone.

Thus by keeping the same conditions of grinding limestone of metamorphic origin will show a coarser granulometry in the raw mix, if compared to sedimentary limestone. There are two qualities of clinkers being manufactured. One is based on metamorphic limestone and the other uses sedimentary fine-grained limestone. Metamorphic crystalline limestone deposits are characterized by high-energy requirements for calcining, since the calcination temperature is 930-1050oC against 850-900oC with sedimentary fine grained limestone. This increase of 80-150oC in calciner equates to an increase in fuel consumption by 40-75 Kcal/Kg clinker.

The material temperature at the kiln inlet goes up from the desired 800 oC to 900oC. kilns are designed for a material temperature of 800oC at the kiln inlet. The rate of burning is reduced, which affects clinker quality. Liquid formation is quite different in both types of limestone as can be seen below.

Calcination of different limestone Start of appearance of liquid Completion of liquid formation Clinkerization temperature. C2S.C3S formation Clinker quality

Metamorphic 1290oC 1390oC 1450oC less time Inferior

Sedimentary 1270 oC 1320oC 1450oC More time Good

Effect of burning rate on CO2 emission Material kiln inlet Residence time Burning rate / minute C2S to C3S zone C2S to C3S time C3S + exothermic heat CO2 emission

Metamorphic 900oC 20 minutes 27.5oC 1390-1450oC 2.18 minute Low High

Sedimentary 800oC 20 minutes 32.5oC 1320-1450oC 4.0 minute High Low

The use of fluxes to reduce the calcination temperature and increase the burning rate, would improve the kinetics of reaction and accelerate the clinkering process.

Once this is done the quality of clinker produced from metamorphic limestone would be improved and this would in turn reduce fuel consumption and CO2 emission -CO2 is the main greenhouse gas (GHG) responsible for global warming. Use of fluxes would also allow a higher percentage of fly ash and slag addition into blended cements, for improved business margins.

The mineralogical composition, for example, affects the pelletizeability of the raw meal and also affects the water content needed in raw slurry, while the burning behavior and the specific heat requirement are modified, inter alia, by the mineral components of the raw meal. The mineral character of clays and coarsely crystalline quartz, in particular, is a major influencing factor, but crystal lattice dislocations, crystal size and intergrowth, admixtures and impurities, natural blending of the phases in the raw material, and other factors, also play a part.

The rates at which reactions take place are generally dependent on the particle size of the reactants, i.e., on the reactive surface areas. Hence the raw meal should be of much fineness that in the burning process even its coarsest particles will react as completely as possible. As a rule , this condition is satisfied by cement raw meal with a residue of not more than 5 – 20 % (by weight) retained on the 90 micro sieve, the actual maximum acceptable percentage being dependent on the composition of the meal and the type of kiln system.

The raw meal fineness constitutes one of the most important factors in the aptitude to clinkering. It is known the finer the raw meal, the easier to burn & the lower the clinkering temperature. The lime combination Degree decreases as raw meal granulometry increases, allowing an increase in the content of free lime. As shown in the graph below :
%
60 50 1000 oC 1100 oC 1200 oC
o 1290 C o 1320 C

The following shown figure represents a raw meal with L.S.F.= 95 % & SR= 2.5, with three different fineness (5, 10 & 15%) represented by the residue in the screen No. 170. We can observe the behavior of free lime with the variation of temperature and fineness. Big grain size of calcium and quartz affecting negatively the combination of raw mix, causing bad granulation. When silica ratio (SiO2/Al2O5+Fe2O3) increases, raw meal burnability decreases and aptitude of clinker granulation decreases. Fig. : Effect of limestone particle size on free CaO content at various burning temperatures đp =average particle size of a fraction : lime Std. KStl = 96 : silica modulus = 3.0 : alumina modulus=2.2

Cao free

40 30 20 10 0 20 40 60 80

1380oC
1450 oC 100 120µm

average particle diameter đp

The result is fine clinker that generates a dust cycle between kiln and cooler, that causes a deficiency in the cooler process thermal efficiency and wear in clinker handling equipments.
CaO (%)

4

LSF=95 SR=2.5 15%
10%

3

2 5% 1

It is important to avoid variable or hard burning mixes as the harder burning and longer retention time involved in controlling free lime, result in large alite -C3S and worse large belite C2S crystals which cause poor grindability. This large crystals tend to cause dusty clinker (normal clinker should contain less than 2% - 1mm particle size) which in turn causes a high recirculation load between cooler & kiln, can exacerbate snow man formation in the cooler and overload the cooler dust collector. The final major factor is the rate of reaction in the kiln, after calcination is complete, transition to melt formation should be as rapid as possible to minimize growth of belite and CaO crystals.

1450

1500

1550

1600

( oC )

Content of the free lime as a function of raw mix fineness and burning temperature.

This transition is delayed by a long lazy flame, which may be due to poor fuel air mixing, or insufficient burner tip momentum. Too much liquid phase or clinker melt is harmful to brick lining and grind-ability. Example of liquid phase control is the case of production of sulphate resisting portland cement. The characteristic difference between OPC & SRC cements is the limited value for TriCalcium Aluminate for which attributed the increase in the formation of ettringite which when it develops and due to it’s high crystallization pressure causes the hardened cement paste to disintegrate. C3A< 3.5 Target decrease C3A ? 1.692F & How to C3A = 2.65A-

Increase F to decrease C3A but consequences silica modulus is decreased accordingly. SM = SiO2 Al2O3 + Fe2O3 liquid phase portion increased with it’s probable negative impact on operation stability, coating profile, plugging, infiltration of brick lining etc. Appropriate action is the increase of SiO2 by addition of Sand

ELEMENT SiO2 Al2O3 Fe2O3 Cao MgO SO3 Na2O K2O TiO2 MnO P2O5 SrO Cl LSF SM AM C3A C4AF AW

OPC Meal 13.35 02.95 01.90 41.44 02.27 00.30 00.16 00.58 00.15 00.03 00.06 00.10 00.107 97.6 02.75 01.56 07.31 09.10 23.97

SRC Meal 13.32 02.42 02.76 41.39 02.14 00.22 00.09 00.42 00.12 00.03 00.04 00.05 00.100 98.1 02.57 00.88 02.79 13.31 25.58

QNCC Typical OPC Clinker Composition

Range SiO2 Al2O3 Fe2O3 Cao MgO SO3 Na2O K2O TiO2 MnO P2O5 SrO Sum F. Lime Cl LSF SM AM C3S C2S C3A C4AF AW L.Ph F. Temp. B.I B.F. Alk. (M) SO3 (M)

Optimum

20.90 4.60 3.05 64.35 3.9 0.80 0.26 0.68 0.23 0.061 0.12 0.22 99.17 0.85 0.036 0.964 2.73 1.51 61.45 13.56 7.03 9.28 25.12 23.99 1434 3.8 109.2 0.99 0.95

90 to 98 2 to 3 1.3 to 2.5 45 to 65 10 to 30 5 to 15 5 to 12 20 to 35 23 to 28 2.6 to 4.5 100 to 120 0.6 to 1.4 0.83 to 1.0

96.00 2.70 1.55 60.00 15.00 7.25 8.00 25.00 25.00 1450 3.50 110.00 0.90 0.85

Kiln-cooling zone is playing an important role for clinker nodule crystalline structure. Clinker melts starts to solidify in the cooling zone and size of clinker granule start to increase due to their agglomeration during cooling process. Normally no coating is built in the Kiln – cooling zone. When clinker cooling is not satisfactory, C3S crystals will explode due to thermal and mechanical stresses, resulting in fine dusty clinker, which is the form of bad clinker granulation. Qualitative clinker granulation is essential as fine & dusty clinker results in uneven air distribution in the cooler & commonly a red river of hot clinker extending well down the cooler.

To enhance clinker granulation and avoid the phenomena of fine clinker the following should be adjusted:Consistent kiln feed – quantity and quality Silica ratio to be decreased relatively. Lime saturation factor to be kept stable in lower side - high LSF results in more fine clinker due to less liquid phase %. Well homogenized kiln feed (raw meal) Medium flame and stable kiln thermal zones graduation. Enough retention time for material in the kiln to confirm completion of all chemical reactions. Control of liquid phase percentage considering alkali ,sand ,MgO etc. Satisfactory cooling – zone length ,fast cooling (quenching)…etc Kiln stable operation.

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