Table of Contents

Chemistry Bible Rev.0; 7 Dec 00






Chemistry Bible Rev.0; 7 Dec 00





Cement is a material that binds together solid bodies (aggregate) by hardening from a plastic state. Many materials act as adhesives or cement according to this definition. The cement referred to above, which is used for civil engineering and the construction industry, is portland cement. Portland cement is hydraulic and develops strength primarily by the hydration of the di- and tri-calcium silicates it contains. Hydraulic means that the paste of cement and water will harden under water. Lime, on the other hand, will harden due to the reaction with carbon dioxide from the air. In 1793, an Englishman by the name of Smeaton found that a form of hydraulic cement was produced when a mixture of limestone and clay were burned together. He was the first producer of portland cement. Another Englishman, Joseph Aspdin obtained the first patent for portland cement in 1824. He burned a mixture of chalk and clay in a lime kiln to form a clinker and ground the clinker to cement. Aspdin is regarded as the inventor of portland cement. The early product did not have the same quality of cement currently produced today. Two main developments have improved the quality of cement: • • Addition of gypsum to regulate the setting time Higher burning temperature to obtain higher lime containing silicates

Today, portland cement (portland cement clinker with a small addition of gypsum) is used worldwide and is the primary construction material for roads, bridges, runways, tunnels, and buildings. In addition, blended cements are produced using portland cement clinker, a small amount of gypsum and another additive such as blast furnace slag, fly ash, or other pozzolans. Some blended cement has improved performance over ordinary portland cement with greater resistance to alkali and sulfate attack. 1.2 DEFINITIONS - cement, concrete, cement types, raw materials

Chemistry Bible Rev.0; 7 Dec 00


sand and iron ore are usually brought in because of their preferred chemical composition. Chemistry Bible Rev.CEMENT CHEMISTRY . concrete is a mix of cement (13%). and coarse aggregate +6mm (48%) which hardens to solid mass Cement types: there are numerous types of cement for many different applications. ASTM defines the chemical and physical requirements Ordinary Rapid hardening Alkali resistant Sulfate resistant White cement Low heat Blended cements general-purpose concrete precast concrete used with reactive aggregates used in applications requiring resistance against sulfate attack special architectural concrete massive concrete like dams mortar bonding brick or block use an addition of slag or other pozzolans to achieve some of the properties of alkali or sulfate resistance Masonry cement Raw Materials: The common raw materials for manufacture of Portland cement are: Limestone / Marble / Marl Clay / Shale Sand Iron ore or pyrite ash Limestone and clay are primarily found near the plant.HANDBOOK Cement: Gypsum: Concrete: cement is a mix of cement clinker and gypsum ground together into a powder. water (7%). fine aggregate –6mm (32%).0. 7 Dec 00 4 . calcium sulfate is used to regulate setting time. where as.FULLER .

Some of these can be utilized in the raw mix feed to the kiln.FULLER . sand A typical analysis of clinker is given in the table below: Chemistry Bible Rev.CEMENT CHEMISTRY . Other materials such as waste oils and solvents can be safely disposed of in the burning zone of the rotary kiln because of the high temperatures. there is considerable interest by our society for the reuse of waste materials. 2. 7 Dec 00 5 .0.1 COMPOSITION . marble.HANDBOOK Today.chemical shorthand The most common compounds in cement chemistry are: Formula SiO2 Al2O3 Fe2O3 CaO CaCO3 MgO MgCO3 K2O Na2O H2O N2 O2 CO CO2 SO2 Name silicium dioxide aluminium oxide iron oxide calcium oxide calcium carbonate magnesium oxide magnesium carbonate potassium oxide sodium oxide water nitrogen oxygen carbon monoxide carbon dioxide sulfur dioxide 79 volume percent in air 21 volume percent in air lime limestone. marl Source quartz.basic calculation/formulations .

51 5. Therefore. resulting in less nodulization. Chemistry Bible Rev.16 2. The amount of melt phase in the burning zone is a function of MS.CEMENT CHEMISTRY . the amount of melt is low.97 2.1 0.88 0. when MS is high. 2. the formation of nodules might be too slow.1 62 0 0.5 1 3 2.61 1. the term ignition loss is defined as the loss in weight by heating the sample to a temperature of ~900°C.3 0 0 0 0 Max limit % 26 10 5 69 4 2 1.5 * In the table.8 Min limit % 17 4 0. a higher MS relates to a harder burning mix.7 0. The material becomes dusty and impedes the kiln operation.HANDBOOK Table 1 CLINKER COMPOSITION SiO2 Al2O3 Fe2O3 CaO MgO K2O+Na2O SO3 Insoluble residue Ignition loss Total Free CaO Clinker % 22. when the MS is too high.7. 7 Dec 00 6 .2 MODULES Modules determine the proportioning of the raw mix.55 64. Generally.22 0. The three commonly used modules are: SILICA MODULUS ALUMINA MODULUS LIME SATURATION FACTOR MS MA LSF The silica modulus is defined as the ratio of silica to the sum of alumina and iron oxide: MS= SiO2 Al2 O3 + Fe2 O3 The silica modulus for clinker is normally between 2.FULLER .0.06 99.4 and 2.

FULLER . 7 Dec 00 7 .CEMENT CHEMISTRY . that can be combined with the acidic oxides has been derived from phase diagrams and can be calculated as follows: CaOmax = 2.0. is defined as the ratio of available lime to the theoretical lime required by the other major oxides in the raw mix to form clinker and is determined from the following equation: CaO LSF= 2. The LSF for clinker is in the range of 88 and 98%.6 and 2.HANDBOOK The alumina modulus is defined as: MA = Al2 O3 Fe2 O3 The alumina modulus for clinker varies between 1. The temperature by which the melt forms depends on the MA.0. 0. The lime saturation factor. a variation of the previous equations has to be used to account for the addition of gypsum to cement. The MA also affects the color of clinker and cement. The LSF formula for cement is then: Chemistry Bible Rev.65*Fe2O3 For cement.8* SiO + 2 O3 + 2O3 . CaO.18*Al2O3 + 0. LSF.80*SiO2 + 1. The higher the MA. The lowest temperature is obtained when the MA is 1. The theoretical maximum amount of lime.6. The amount of CaO has to be reduced by the amount bound in gypsum CaSO4.65* Fe 2 118* Al The LSF is usually expressed as a percentage. the lighter the cement.

. 7 Dec 00 8 .Fe O CaO C AF Note: The short formula designation is used throughout the cement industry.7 * SO3 2 .FULLER . the BOGUE formulas for clinker are: 3 2 2 3 2 3 CS= 4.07*CaO –7. the lime is combined with the acidic oxides to form cementitious minerals. The actual amount present of any mineral can be determined by microscopy or faster by Xray diffraction.CEMENT CHEMISTRY .HANDBOOK LSF = CaO − 0.SiO 2 3 CS 3 3CaO.0.72* Al O Chemistry Bible Rev.43* Fe O – 6.8* SiO2 +1. the calculation is only approximate.18* Al2 O3 + 0. however.Al O 2 3 2 3 CA 4 4CaO.Al O . The main minerals are: Table 2 CLINKER MINERALS Formula Short formula 2 3 Max weight % 70 45 18 15 2 Min weight % 35 20 3 1 0.3 MINERAL COMPOSITION During burning in the cement kiln.5 Alite Belite Tricalcium aluminate Calcium alumino ferrite Free lime 3CaO.65* Fe2 O3 2. It is possible to calculate the amount of the four main minerals by using the BOGUE formulas.60* SiO – 1.SiO 2 CS 2 2CaO. Using % wt.

The minerals in clinker are mainly found as crystals. MgO can cause late expansion in concrete.0. Cements with higher MgO contents 4-5%. A smaller amount is present in the so-called glass phase.08* Fe O + 5. however. The liquid phase @ 1450°C is determined by the following equation: Chemistry Bible Rev. The liquid phase ranges from 20 to 27% in normal clinker. During burning. These are free lime (CaO) . SO comes from 2 the sulfur in the fuel used and from sulfur in the raw materials (pyrites FeS ).FULLER . A higher amount indicates poor burning or faulty composition of the raw mix.CEMENT CHEMISTRY .HANDBOOK 2 2 2 3 2 3 CS= 8. some liquid phase is formed at the high temperature in the burning zone (BZ). other minerals are present and have to be taken into 4 account. The free lime should be under 2. 7 Dec 00 9 .7544* C S ) 3 2 3 2 3 CA = 4 2.0%.69* Fe O 2 3 C AF = 3. For other types of cement.1.07* Al O – 3.60* SiO + 1. A maximum of 6% MgO is allowed in ordinary portland cement.65*Al O . calcium sulfate (CaSO ) and periclase (MgO). the maximum limit varies.04*Fe O As mentioned above. Too high a free lime will result in volume instability in the cement mortar or concrete. Calcium sulfate in cement 3 comes from the addition of gypsum and from clinker. some of the liquid does not have time to form crystals during cooling. In clinker.07*CaO 2 2 3 (or C S= 2.867*SiO -0. rapid cooling of the clinker is of more value for offsetting the adverse effects of high magnesia contents.

00A + 2. Gypsum occurs in nature as gypsum rock. The formula for gypsum is: 4 2 CaSO .CEMENT CHEMISTRY .which is the hemi-hydrate form (plaster of paris) .0. 7 Dec 00 10 .25F + (MgO + K O + Na O + SO ) 3.HANDBOOK 2 2 3 % Liquid Phase = 3. The most common types of cement can be divided into three main groups: a) PORTLAND CEMENTS: Chemistry Bible Rev.0. If the addition rate is small.which is the di-hydrate form . surplus gypsum from fertilizer factories or cement manufacturing exhaust gas scrubbers. The amount of gypsum added is 3 to 5% by weight.which is the anhydrite form CaSO . TYPES OF CEMENT The clinker from the kiln system is ground to cement with a small addition of gypsum in order to control the time of setting. the cement will set rapidly when water is added. Other sources of gypsum are waste gypsum from exhaust gas desulfurisation at power plants. If no gypsum is present. the product can still be called portland cement.5H O 4 CaSO The gypsum molecule is crystallized with two molecules of water.FULLER .2H O 4 2 . Other materials can be added to clinker and gypsum to make cement.

SULFATE RESISTANT CEMENT is used where a higher resistance is required Chemistry Bible Rev. The most widely used type is ORDINARY PORTLAND CEMENT.CEMENT CHEMISTRY .FULLER . 7 Dec 00 11 . RAPID HARDENING CEMENT is a portland cement that develops strength faster than ordinary portland cement. Good clinker quality is needed and the addition of gypsum is a little higher to maintain setting time and increase strength development.HANDBOOK ORDINARY PORTLAND CEMENT RAPID HARDENING CEMENT SULFATE RESISTANT CEMENT LOW HEAT CEMENT WHITE CEMENT b) COMPOSITE CEMENTS BLASTFURNACE CEMENT FLY ASH CEMENT POZZOLAN CEMENT OTHER BLENDED CEMENTS c) OIL WELL CEMENTS a) PORTLAND CEMENTS are by far the most common type of cements produced around the world.0. It is manufactured by grinding the clinker and gypsum finer in the cement mill.

rapid hardening mortar than ordinary portland cement. WHITE CEMENT is used where a white color is wanted for a facade of buildings. the final strength may be higher.0. A pozzolana is a material which is capable of reacting with lime in Chemistry Bible Rev.FULLER . in large concrete structures like dams. and a small addition of an air-entraining agent to produce a more workable. Although. LOW HEAT CEMENT is used where low heat development during hardening is required. granulated slag. It can also be made by intergrinding mixtures of portland cement with hydrated lime.HANDBOOK 3 to sulfate-bearing waters. Pozzolanic cements are produced by mixing together portland cement and a pozzolana. Some additions become hydraulically activated as they react with the Portland cement clinker.CEMENT CHEMISTRY . The cement composition has a lower content of C A. b) COMPOSITE CEMENTS also known as blended cements start with Portland cement clinker and gypsum but also have the addition of another material. 7 Dec 00 12 . i. To mention a few: Blastfurnace slag cement is a cement made by grinding together portland cement clinker and granulated blastfurnace slag in the proper proportions. limestone.e. The rate of strength development is lower than that of ordinary portland cement. less than 8%. Masonry cement is a combination of portland cement clinker. or other waterproofing agents with inert fillers. It is manufactured from raw materials with low content of iron chromium and manganese.

c) OIL WELL CEMENTS Oil well cements are used for cementing the steel casing of gas & oil wells to the walls of the bore-hole and to seal porous formations. The European standard has three main strength classes each divided into two subgroups or 6 classes in all. Tables 3 and 4 show some of the physical requirements defined by ASTM.0. Today. portland cements more coarsely ground than normal. there are two main standards: • • The US standard defined in ASTM C 150 The European standard EN 197-1 ASTM uses 5 main classes for Portland cement. Usually.HANDBOOK the presence of water at ordinary temperatures to produce cementitious compounds.CEMENT CHEMISTRY . 7 Dec 00 13 . There are also a number of composite or blended cements defined by ASTM.FULLER . with the addition of special retarders to allow for slow-setting conditions are used. Cement standards define the various types of cement. Table 3 ASTM CEMENT TYPES Compressive Strengths – for ASTM C109 Cubes Number Type of Cement 3 days compressive strength 7 days compressive strength 28 days compressive strength Chemistry Bible Rev.

Fineness.HANDBOOK MPa I IA II Ordinary Portland cement OPC air entraining Moderate sulfate resistant Moderate heat of hydration II A III III A IV V II + air entraining High early strength III + air entraining Low heat of hydration High sulfate resistance 8 8 24 19 12 10 10 MPa 19 16 17 MPa 14 7 15 17 21 Note: SI units are the standard . 7 Dec 00 14 .23.FULLER .CEMENT CHEMISTRY .To convert to psi : SI * 142. Table 4 ASTM CEMENT TYPES Air Content. Soundness and Setting Time Chemistry Bible Rev.0.

80 <0.80 <0.CEMENT CHEMISTRY .FULLER .HANDBOOK ASTM TYPE Air content Fineness Blaine 2 Autoclave expansion Setting minutes vol% I IA II II A III III A IV V Max 12 Min=16.80 <0.min 45 45 45 45 45 45 45 45 max 375 375 375 375 375 375 375 375 >280 >280 <0.80 Initial .max= 22 Max 12 Min=16.80 Chemistry Bible Rev.80 <0.80 <0.0.max= 22 Max 12 Max 12 m /kg >280 >280 >280 >280 % <0. 7 Dec 00 15 .max= 22 Max 12 Min=16.80 <0.

79 35-64 20-34 5-19 65-89 45-64 40-64 20-39 M=different materials L=limestone W=calcareous fly ash T=burnt shale V=siliciceous fly ash Q=industrial pozzolana P=Natural pozzolana II/A-S II/B-S II/A-D 80-94 65-79 90-94 S=Granulated blastfurnace slag D=Silica fume Chemistry Bible Rev. K .0. 7 Dec 00 16 .% 95-100 Additive Gypsum Filler II Portland slag cement Portland silica fume cement Portland pozzolana cement II/A-P II/B-P II/A-Q II/B-Q Portland fly ash cement II/A-V II/B-V II/A-W II/B-W Portland burnt shale cement Portland l/st cement II/A-T II/B-T II/A-L II/B-L Portland composite cement III Blastfurnace cement II/A-M II/B-M III/A III/B III/C IV Pozzolanic cement IV/A IV/B V Composite cement V/A V/B 80-94 65-79 80-94 65-79 80-94 65-79 80-94 65-79 80-94 65-79 80-94 65-79 80-94 65.FULLER .HANDBOOK Table 5 European Standard EN 197-1 Types of Cement Cement type I Designation Portland cement Notation I Clinker .CEMENT CHEMISTRY .

5-62. The standards also specify some chemical requirements.5 52.III. & V I. 7 Dec 00 17 .5 R 42.5 R 52. & V I.5 For both ASTM and EN. & V I. the three main strength classes are divided into two subgroups or 6 classes in all.5 42.5 >=52.IV.IV. & V 32. Table 6 European Standards for Strengths Type Class 2 days compressive strength MPa I.IV.5R >=10 >=10 >=20 >=20 >=30 7 days compressive strength MPa >=16 28 days compressive strength MPa 32. For these it is necessary to reference the two standards. & V I.III.5-52.II.IV.0.II.II.FULLER .5 42.5 42.II.IV.HANDBOOK All of the above European types of cement are the result of many years of work on a unification for the different standards.5 32. In European standards. For ASTM they are: Chemistry Bible Rev.II.5-62.CEMENT CHEMISTRY .III.5 32.II.III.III. & V I.III.5 >=52. there are a number of other physical requirements.5-52.IV.

max% Optional requirements: 3 C A max%.5 Not applicable Not applicable C A > 8% Ign.5 Not applicable 4.0 6. max% 4 3 8 15 7 5 25 C AF+2(C A).HANDBOOK Table 7 ASTM Chemical Specifications Cement type 2 I and I A II and II A 20.5 6.3 6.0 0.0 6.max% 3 3. max% Ins.0 6.0 0.loss.0 III and III A IV V SiO .3 SO .75 35 40 3.0 3.max% 2 C S.75 C S .75 2.res.0 2.0 3. max% MgO.0. max% 3 6. max% 3 3.FULLER .0 0.% 2 3 Al O .0 0.0 6. 8 Chemistry Bible Rev.for moderate sulfate res.75 3.0 2.0 3. min.75 3.min% 3 C A.CEMENT CHEMISTRY . max% 3 C A <= 8% 3 SO . max % 2 3 Fe O . 7 Dec 00 18 .5 0.

3 CEMENT QUALITY . i.MAIN FACTORS Cement quality is just as important for the manufacturer of the product as it is for the producers of concrete and concrete products.60 0. The consumer has a range of requirements for the cement depending on the type of concrete product.for high sulfate rest. withstand alkali aggregate reaction and at the same time have a good appearance in the finished structure. The cement manufacturers have to meet the standards.60 0. contractors and the private consumer. heat of hydration 2 2 58 Na O+0.e. or pumped concrete to mention a few. The plants also have a role in fulfilling environmental requirements and assisting in the disposal of various waste products. Chemistry Bible Rev.HANDBOOK 3 C A max%.CEMENT CHEMISTRY . 7 Dec 00 19 . The end user wants a durable concrete which will stand up to heavy usage on infrastructure.60 0. max %. all purpose ready mix. precast. low alkali 0.658K O. max%. the clients requirements and at the same time be competitive.mod.0.60 0.60 3.FULLER . 3 3 5 C S+C A. be frost resistant.

C AF The main reactions at hydration in an idealized form are: 3 2 x y 2 1) C S + (3-x+y) H O = C SH + (3-x) Ca(OH) 2 2 x y 2 2) C S + (2-x+y) H O = C SH + (2-x) Ca(OH) 3 2 2 8 4 19 3) C A + 13. the cement milling.5 H O = ½ (C AH + C AH ) 3 2 3 6 4) C A + 6 H O = C AH 3 2 2 3 19 5) C A + Ca(OH) + 18 H O = C AH Chemistry Bible Rev. The chemistry of the clinker is important. For example.CEMENT CHEMISTRY . Even ordinary portland cement has subtle differences. the gypsum addition rate and with limestone where up to 5% might have been added during grinding. and any changes to the cement after milling. The main minerals in the clinker are: • 3 2 3 4 C S.FULLER . The clinker mineral composition has to be considered. 7 Dec 00 20 .0. C S. C A. The cement fineness can be varied during grinding with a finer product reacting faster. Fineness is expressed as: specific surface area (Blaine). residue and particle size distribution. the fineness. Composition can also vary within a single type of cement.HANDBOOK The cement quality depends on the clinker manufacturing process.

Of prime importance is the state of the gypsum. hemi-. False set can happen either by fast set of gypsum hemi-hydrate or because of a slow reaction Chemistry Bible Rev. Each reaction differs in velocity.FULLER . This stiffening can be broken upon remixing without additional water. in the cement as it first reacts with water. as di-. CaSO .2 H O In all of the above reactions. 7 Dec 00 21 .3 CaSO . the gypsum and 3 C A reactions with water can result in normal. or anhydrite. volume change. and in the nature of the hydration products.CEMENT CHEMISTRY .H 3 4 2 3 4 12 7) C A + CaSO + 12H O = C A. Upon mixing with water. These reactions are the background for the setting time and strength development to the solid state from the plastic phase when water is first added to the cement.H 4 3 8) C AF – reactions similar to C A 2 2 9) CaO + H O = Ca(OH) 2 2 10) MgO + H O = Mg(OH) 4 1 2 1 4 2 11) CaSO + 2 H O = CaSO . Depending upon that state. water reacts with the hydration product minerals increasing the volume of the solid phase.2 H O 4 2 2 2 2 4 2 12) CaSO .0.HANDBOOK 3 4 2 3 4 31 6) C A +3 CaSO + 31H O = C A. crystallization of reformed gypsum causes stiffening. false or flash set. / H O + 1 / H O = CaSO . False set is the premature stiffening of the cement paste due to most of the gypsum being either hemi-hydrate or soluble anhydrite due to overheating.

3 3

between C A with water. The slow reacting C A can be caused by prehydration

or by carbonation with CO . False set can be prevented by lowering the mill exit temperature, thereby, reducing the degree of gypsum dehydration, the amount of gypsum added to the mix, or replacing part of the gypsum with a natural insoluble anhydrite.


On the other hand, flash set occurs if the C A is more reactive than gypsum with water. The setting is characterized by a high evolution of heat and short setting time. Flash set can be prevented by adding more gypsum to the cement or by dehydrating the gypsum to a more reactive form, i.e. hemi-hydrate or anhydrite.

Therefore, as the cement is being ground, the mill material temperature must carefully be controlled. Between 90-130°C, the gypsum changes into calcium sulfate hemihydrate (plaster of paris) by releasing 1.5 molecule water:
4 2 4 2 2

CaSO ,2H O
4 2

CaSO ,½ H O + 1½ H O
4 2

(a) (b)

CaSO ,½H O

CaSO + ½ H O

The cement mill material temperature is controlled primarily by cooling the mill with an internal water spray in the second compartment. Additional cooling is accomplished with air in the separator. The cement mill exit temperature should not reach 130°C and is usually targeted at 110°C.

Chemistry Bible Rev.0; 7 Dec 00



Finally, if the cement material temperature has not been controlled in the mill system, the cement might enter the storage silo at too high a temperature causing dehydration of the gypsum. The rate of the transformation increases with temperature and with falling dew point. The change after equation (a) is rapid at a temperature of 90-130°C. The water molecule released can give rise to formation of lumps in the cement and to scaling on the storage silo wall by
2 4 . . 4 2

formation of Syngenite K SO CaS0 H O.

4.1 MANUFACTURE OF CEMENT - grey, mixed and white cement - wet, dry and semidry process The manufacture of Portland cement is divided into the three main parts: a) b) c) Preparation of the kiln feed Burning in the kiln Grinding of the clinker with gypsum and other additions

The description here will concentrate on the process for ordinary grey cement with some comments on the other types of cement. The dry process is used to make the majority of the cement produced in the world. The wet process, however, is still used where fuel cost has allowed it. The wet process can furthermore be justified where the raw materials are very wet such as chalk, a soft limestone, and clay. An intermediate solution is the semi-dry process where the raw mix is prepared as slurry. The slurry can then be filtered to remove a portion of the water before the burning or the slurry may be pumped directly into a dryer crusher working in unison with the kiln. 4.2 RAW MIX

Chemistry Bible Rev.0; 7 Dec 00


FULLER - CEMENT CHEMISTRY - HANDBOOK The raw mix must have a composition that will produce a clinker of the proper analysis. The difference in the composition of the raw mix and the clinker is threefold. First, is the change in each of the materials as they are heated up in the kiln. The changes are due to a loss in weight mainly from the release of carbon dioxide and water. Second, is a change due to absorption of ash from coal used as fuel. There is also a change due to absorption of sulfur in the fuel. Finally, there is a change due to the small dust loss in the exhaust gas. Some of this dust is returned to the process but some might be wasted as in a bypass. In a wet process, the dust may be discarded in order to reduce the alkali content in the clinker. The raw mix must therefore compensate for these changes and losses; otherwise, the clinker will not have the correct chemical and mineralogical composition. The way in which this is done will be explained below. 4.3 RAW MATERIALS

Many raw materials are suitable for the production of cement. In principle, as long as they can be mixed to give the right composition of the clinker, they can be used. There are some restrictions naturally. They must be available in large quantities and be economically feasible. In addition, there might also be restrictions on use due to minor components in the raw materials. Limestone is the largest component used in producing cement. It is available as CaCO3 in marble, limestone, chalk and marl. Limestone is sometimes found together with magnesium carbonate. Only small amounts of MgO can be tolerated in cement due to the risk of the expansion reaction in the concrete. Limestone containing a large amount of magnesium carbonate is called dolomite. In nature, limestone is found in many places mixed with clay and/or shale. Clay and shale contain SiO2, Al2O3 and Fe2O3. In some cases a type of limestone is found that is quite close in chemical composition to the cement composition. When the limestone is of a higher purity than the requirement for the raw mix,

Chemistry Bible Rev.0; 7 Dec 00


the ratio of alumina to iron oxide: MA = Al2 O3 Fe2 O3 Bauxite an alumina mineral rich in Al2O3 and can be used to increase the MA. The number of components used in the raw mix is typically 4-5 raw materials depending upon the need for correction of the three main modules: LSF. The chemical variation in the raw material is also important. It is a very hard and abrasive mineral. MA.8* SiO + 2 O3 + 2O3 . this is higher in SiO2 content. MS. If there are great variations.0. Chemistry Bible Rev. The amount of limestone is calculated using the formula below: CaO LSF= 2. or as a waste product from the fertilizer industry. such as pyrite ash. 7 Dec 00 25 .HANDBOOK then other raw materials must be added to the mix. one of the waste materials from the power generation industry is also used as a raw material. It is used to regulate or reduce the alumina modulus. PFA. 0. more homogenization will be required.CEMENT CHEMISTRY . Fly ash. Typically.65* Fe 2 118* Al Sand is a mineral very rich in silica. This is known as pulverized fly ash.FULLER . usually an iron oxide. SiO2. It is used when the mix is insufficient in silica. The physical nature of a raw material is also important. Very abrasive materials like sand and basalt are costly to crush and grind to the fine state needed in the raw mix. It will increase the MS or the silica ratio: MS = SiO2 Al 2 O3 + Fe2 O3 Iron can be used in the form of iron ore. Very wet materials can be the reason for choosing the wet or semi-dry process.

which can give an expansion in concrete. as shown in table no.0.FULLER .8 below. An analysis can be performed quickly using X-ray fluorescent analysis.4 CHEMICAL COMPOSITION AND CONTROL OF RAW MIX The chemical composition of the raw mix has to be prepared correctly to yield a good clinker. Also.e. A typical calculation of a raw mix and the corresponding clinker can be made using a simple spreadsheet like EXCEL with its SOLVER function.HANDBOOK 4. 7 Dec 00 26 . Low alkali cement is needed when the aggregate contains reactive silica. The first step in the mix design is the determination of the chemical composition of the raw materials. It is common to have an approximate analysis of each raw material and use this for the calculation of the mix ratios. the variation in the raw mix going to the kiln has to be small to obtain good burning conditions for the kiln and preheater. Timely adjustments can then be made to the raw mill weighfeeders. A sample after the raw mill is easily obtained for analysis.64 The alkalies often have to be restricted to satisfy a requirement for low alkali cement. The calculations made in the table show that 5 raw materials have been available at this plant.658*K2O = = = = 94 2. i. The four conditions here are: LSF MS MA Na2O+ 0. This has made it possible to satisfy 4 conditions. Chemistry Bible Rev. one less than the number of raw materials.75 1.CEMENT CHEMISTRY .90 0. XRF.

49 0.91 0.36 2.32 56.67 0.68 1 1 1.45 2.39 18.07 Raw meal Raw meal (LOI free) 22.72 9.64 43.32 2.658*K2O MS MA CaO(SO3) C3S C2S C3A C4AF Min.7 0.81 1.33 0.64 2.76 0.58 26.23 51.56 0.11 1.03 0.73 0.29 0.085 94 95 2.007 0.70 0.81 0.30 28.0 4.14 5.35 0.FULLER .79 0.07 0.00 83.02 0.00 99. The chloride content has to be restricted in preheater kiln systems to 0.17 3 3 14.07 Coal ash 970988 36.21 Bottom ash 980577 39.67 2.61 34.84 Sand 980575 78.19 0.84 1.68 0.87 2.84 0.05 0.42 1.20 0.00 93 93.05 0.51 2.02 1. weight% Weight % (X) Max.95 100.010 0.31 4.79 65.31 2.47 3.98 0.04 2.HANDBOOK Table 8 Calculation of Raw Mix RAWMIX NO: HEAT CONSUMPTION COAL HEAT VALUE Hi COAL ASH Limeston e 980257 5.14 2.71 0.CEMENT CHEMISTRY .14 0.50 7.50 0.53 99.53 0.0 0.13 0.64 14.53 0.0.012 0.29 0.006 0. Chloride is a volatile component and can form coatings together with alkalies in the preheater.00 99.00 4.52 1 750 7420 9.83 0.95 100.44 0.76 1.14 5.72 0. weight % 94 0.07 0.03 317 318 6.06 Fly ash 980578 54.009 0.0 99.83 0.28 17.00 The chloride content is also shown.08 6.81 2.09 0.29 0.34 8.2 Clinker Setpoint X-PLANT SiO2 Al2O3 Fe2O3 CaO MgO Mn2O3 TiO2 P2O5 K2O Na2O SO3 LOI @900 oC TOTAL ClC Free CaO LSF(SO3) LSF Na2O+0.06 0.58 0.87 2.15 99.030 0.78 0.93 0.5 PHYSICAL CONTROL AND COMPOSITION OF RAW MIX The raw mix must contain the proper fineness and be homogenized before Chemistry Bible Rev.05 0.0 1.4 Shale 980576 54.04 0.02 0.98 8.49 80.19 40.20 0. 4.07 -3 0 2.17 0.03 0.75 1.12 1.34 8.90 65. 7 Dec 00 27 .76 0.88 0.53 0.02 0.87 21.09 31.08 1.130 94 95 2.13 0.03 0.33 0. .36 0.96 0.64 99.14 0.48 0.28 9.41 3.34 0.006 0.13 0.00 1.47 5.17 0 2 0.47 0.71 7.05 0.0 2.09 10.17 2.12 7.52 0.95 0.19 2.49 0.90 99.43 0.04 0.84 15.28 5.48 99.010 0.75 1.51 66.70 5.00 4.29 0.11 90.44 99.80 99.015% by weight in the kiln feed.000 22.44 2.00 7.40 1.73 0.74 99.69 3.80 100.

10 and 15% residue on 0. 7 Dec 00 28 . The free CaO is compared to the free CaO content expected or found on a standard raw mix and classified as hard. The clinker formed is then crushed and ground determining the amount of free CaO. The fineness of the raw mix is measured on sieves .HANDBOOK entering the kiln. 4. In the wet process.5 to 1. The Chemistry Bible Rev. normal or easy burnability. then the raw mix may have to be ground finer or the composition might have to be altered. the kiln feed is slurry with water content of 33 to 40%. three sets of nodules each of different sieve residues (5. In the dry process. the slurry moisture should be as low as possible but still be transportable via slurry pumps. Usually.5%. Free silica (quartz) will for instance result in poor reactivity or burnability of the material in the burning zone.6 BURNABILITY OF RAW MIX The reactivity of the kiln feed for slurry or raw meal is checked by the burnability test in the laboratory.09 mm • 200µ or 0.5-1.FULLER .66 kg/kg clinker.CEMENT CHEMISTRY . If the raw mix is hard to burn. while a moisture content of 35% requires evaporation of 0.83 kg water/kg clinker.0.09-mm sieve) are burned for a given time and at a given temperature.The normal sieves with respective residues used are: 90µ or 0. For the old fashioned wet process and for the semi-dry process. The amount of water that is evaporated from slurry with a moisture content of 30% is 0. the kiln feed is a dry powder with a typical moisture content of 0. the composition of the residue is important. When the coarse particles have a similar composition to the kiln feed (less quartz) then a greater amount of residue can be tolerated.5% retained (~ equivalent to ASTM 70) 10-20% retained (equivalent to ASTM 170) Also.20 mm • 0. The procedures can vary from different kiln suppliers but in principle a few small nodules are made of the raw mix ground to a fixed sieve residue. The first changes would normally be made to the MS or LSF.

4) 5) Burning Zone: 1000-1450°C.12*(R125) where: A44= acid insoluble residue> 44µ in % R125 = total residue > 125µ in % 4. the material is 80 to 95% calcined when entering the kiln. CaO and MgO are formed. For dry preheater kilns without a precalciner. 7 Dec 00 29 .HANDBOOK burnability can be estimated from the below formula: CaO (1400oC) = 0.0.Smaller kiln Chemistry Bible Rev. cooling zone. When a calciner is installed. the melt solidifies and the material crystallizes.CEMENT CHEMISTRY . A calciner temperature of ~ 875°C will usually result in a calcination of approximately 9095%.35*(LSF-96)+1.Lower fuel consumption . evaporation of free water Preheating Zone: 100-750°C.58*(MS-1. The CO2 leaves the kiln with the exhaust gas. some liquid is formed and the fusion forms clinker minerals C2S and then C3S.6)+0.Less replacement of refractory due to longer lining life in the burning zone . decomposition of carbonates CaCO3.FULLER . loss of bound water in clays Calcining Zone: 750-1000°C. the material entering the rotary kiln is 40 to 50% calcined. The advantages of a modern dry kiln with a preheater compared to a long wet kiln are: .7 CLINKERISATION The reaction zones that occur as the raw mix is fed to the pyro system are: 1) 2) 3) Drying Zone: < 100°C.55*(A44)+0. MgCO3 and others in the calcination zone.Smaller kiln . Cooling Zone: 1450-1300°C.Better process control .Larger production capacity The advantages of a precalciner dry kiln compared to a preheater kiln are: .

The coating in the burning zone can become quite porous and unstable.Better and easier process control . o the liquid phase will start forming around 1340 C and amounts to 20-25 %.Longer refractory life in the burning zone .Larger production capacity 4. Grinding of fine clinker calls for a higher power consumption in the cement mill.HANDBOOK . .8 INFLUENCE OF THE RAW MIX ON CLINKER FORMATION AND BURNABILITY The clinker formation is very important for plant operation and for cement quality.FULLER . The formation is a function of particle size and the amount of liquid.Two step firing with approx. 7 Dec 00 30 . An Chemistry Bible Rev. 60% firing in the calciner and 40% firing in the kiln.CEMENT CHEMISTRY . The two factors determining the clinker formation and the clinker size are: a) Agglomeration and nodulization in the burning zone due to liquid formation 3 b) Formation and growth of C S crystals working against nodulization The nodulization depends on the liquid to bind the fine particles together. In the rotary kiln. Fine dusty clinker will be difficult to handle in the grate cooler and a large dust circulation may start between the cooler and the burning zone.0.

Alite Birefringence: difference between refractive indices of blue/red light • • • • Chemistry Bible Rev.CEMENT CHEMISTRY . Belite size: reflects retention time in burning zone above 1400°C. 3 Formation of C S starts. 7 Dec 00 31 . Four main characteristics of clinker formation are: Alite size: measure of kiln burning zone temperature rise 1200-1450°C where belite is combining w/ CaO to form alite crystals. whereas. Rapid cooling is desired resulting in clear crystals. Rapid heating is desirable w/ alite size ranging from 15-20µ . Slower cooling gives yellow to amber colored crystals.0.FULLER . The formation and growth of crystals in the burning zone eventually stops the agglomeration. Maximum retention time is desired w/ average crystal length of 25-40µ . the rate increases and the size of the crystals increase.HANDBOOK increase in temperature does not increase the amount of melt substantially. Shorter retention time = 5-10µ . slow heating results in sizes of 60µ or greater. Belite color: rate of initial cooling to below 1000°C.

HANDBOOK related to maximum kiln temperature which is desired. 7 Dec 00 32 . Figure 1 Melt Formation as a Function of Temperature Figure 2 % Liquid as a Function of MS. birefringence of 0.CEMENT CHEMISTRY .0080.FULLER .010. MA and LSF Chemistry Bible Rev.0. A cooler burning zone yields ~ 0.002.

5. 7 Dec 00 33 .FULLER . a higher LSF will result in a higher burning zone temperature and above a certain level the nodulization is impeded and the clinker gets more dusty. A lower MA results in a 3 higher liquid phase at a lower temperature. A higher LSF will give more C S formation. Depending upon the level of LSF. PROCESS AND KILNS 5. Lowering the MS will give better burning and nodulzation. The wet kiln had to perform drying.HANDBOOK The raw mix chemistry has a major influence on the process.1 TYPES OF KILNS . Homogenization in silos and large slurry basins blended the slurry perfectly. However. A high MS will result in less liquid phase formation and require a higher burning temperature. calcination.0. dry & semi-dry The dry process is used predominantly today because of the lower heat consumption and the better process control compared to the wet process. preheating.wet.CEMENT CHEMISTRY . the wet kiln has some limitations: Chemistry Bible Rev. Fuel was cheap and the process of slurry preparation was easy. 5.2 WET KILN The wet kiln was for many years the standard equipment in the industry. burning and often clinker cooling in one piece of equipment. The wet process is only used when fuel is very cheap or the raw materials are very wet not making it economically feasible to replace it.

The material going into the kiln after the preheater has a degree of calcination of 40 to 50 %.3. A small calciner is built into the riser duct and the air for combustion is drawn through the kiln. The kiln has to be larger for a given production.9 below. The layout of the different kiln types is shown on the figure on enclosure 2. A damper in the tertiary air duct allows Chemistry Bible Rev. ILC-E. The preheater is a single string with the calciner built into the riser duct. This means that the necessary amount of heat exchange in the kiln is larger than in the kiln types with a separate calciner. 5. The last half of the calcination takes place in the kiln. It has been superceded by the more efficient preheater kiln systems 5.2 SP KILN The Suspension Preheater type. Combustion air is drawn from the grate cooler through a separate tertiary air duct. SP. has a calciner in line with the kiln. has preheater cyclones but no calciner.1 LONG DRY KILN The long dry kiln with a cross section for heat exchange is not installed any more.HANDBOOK -Heavy fuel consumption -Process control difficult -Production over 1500 tpd clinker difficult -High refractory cost 5.3.FULLER . The number of cyclones is 4 to 6.3. 5. has no tertiary air duct as all the air passes through the kiln. the charge is fluidized by CO2 giving the material a chance to flow freely. Due to the calcination in the kiln.CEMENT CHEMISTRY .0. ILC. 5.3 DRY KILN A brief review of the FLS/FULLER dry kiln types is found in table no.3 ILC-E KILN The In-Line-Calciner using Excess Air type. The table is included because there is a connection between cement chemistry and the choice of kiln type. 7 Dec 00 34 .4 ILC KILN The In-Line-Calciner type.3.

There is only one main ID fan.HANDBOOK for balancing the air between the calciner and the kiln. 5. The firing in the two calciners will be: -SLC-calciner: -ILC-calciner: 40-50% of total firing 10-15% of total firing Table 9 Comparison of Kiln Systems Type tertiary air production. . 5. SLC-I. is a single string system with the calciner placed at the side of the riser duct from the kiln. The gas stream from the calciner is mixed with the gas from the kiln riser duct and pass through one string of preheater cyclones. SLC.3. The combustion air for the calciner is atmospheric air heated in the grate cooler and transported through a tertiary air duct.FULLER .3. 5. The system is a development of the SLC system.5 SLC KILN The Separate-Line-Calciner type. mtpd SLC Yes 11000 SLC-I Yes 9000 SLC-S yes 4500 ILC Yes 7500 ILC-E no 4000 SP no 3500 Chemistry Bible Rev. The gas from the calciner and the gas from the kiln are not mixed and pass through two separate strings of preheater.CEMENT CHEMISTRY .0.6 SLC-S KILN The Separate-Line-Calciner –Special type. 7 Dec 00 35 . The SLC-I system can be used for upgrading of a SLC system by the installation of a small calciner in the kiln string.3. It has the two strings as the SLC system but with a calciner also in the kiln string. An adjustable restrictor at the top of the riser duct makes the distribution of air between the calciner/tertiary air duct/cooler and the kiln/riser duct. The calciner is placed in parallel to the kiln riser duct.7 SLC-I KILN Separate-Line-Calciner –with In-line-calciner in kiln string type. is a double string preheater with the calciner in one string. SLC-S.

5 0.8-1.2 0.2 0.0-1. The plant should be aware of the different minor constituents to prevent any problems. sodium. 5.FULLER . The heat consumption in the kiln is 750 kcal/kg.8-1. The four most important are: potassium. it is necessary to analyse the coal ash to allow for this addition to the raw mix.0-1.015 22/24 40 1. KWh/t FOLAX.4 ASH ABSORPTION The ash from the coal used for combustion will be absorbed in the clinker. The four volatile elements mentioned above evaporate in the burning zone and condense again in the colder parts of the kiln system. There are others but they are normally of minor importance.0-1.4% is used.0-1.5 0. KWh/t min.5 0.production max. heavy metals or certain organic compounds can have important implications on the environment for a given plant. The colder parts are the Chemistry Bible Rev.023 11/13 17/19 70 1.5 1. These minor materials. sulfur and chloride.HANDBOOK calciner. In the example. % fuel bypass.5 1.023 5 30 .0-1.2 0.015 55/60 100 Yes 55 SLC:40/50 ILC:10/15 100 Yes 55/60 30 yes 55/60 60 medium 15/25 25 no 12/14 18/20 70 1.5 0.4 = 0. 5.2 0.015 22/24 70 1. 7 Dec 00 36 .0-1. This is shown on the calculation sheet above (table 8). fuel and waste products. The components can come from the raw materials. max% of kiln gas inferior fuel in calciner UNAX.015 22/24 70 1.content in % (clinker basis) % Na2Oeq SO3 Cl 22/24 40 1.95 % of clinker Therefore. The amount of ash absorbed is then: Ash absorption = (750/7420) * 9.6 0.0-1.8-1.8-1. a coal with a heat value of 7420 kcal/kg and an ash content of 9.0.5 VOLATILE MATTER Some of the chemicals in the materials going into the burning zone evaporate.0-1.CEMENT CHEMISTRY .6 0.

FULLER . The volatiles that do not leave the system with the exhaust gas either remain in circulation in the kiln system or leave with the clinker. Volatiles will also condense on the raw meal particles. The volatiles can accumulate in the kiln and preheater causing problems with in build-up in the cyclones and riser duct. A portion of the volatile material leaves the system with the exhaust gas. This is referred to as a valve V. as they are colder than the gas carrying the volatiles. It is important to be able to foresee any problems that may occur before the start up of a new plant or a conversion of an existing plant to prevent the possibilities of plugging.CEMENT CHEMISTRY .0. The part of the volatile leaving the kiln with the clinker is the residual part called R. The portion that evaporates is defined as the evaporation factor called ε (epsilon). Some of the volatiles may escape from the kiln system partly being caught in the filter or escaping into the atmosphere. A simple layout of a kiln system is shown below: Figure 2 Circulation of volatile in simple kiln system ε Chemistry Bible Rev.HANDBOOK outer walls causing coating and build-up. 7 Dec 00 37 . An internal circulation of volatiles takes place and the circulation factor is called K. A certain portion of the volatiles in the material flowing into the burning zone of the kiln will evaporate at the high temperature.

The enclosed table and figure give evaporation factors and valves for typical cases. It is possible to calculate the circulation K and the residual in clinker R when the evaporation factor ε and the valve V are known.0. Table 10 Melting and Boiling Points of Alkali Salts COMPOUND K Na Chemistry Bible Rev.c/b V = e/d= (a-c)/(b-c) K = b/a R = c/a For one unit of feed: a = 1 the material balance is: K*(1-ε ) + Kε V = 1. K = 1/(1-ε (1-V)) . R is the amount going into the clinker.CEMENT CHEMISTRY .HANDBOOK Evaporation factor Valve Circulation factor Residual component ε = d/b= (b-c)/b=1. 7 Dec 00 38 . R = K*(1-ε ) The circulation factor K is the amount of compound going to the burning zone when feeding a unit of 1 (one) to the system.FULLER .

° C -oxide -carbonate -sulfate -chloride -hydroxide Decompose 894 1074 768 360 350 C C Sublime 850 884 801 328 1275 C Decompose 1689 1411 1320 Decompose Decompose 1440 1390 Chemistry Bible Rev. 7 Dec 00 39 . ° Melting temp.HANDBOOK Melting temp. ° Boiling temp.0.FULLER . ° Boiling temp.CEMENT CHEMISTRY .

30 SO3 0.HANDBOOK Table 11 Typical values for ε and V Symbol K2O Na2O 0.70 0.35-0. This is at times used to increase the evaporation in the burning zone by adding CaCl2.35 0. SO2 in the preheater also reacts with calcium carbonate with a maximum around 800°C.CEMENT CHEMISTRY .85 ~1 ~1 0.2-stage kiln Kiln valve. sulfur not bound as alkali sulfates.10-0.60 0.60 0.60 0. Sulfur in combination with alkalies behaves differently than SO2 from fuel.40 0.05 0.50 0.50 0.60 ~1 ~1 0.20 0.40 0.60 0. 50% of the sulphur burns off in the top stages of the preheater tower.70 ~1 ~1 0. dust operating Long dry kiln Kiln valve.50 0.30 ~1 0.40 0.996 0. CaCO3 assisted by moisture catches some of it in the rawmill.35 0.40 0.70 Cl 0.80 0.25 ε 0.precalciner kiln Cyclone preheater valve 1stage Cyclone preheater valve 2stage Cyclone preheater valve 1stage Dedusting cyclone valve Raw mill valve Cooling tower valve Electrostatic precipitator valve The evaporation of alkalies is larger when chloride is high.80 Evaporation factor Kiln valve.15-0. Excess sulfur.1-stage kiln Kiln valve.0.45 0.70 0.4-stage kiln Kiln valve.20 0. can be calculated as: Chemistry Bible Rev.50 0.70 Vo Vo Vo Vo Vo Vo Vo Vc Vc Vc Vc Vm Vkt Vf 0.35 0.30 0.70 ~1 0. Sulfur is difficult to evaluate.80 ~1 ~1 0.40 0.80 0. Some sulfur in the raw mix is present free in various organic compounds or in pyrites. Approximately.50 0.40 0.60 ~1 0.wet kiln.nodule operating Kiln valve.20-0.60 0. 7 Dec 00 40 .50-0.55 0.990-0.55 0.15 0.wet kiln.80 ~1 0.20 0.FULLER .60 0.45 0.

850*%K2O-650*%Na2O < 250 g/100 kg clinker where: All percentages are calculated on clinker basis SO3 is total from rawmix + fuel To ensure trouble free operation of a preheater kiln the following limits apply: Table 12 Limits for Volatiles Raw mix burnability Na2O + K2O (% clinker basis) Cl (% on clinker basis) SO3 (% on clinker basis) from raw mix + fuel .0 % Max 0. requiring Chemistry Bible Rev.) 5.FULLER .6 MAIN FEATURES DURING BURNING Easy Max 1.6 % Max 1. The standard deviation for LSF should be less than 1% and corresponding less than 0. as well as.1 for MS and MA. Some dust will be removed with the bypass gas (2-3% with 10% bypass.023 % Max 1. 7 Dec 00 41 .023 % Max 0.0.CEMENT CHEMISTRY . Or excess sulfur under 250 g/100 kg clinker If the natural valves are insufficient. then a kiln bypass can be installed. The bypass will take part of the kiln gas before the preheater and transport it to a separate cooling and dedusting system. Large variations will result in irregular kiln operation resulting in problems with ring formation and coating in the preheater. The bypass gas has to be cooled immediately to 350oC to avoid clogging.0% Chemical control during operation of the kiln system is divided into the following: -Feed composition -Product quality of clinker -Emission control -Fuel -Preheater The raw meal must have the correct quality with little variation. The cooling takes place in a swirling chamber with atmospheric air.5 % Hard Max 1.HANDBOOK Excess S = 1000*%SO3.

SO2 and other constituents in the exhaust gas. natural gas. fuel oil. Fuel analysis should be made regularly by either the supplier or the plant laboratory.FULLER . 7 Dec 00 42 . Pulverised coal is usually produced at the site in a coal mill that dries and grinds the raw coal to a fineness of approximately 15% retained on the 0. An important component in heavy fuel oil and coal is the sulfur content. and alkalies. The results have to be reported back to the authorities.09-mm sieve and moisture content of 1 to 2 %. Performing a free lime analysis on an hourly basis monitors the product quality of the clinker. sulfur. The analysis can be made either on an average hourly sample or on an hourly spot sample. 6. HEAT OF REACTION & HEAT TRANSFER Chemistry Bible Rev. Coal with low content of volatiles like semi-anthracite has to be ground very fine to promote ignition. This can be followed by regular sampling of the material going into the kiln and analyse for chloride.CEMENT CHEMISTRY . Some types of coal with high gas content have a high tendency toward self-ignition. which has to be taken into account. The plants have to control and continuously register plant emission of dust.HANDBOOK higher fuel consumption. Sulfur content in heavy fuel oil above 5% will usually cause build up problems. The sulfur has to be taken into account together with the alkalies. The residue and the moisture content vary according to the type of coal. or waste products.0. The type of fuel used in cement production is either pulverised coal. The preheater has to be kept free from coating that can clog the cyclone outlet or increase the pressure drop in the riser duct. Environmental authorities stipulate emission control in many countries.

heat is lost from the kiln system as: • • • • Radiation loss from all outer surfaces Heat loss with the gasses from the kiln Excess hot air from the clinker cooler Heat loss with hot clinker Heat effects the chemical reactions. The order of magnitude of the heat of recarbonation is normally evaluated from the temperature profile and the temperature difference between the lowermost and second lowermost cyclone in the preheater tower. Kaolinite metakaolinite Heat change Endothermic Endothermic Endothermic Chemistry Bible Rev. The first is due to the heat of reaction for the transformation to clinker. is a typical endothermic reaction: CaCO3 CaO + CO2 – 422 kcal/g The double arrow signifies that the reaction can be reversed.FULLER . The dissociation of CaCO3. 7 Dec 00 43 .400 400 . when a reaction is accompanied by heat evolution. then the reaction is endothermic. Basically. Secondly. the formation of solutions and changes in the state of aggregation such as melting or vaporization. In the preheater. The analysis is made in the laboratory of the equipment supplier.HANDBOOK The chemical change from raw material to clinker requires heat for two reasons.750 Reaction Evaporation of free water Absorbed water evaporates Decomposition of clay minerals. The heat effects are called exothermic. because the clinker process is not an ideal or 100 % effective process.CEMENT CHEMISTRY . there are the following heat changes: Table 13 Reactions During Heating Temp °C <100 100 . When planning a new plant or when making a kiln conversion it is important to know the heat of reaction for the process. this is called recarbonation. When heat is absorbed. calcium carbonate.0.

0. Reduction does not normally take place in the kiln system apart from a reducing zone in the riser duct of the preheater to reduce the emission of NOx. The first five reactions in the table take place rapidly with a velocity determined by the transfer of heat from the gas to the solid material.FULLER .1300 1300 . heat losses exist in the system. 7 Dec 00 44 .900 600 .1000 800 .CEMENT CHEMISTRY .1380 1250 .1500 Decomposition of metakaolinite to free reactive oxides Endothermic Decomposition of carbonates to free reactive oxides Endothermic Reactive oxides form intermediate or final clinker Exothermic minerals Formation of clinker melt from aluminates and ferrites formation of aliteC3S the principal clinker mineral Endothermic Endothermic The reactions within the kiln system take place at a slightly negative pressure and in an oxidizing atmosphere. An example of the heat of reaction is: Table 14 Heat of reaction Evaporation of combined water Decomposition of clay minerals Dissociation of carbonates Formation of clinker minerals Combustibles in the raw mix Total heat of reaction Kcal/kg 20 35 475 -130 -15 385 The heat of reaction is the theoretical heat consumption for the kiln system.HANDBOOK 600 . The last two reactions are determined first by the contact rate of the reactive components present in the solid phases and later in the burning zone by diffusion of the reactive components in the clinker liquid phase. Since the process is not ideal. The total of the heat reactions during clinker formation is endothermic. The losses of Chemistry Bible Rev.

0. i. there is only a temperature difference of 5°C between the exit gas and material leaving the cyclone.1 TYPES OF FUEL Chemistry Bible Rev. 7 Dec 00 45 .FUEL 7. however. radiation loss ♦ Excess air from the clinker cooler ♦ Heat lost with clinker after the cooler Some of the loss can be utilized for drying of the raw materials and of raw coal.HANDBOOK heat come from the following: ♦ Hot exhaust gas ♦ Heat loss from surfaces of the kiln system.CEMENT CHEMISTRY .e. At the high temperature in the lower cyclones these cyclones do not usually have an internal vortex. 7. The vortex or central pipe is difficult to construct in a material that will last at the high temperatures.FULLER . There is. Table 15 Typical Heat Consumption for Different Systems Specific heat consumption for kiln systems Wet kiln Long dry kiln 1-stage preheater kiln 2-stage preheater kiln 4-stage preheater kiln Semi-dry kiln w/ preheater & calciner 5-stage kiln w/ preheater & calciner 5-stage preheater kiln w/calciner and latest cooler type kcal/kg clinker 1400 1100 1000 900 800 950 725 690 The dry process is always chosen unless the raw materials have moisture contents above 20-30%. The efficiency of the heat exchange in a cyclone is the same as the separation efficiency due to the rapid heat transfer between material and gas. Usually. This is due to the change in the design of the cyclones. a variation in efficiency between the cyclones as we go lower down in the preheater.

ash and water.8 10 70 3 1 3 6625 6310 9.CEMENT CHEMISTRY .1 7. Coal originates from plants.0.1 5.2 7. 7 Dec 00 46 . Many waste products from a variety of industrial sources are also used as a fuel source. The age of coal results in different composition and quality. They are easier to ignite than the older coal.8 18. 7. fuel oil and natural gas.4 17.2 COAL Coal is found all over the globe. They are also prone to self-ignition during storage. The carbon is the main constituent in the coal. but there are also hydrocarbons.5 6. The most common fuel is coal with heavy fuel oil being second.5 Combustion air and gas Combustion air required Composition of combustion gases Wet .FULLER . oxygen.6 7. Anthracite and hard coal are old types. Table 16 CLASSIFICATION OF COALS Lignite Total moisture Volatiles Hygroscopic water Ash % % % % 40-50 40 – 50 10-25 5-25 Bituminous coal 5-10 10 – 40 1-3 10-20 Anthracite 0–3 5 1 5-10 Examples of commercial grades of coals Chemical composition: Carbon Hydrogen Sulphur Nitrogen + oxygen Heat value Gross Net C H S N+O Hs Hi weight volume Total CO2 + SO2 H2 O % % % % Kcal/kg Kcal/kg Kg/kg Nm3/kg Nm3/kg vol% vol% 56 4 1 19 5120 4820 7.0 17. The coal is then changed into coke.5 78 2 1 2 7100 6900 9. Younger coal has a higher gas content than older coal.6 6. Heating the coal in a non-oxidising atmosphere drives out some of these constituents as gas also referred to as volatiles and tar.9 7.1. Natural gas is used where available and is an excellent fuel. Raw coal is a combination of coal.9 4.HANDBOOK The most common types of fuel are: coal. while lignite and peat are younger types. 0% oxygen Chemistry Bible Rev. nitrogen and sulfur often as pyrites FeS2. that over many millenniums have been transformed into coal.

5 1. which is of value especially for vertical coal mills. Chemistry Bible Rev.9 38 76. Fixed carbon is the residue remaining after the volatile matter is driven off.0 %Sulfur 4 4 Gross Heat Value (kcal/kg) 8000 8000 Hardgrove 60-100 25-30 Proximate analysis of coal: The proximate analysis of a coal sample gives values for moisture. ash. The ° ash content is found by heating the sample to 800 C. ash and fixed carbon. as it will be a part of the clinker. The amount and composition of ash varies from one coal to another.HANDBOOK N2 Dew point vol% °C 72.0.CEMENT CHEMISTRY . which can be found in other reference material. It is performed under detailed laboratory procedures. Some coals have a very abrasive ash and a high wear index.FULLER .2 46 75. The volatile matter is ° the portion of the coal when heated to 900 C without air is driven off as gases. fixed carbon.6 31 Table 17 Typical Petroleum Cokes Type Green delayed Fluid %H2O 8 0 %Volatiles 11 5 %Fixed C 82 86 %Ash 0. where the free moisture is the moisture lost by air-drying. The moisture in coal is divided into free moisture and hygroscopic moisture. The volatile matter. and moisture add up to 100%. The amount of ash and its composition has to be known. 7 Dec 00 47 . volatile matter.

carbon. The common safety index is the ratio of % fixed carbon to % volatiles. sulphur.CEMENT CHEMISTRY . 7 Dec 00 48 . The safety index for coal varies from 1 for high volatile lignite up to 15-16 for petcoke and anthracite.FULLER .HANDBOOK Coal dust can be dangerous and cause explosions. Ultimate analysis of coal: In the ultimate analysis of coal.0. The approximate calculation is: Hnet = Hgross – 5. the inorganic composition is determined on the coal ash.1. For that reason a safety index for a particular coal is assigned according to the characteristics of the coal. The difference between the gross and net heat value is the heat of evaporation of the water from combustion and the evaporation of the water.85(9*%H + % Water in sample) 7. A high safety index means a lower chance for a coal dust explosion. Heat value: The heat value or calorific value is important for the evaluation of the coal and for the heat economy of the kiln. Chemical analysis: In the chemical analysis of coal. It can also self-ignite at room temperature. The fuel oil most commonly used [kcal/kg] Chemistry Bible Rev. nitrogen and oxygen are determined. The values are used for the calculation of the raw mix and clinker composition. hydrogen.3 FUEL OIL Fuel oil is used for cement kilns at many plants.

7 12.960 0.80 13.485 10875 10200 14.870 0. Specific gravity changes with temperature.480 10550 9900 14. 7 Dec 00 49 .9 0. An important value is the specific gravity because the calorific value is related to it.4 11.4 1. Some oils require a temperature of 120°C others have a higher requirement up to 170°C.0 10. the viscosity has to be 2° Engler (or 18 centiStoke) for proper atomisation of the oil. Hs Net.880 0 0.0 11. changes from place to place.9 11.2 12.8 11.1 0.960 0. 0% O2 CO2+SO2 Combustion gases H2O N2 Dew point Theoretical flame temperature C C The composition of fuel oils does not vary as much as coals.4 74.68 13. Another important value is the viscosity of the oil.4 0.880 120 0.905 0.CEMENT CHEMISTRY .HANDBOOK is a heavy fuel oil. The sulfur content could be quite high and should be limited to a maximum of 5% Chemistry Bible Rev.1 11.1 11. There are.FULLER .8 74.895 0. however.5 49 2120 86. Typical analysis for oil is: Table 18 TYPICAL FUEL OILS Gas oil C% Composition H% S% 0C 15oC Specific gravity.8 2. The volume consumption of the oil has to be converted into a weight consumption in order to calculate the heat input.0.3 12.8 0. The different organic components may vary.51 14.1 11.0 74.2 11.880 0. kg/litre At 2° Engler Temperature in °C for 2° Engler Kcal/kg/oC Kcal/kg Kcal/kg Kg/kg Nm /kg Nm3/kg % % % o o 3 o Light fuel oil 86.865 60 0.3 50 2160 Specific heat Calorific value Gross. The lighter fuel oil types are often used for lighting up kilns.3 50 2120 Heavy fuel oil 86. For the burners at Fuller and FLS. HI Air for combustion Wet. This is important to take into account when a heat balance has to be made.465 10375 9750 14.

1.4 GAS Natural gas is an excellent fuel source for cement kilns because it is neat and clean as well as being easy to use. Although.FULLER .0.CEMENT CHEMISTRY . there is a risk for explosions and special safeguards have to be installed and maintained. 7 Dec 00 50 . The table below has typical values for natural gas: Table 19 Examples of Typical Natural Gases Overseas Chemistry Bible Rev. The installation is simple and the composition of the gas has very little variation.HANDBOOK S. 7.

60 9.96 10.73 0. Chemistry Bible Rev.60 59 Compositio n North Sea (typical) Sahara 86. 0% oxygen free) 51 .70 58 Calorific value Air for combustion Combustion gases Total CO2 H2O N2 Dew point 91.80 0.33 9700 8760 12. 7 Dec 00 wet .HANDBOOK Dutch CH4 C2H6 C3H8 C4H10 < C5 Gross Net Vol% Vol% Vol% Vol% Vol% Kcal/Nm3 Kcal/Nm3 Kg/Nm3 Nm3/Nm3 Nm3/Nm3 Vol% Vol% Vol% O C (Groningen) 81.06 0.80 18.38 0.FULLER .CEMENT CHEMISTRY .30 0.20 9.76 2.60 17.63 1.13 0.50 71.50 9.75 10.70 71.80 18.91 8.52 10.44 9.42 2.0.60 9.16 8500 7580 10.60 71.80 11.70 59 * The natural gas contains varying amounts of nitrogen.50 0.80 3.09 10780 9750 13.

11 5.43 0.12 0.32 0.55 0.1 2.66 0.47 0.638 0.50 89.13 0.03 0.09 0.80 6.60 1.37 0.10 0.05 0. and used solvents.13 17.02 0. the volume of the combustion products is high and has a high dew point.29 7. OH Dallas.00 0.29 8.599 0.11 2. Proper precautions Chemistry Bible Rev.44 0. but this is compensated by a low requirement for primary air.50 0.73 0.00 5.14 0.82 1.00 0.00 0.604 0.54 86.05 0.78 2.29 0.28 0.06 0.69 95.60 0.61 0.22 0.10 0.85 0.42 8. WI New York.00 0.e.C. Therefore. CA Washington.50 2.CEMENT CHEMISTRY .62 0.37 91. UT San Francisco.00 2.07 … 0. CA Milwaukee. AZ Salt Lake City.26 1.00 0.02 … … 0.597 0. the kiln lining has to be hot prior to starting the gas burner without a pilot.03 0.62 0.06 He 0. used lubrication oil.HANDBOOK Table 20 Domestic Natural Gas Properties Gross City Heating Value Baltimore.93 0. MA Columbus.25 4.73 2.39 1.84 0.15 3.50 0.624 0.586 94.01 2.614 0.1.69 1.19 3.82 3.595 0. It is an advantage that the content of sulfur is low. TX Houston.28 0.26 0.40 2.70 0.01 He Gas is difficult to ignite with an ignition temperature of 600°C.01 94.06 0.30 92.30 0.79 86.03 0.60 2.641 0.94 0.48 0.07 0.06 0.63 0.5 WASTE FUELS A variety of waste fuels are burned at cement plants.0. MO Los Angeles. TX Kansas City. i. MD Birmingham.91 1. waste plastic.90 1.66 2.58 7. 0.695 0.50 0.93 0.50 72.17 88.623 0. NY Phoenix.30 0.627 0. They consist of old tires.52 87.590 0.22 0.50 3.05 0.63 0.FULLER .14 93. The heat loss with the exit gas is consequently high.00 0.16 0. 7.89 0.27 0.51 93.31 1.40 93. D.42 0.06 0. (Btu/ft ) 1051 1024 1057 1028 1093 1031 945 1084 1051 1049 1071 1082 1086 1042 3 Specific Gravity CH4 C2H6 C3H8 Components of Gas (% volume) C4H10 C5H12 C6H12 CO2 + N2 Misc.10 0.24 0.67 0. AL Boston.633 0. 7 Dec 00 52 .

2 11.20 0. Cement plants have accepted the responsibility for disposing of these many different wastes and in some cases are financially rewarded.08 Moisture (%wt.0.51 Ash (%wt.5 16.) 84.49 25. which is oxidised.5 8.15 9. The oxidisation of coal can start at room temperature with a coal of high reactivity or high volatile content.52 0.02 0 1.02 75.2 20.48 0.7 43.05 0.4 23.13 0.0 21.56 0.COMBUSTION Combustion is the chemical reaction between oxygen and fuel.3 81.33 1.0 1.56 0 0. or burns to carbon dioxide CO2 with the evolution of heat.41 0.06 99.04 1. Ignition of the raw coal can take place in the storage area if the material is not stacked properly.02 Dry Combustible (%wt.6 84.) 0. the ignition temperature.0 2.1 5.39 6. The main component of coal and fuel oil is carbon. If the temperature surpasses a certain limit.0 72.HANDBOOK have to be in effect to protect not only the personnel but the environment as well.44 6.67 98.FULLER .4 Heating value (Btu/lb) 7572 8613 7652 8484 10996 11054 8899 19161 12283 7907 Volatiles (%wt.51 74.02 99.7 9.73 Sulfur (%wt.61 93.27 23. 7 Dec 00 53 .79 0.13 4.73 15.) 10.72 0.87 95.80 0.) Density (lb/ft3) 78.06 1. a fire can easily start if oxygen is available. Chemistry Bible Rev. The ignition temperature for coals varies in relation to the gas or volatile content.0 1.9 93. Table 21 Typical Waste Fuel Analysis Type of Waste Paper Wood Rags Garbage Coated fabric: rubber Coated felt: vinyl Coated fabric: vinyl Polyethylene film Foam: scrap Tape: resincovered glass Fabric: nylon Vinyl scrap 13202 11428 100.0 75.7 10.0 10.72 0.87 81.3 56.1 9.5 1.CEMENT CHEMISTRY .) 6.2 80.6 53.8 88.9 10.

HANDBOOK Lignites and bituminous coals with volatile content over 30% have low ignition temperatures whereas anthracite. The flame is luminous because carbon or soot particles are formed during the combustion.0. Chemistry Bible Rev. In the burner. The temperature of the primary and secondary air is also important.FULLER . For coal. The radiation follows: R= e*k*( T14. The maximum theoretical flame temperature is found by fuel ignition with the stoichiometric air requirement. The flame front travels with a certain velocity increasing with temperature and is also dependent on the injected air/fuel stream for a steady combustion to be maintained. The heat is transferred from the flame to the lining and the charge in the kiln by radiation. The oil droplets evaporate to gas that ignites and burns. natural gas can burn with hardly any visible flame. The rest of the fine and porous coal particles burn with a visible flame due to the emission from the fine particles in the flame. The temperature of the flame can be calculated under ideal conditions.T24) [kW/m2] e = coefficient of emission. The practical value is approximately 80 to 85% of the calculated one. In contrast. The mixing depends on the direction of the stream and of the mixing energy or velocity. fuel is mixed with primary air as the two streams exit the burner nozzle. the water will evaporate first followed by gas evolution from the volatile portion of coal. Coal with a low content of gas like anthracite and semi-anthracite requires a high ignition temperature. 7 Dec 00 54 .CEMENT CHEMISTRY . petcoke and semi-anthracite require a high ignition temperature. The conditions for fuel oil are similar to coal. and usually a small amount of primary air is used. The fine coal particles will oxidise to CO and later to CO2 as more oxygen becomes available. The ignition of oil is more difficult than with coal due to the slower mixing of air and oil and to the evaporation of the oil droplets. max=1.

HANDBOOK K is a constant T1 and T2 are surface temperatures in °Kelvin The coefficient of emission for coal e is close to ~1 at the coal flame temperature.FULLER .09 mm 1 % + 0. This is one of the determining factors for the length of the burning zone. the value of e is 0. The coal fineness depends on the type of coal as seen from table 22: Table 22 Coal Properties Type Anthracite SemiAnthracite Low volatile bituminous coal Bituminous coal High volatile bituminous coal Lignite Volatiles % <5 5 – 15 15 – 20 20-30 30 – 40 40 – 50 Ash % 5 3-5 5–8 8 – 10 10 – 20 15 – 30 Hygroscopic water. Radiant heat is transferred quickly to the lining and to the charge surface. 7 Dec 00 55 . For oil. The coal mill can be an airswept ball mill with separator or a vertical mill. The heat transfer is better when the charge is turning over rather than sliding on the lining.09 mm 3 – 4 % + 0.7 to 0.6. 9. % <2 2–6 2–6 2–6 2–6 10 – 25 Sieve residues of coal meal 5-7% +0. The relationships between the hardgrove index and the grindability in kWh/t for different types of grinding applications are given below. This is due to the content of particles in the coal flame.CEMENT CHEMISTRY .1 FINENESS OF COAL The coal has to be dried and ground in a coal mill. COAL & OIL 9.2 mm residues increasing to coarser values 30% + 0.2 mm The grindability is usually given as a hardgrove index number.0.9 and for gas only 0. The Hardgrove index for coals can vary Chemistry Bible Rev.2 to 0. But the transfer of heat by conduction into the charge from the charge surface and from the lining is a lot slower.

09 mm Vertical mill. 9 il . a ball mill might be chosen or a vertical mill with stronger wear resistant parts. An important aspect for the choice between a ball mill and a vertical mill is the wear index. m 9 0 + 0 9 . % l a i 2 % b lm l. 0 1 %+ . 20% + 0. 20% + 0. 10% +0. 0 9 + 0 m + 0 0 .CEMENT CHEMISTRY . 10% + 0. % 5 a ic lm il. % + 0 1 0 l a ic m il. in a i y K / g t 0 3 5 2 0 2 5 1 0 1 5 0 4 0 R R E G N ADGOV .09 mm H 0 4 5 3 s p c r d b lit . Figure 3 HARDGROVE-GRINDABILITIES 40 35 spec. 0 r a e ic v t lm il. mm .HANDBOOK from 40 to over 100 for very soft lignite or petcoke.2 DRYING OF COAL Raw coal contains varying amounts of water. 0 mb a lm mv e t r 9 mr 0 V e t 0 x e 8 0 0 9 9 0 .W h e . 5%+0. Some coals have a high ash content with an abrasive constituent resulting in a high rate of wear.FULLER . The coal is dried in the coal mill only to the recommended minimum Chemistry Bible Rev. 0 6 7 H a d r e in r g o v d 0 .KWh/t 30 25 20 15 10 5 0 40 50 60 70 80 90 Hardgrove index ballmill.09 mm ballmill. The raw coal has to be dried to facilitate grinding and handling but the drying must not go beyond the limit of safety.09 mm ballmill.RI A D I I E BL I S T 0 5 l a i 5 + b lm l.09 mm vertical mill. 5%+ 0.09mm vertical mill.0. 7 Dec 00 56 . In such cases. 2 % 0 m 9.grindability.

3 ASH CONTENT 57 Chemistry Bible Rev. The ratio of the change in sample weight between 30 and 105°C divided by the weight at 105°C.CEMENT CHEMISTRY . For example.FULLER . represents the hygroscopic moisture. a coal mill outlet temperature of between 60 and 80°C is correct. The inlet temperature to the coal mill can be as high as 300 to 350°C. Figure 4 Recommended moisture in coal dust Residual moisture. Presented here is an overview of the program. This residual moisture content is found by using the graph in figure 4 below according to the actual hygroscopic moisture of the coal. The plant laboratory determines the hygroscopic moisture and residual moistures at various drying temperatures.0. to dry one kg of coal with 10% moisture 1. Usually. or surface moisture. A graph of the residual moistures at various drying temperatures shows the correct operating temperature for the outlet of the coal mill. Further drying of the coal sample at various temperatures between 30 and 105°C drives off the remaining water. Free moisture. A detailed procedure to determine surface and hygroscopic moisture of coal meal is found in another reference.% 9.HANDBOOK residual moisture content to reduce the risk for fires and explosions. 7 Dec 00 . is the water lost by air drying a prepared coal sample at an ambient temperature of 30°C. The inlet temperature depends on the quantity of air through the mill.2 kg drying air at 300°C is required. and requires the dew point of the outlet air after the coal mill to be 20°C higher than the outlet air temperature to avoid condensation and clogging in the transport system following the mill.% 12 10 8 6 4 2 0 1 2 3 4 5 6 Hygroscopic w ater.

sulfur dioxide and water. it can be difficult to obtain a sufficiently high flame temperature for the process. calciner and preheater. This reduces the flame temperature. The ash analysis is performed by the plant laboratory or by the coal supplier. 9. These volatile components will participate in the internal circulation of volatile components in the kiln. These constituents have to be taken into consideration for the calculation of the raw mix and of the clinker composition.5 MINOR COMPONENTS Coal also contains alkalies. The ash content of coal will consume some heat during combustion due to chemical changes of the minerals in the coal. a certain amount of excess air is used to obtain complete combustion without formation of carbon monoxide.FULLER . It is necessary to know the exact composition of the ash because it combines with the raw mix in the kiln system. Sometimes a very high gas content can result in problems with the mixing air. hydrogen and sulfur in the flame into the combustion products of carbon dioxide. This can impede ignition and proper burning which can result in a low flame temperature. 9. sulfur and chloride. 9. The reactions are: C+ O2 CO2 + heat Chemistry Bible Rev.4 GAS CONTENT The gas content is important for the ignition of the coal. In coals with a high ash content. 7 Dec 00 58 .0. Anthracite and some petcoke have low gas contents and consequently are very difficult to ignite.6 REQUIREMENT FOR AIR The combustion of fuel requires air to oxidise the carbon.CEMENT CHEMISTRY . Only very fine grinding can compensate for the lack of gas.HANDBOOK The ash content in various coals differs in quantity as well as composition. In addition.

The excess air in the combustion air is calculated from the formula: λ = 1/(1-79/21*O2/(100-CO2-O2)) For example. the amount of CO2 is 0.21*1. can be calculated by: Omin = (0.0889*C +0.FULLER . O. λ . of the fuel Combustion takes place with surplus air to ensure complete combustion.2231*H – 0. The minimum amount of oxygen required for combustion. H.20% when O2= 3.HANDBOOK 4H + O2 S + O2 2H2O + heat SO2 + heat The water content in the coal is evaporated. H2O are in %wt.0333*S +0. S.01)*(32/12*C+16/2*H +32/16*S+32/14*N-O) [kg O/kg fuel] Therefore the required amount of air. the amount of excess air is 1. If there is incomplete combustion CO is present and the formula cannot be used. Omin.CEMENT CHEMISTRY .6 vol% and CO2=15.4 vol%. Incomplete combustion increases the heat consumption of the kiln appreciably and it is dangerous for the precipitator. The kiln exhaust will also contain CO2 from the decarbonation of carbonates in the raw mix. The surplus of air is referred to as excess air and is symbolised by the Greek letter lambda.28 Nm3 per one kg of clinker. Lmin. 7 Dec 00 59 . Chemistry Bible Rev.429)] [Nm3O/kg fuel] [Nm3air/kg fuel] The total volume of the combustion gas is: Vmin= 0. N.0263*O + 0.0.55 kg or 0.0124*H2O [Nm3gas/kg fuel] Where: C. is: Lmin = (Omin / 1.429) Lmin = [Omin / (0. For a normal raw mix.

7 Dec 00 60 .0124*H O [Nm gas/kg fuel] This amount has to be increased by the excess air: λ = 1/(1-79/21*O2/(100-CO2-O2)) The CO2 released by the heating of carbonates in the preheater.28 Nm3. By having the exhaust gas go to a raw mill and/or conditioning tower. the calcium sulfate ends up evaporating in the burning zone leading to an internal cycle condensing at the backend of the kiln. However. They are oxidised in the preheater and a portion escapes with the exhaust gas.HANDBOOK 10. The amount for a normal clinker is approximately 0. NOx is formed by combustion in the kiln and calciner. scrubbing of the SO2 takes place reducing the emissions. Fuel NOx is formed when combustion occurs below 1200°C. PROCESS GAS The process gas contains combustion products from the fuel with some excess air. SO2 is present in the exhaust gases from oxidation of the fuel S and decomposition of sulfates. Finally. there is the additional volume from evaporation of water in the raw mix.2231*H – 0. Na2O. the preheater gases are taken to a raw mill and/or coal mill and used for drying the respective material. The amount of combustion gas can be calculated from the equation: min 2 3 V = 0.0263*O + 0. as well as. Due to the lower volatility.0333*S +0.0. In most systems. Most of the SO2 is totally scrubbed in the preheater by K2O. the alkali sulfates will most likely leave the system with the clinker.CEMENT CHEMISTRY . and CaO. The various components are described further. calciner and kiln must also be added. The amount of fuel NOx depends on:  Amount of N in fuel Chemistry Bible Rev. The exhaust gas also contains SO2 from the sulfides and pyritic sulfur present in the raw materials.FULLER .55 kg per kg of clinker or 0.0889*C +0. products from heating the raw mix.

A harder burning mix will always lead towards a higher NO. excess combustion air and high secondary air temperature will all increase NO formation. It is x 2 common to express NO as NO for regulatory purposes. The NOx formed can be reduced in different ways. overburning should be avoided.HANDBOOK   Excess oxygen Flame temperature When combustion temperatures are higher than 1200°C. however. While fuel moisture.FULLER . 7 Dec 00 61 . Thermal NO produced in the kiln-burning zone is related to:        Flame temperature Flame shape Type of fuel Excess oxygen Gas retention time in the burning zone Load temperature Load retention time in the burning zone A short. Thermal NO increases with flame temperature above 1200°C. the NOx formed is thermal NOx. and with increasing free oxygen.CEMENT CHEMISTRY . Ammonia can be injected in the top cyclone. which is Chemistry Bible Rev. with retention time. Another way is to have a reduction zone in the calciner. The NOx formed is predominantly NO. This happens in the kiln-burning zone. hot flame. a small part (5%) of which in the colder parts of the preheater is oxidised to NO2. dust insufflation. or a high dust entrainment in secondary air will reduce the NO.0.

HANDBOOK the feature of the low-NOx calciner. CO is usually formed from incomplete combustion of the fuel. The above holds true when the level of organic C in the raw material is 1.FULLER . At temperatures around 680°C. CO emissions at the stack may be contributed from poor mixing of the fuel/combustion air or not enough combustion air in the burning zone. Organic C found in the raw materials tend to oxidise at temperatures below 680°C with roughly 20% of the oxidation forms CO regardless of the amount of oxygen present. For example.4 g/kg clinker or more. oxidation of CO to CO2 takes place in the presence of excess oxygen. In the reduction zone. 7 Dec 00 62 .0. 2 g C/kg clinker with a 15% conversion rate corresponds to about 250 ppm CO at 5% oxygen. the following reaction takes place between 800-1100°C reducing the NOx emissions: [N] + NO N2 + [O] Another component sometimes found in the exhaust gas is CO. Chemistry Bible Rev.CEMENT CHEMISTRY .

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