5/23/2019 1.

2 Chemical composition of limestone

Small Scale Production of Lime for Building

1. General Information
1.1 Geological description of limestone
1.2 Chemical composition of limestone
1.3 Physical characteristics of limestone
1.4 Classification of limestone
1.5 Chemical reactions in the production of lime
1.6 Common uses of lime in developing countries

1. General Information

1.1 Geological description of limestone

Limestone is a sedimentary rock composed mainly of calcium and magnesium carbonate. It is formed by the deposition either of the skeletons
of small creatures and/or plants (organic limestones), or by chemical precipitation, or by deposition of fragments of limestone rock, on the
beds of seas and lakes. Limestones are contaminated to a greater or lesser extent by the deposition of sand" or clay which are the source of
the impurities found in them. Usually there is a difference in quality in a deposit from one layer to the next. The purest carbonates and the
most suitable from the production point of view tend to be the thick bedded type. Carbonate deposits may be found in horizontal layers as
deposited, or at an angle from the horizontal due to earth movements. They will vary in density, hardness and chemical purity.

1.2 Chemical composition of limestone

Limestone is made up of varying proportions of the following chemicals with calcium and magnesium carbonate being the two major
components.

Calcium carbonate CaCO3

Magnesium MgCO3
carbonate

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Silica SiO2

Alumina Al2O3

Iron oxide Fe2O3

Sulphate SO3

Phosphorus P2O5

Potash K2O

Soda Na2O

The two main impurities are silica and alumina with iron as the third.

For a general purpose lime, a limestone with an SiO2 content of up to 3.5 % and Al2O3 content of up to 2.5 % may be used where purer stone
is not available, whereas lime for building or road construction purposes may have an SiO2 content of up to 10% (perhaps slightly more) and
an Al2O3 content of 5 %. An Al2O3 proportion of greater than 5% will produce a semi-hydraulic or hydraulic lime.

1.3 Physical characteristics of limestone

The colour of most limestones is varying shades of grey and tan. The greyness is caused by the presence of carbonaceous impurities-and the
tan by the presence of iron.

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It has been found that all limestones are crystalline but with varying crystal sizes, unit formity, and crystal arrangement. This ret suits in
stone with a corresponding variance in density and hardness (Boynton p. 21). For lime production purposes there are two factors related to
limestones' crystallinity and crystal structure which are of specifc interest:

Density or porosity is determined as the percentage of pore space in the stone's total volume. It ranges from 0.3% - 12%. At the lower end are
the dense types (marble), and at the upper the more porous (chalk). Generally, the finer the crystal size, the higher the porosity but there are
anomalies which suggest that each case be considered separately. A high porosity makes for a relatively faster rate of calcination and a more
reactive quicklime.

Limestone varies in hardness from between 2 and 4 on Moh's scale with dolomitic lime being slightly harder than the high calcium varieties.
Limestone is in most cases soft enough to be scratched with a knife. Marbles and travertines have the highest compressive strength whilst
chalk has the lowest.

Due to the variance in porosity, the bulk densities of various limestones range from 2000 kg/m3 for the more porous to 2800 kg/m3 for the
most dense.

The specific gravities of limestones range from 2.65-2.75 for high calcium limestones and 2.75-2.9 for dolomitic limestones. Chalk has a
specific gravity of between 1.4 and 2.

1.4 Classification of limestone

High calcium limestone is composed primarily of the minerals calcite or Aragonite (CaCO3) with a total oxide (CaO + MgO) content of over
95 % It can be a fine to a coarse "rained stone of varying porosity and hardness. Chalk is a soft, fine "rained, highly porous limestone. The
pure, white chalks can have up to 99 %calcium carbonate whereas the grey variety can have up to 20 % impurities i.e. only 80 % CaCO3.
Dolomitic and magnesian limestones, in addition to the CaCO3, contain a relatively large proportion of MgCO3. Usually limestones
containing 20 % to 44 % MgCO3 are referred to as "dolomite" or as dolomitic limestone, and those containing between 5 -20 % MgCO3, as
magnesian limestone. They both vary in purity, density, hardness and colour. Marble is a metamorphosed limestone. It is either high calcium
or dolomitic and highly crystalline, dense and hard, and varies in purity. Oolitic limestorne is a chemically precipitated limestone of high
purity. Travertine is a hard limestone formed by chemical precipitation in hot springs. Tufa has the same derivation but is softer and more
porous. Hydraulic limestones, sometimes referred to as argillaceous limestones have a high proportion of clay and silicia ( 15-20 %) and can
be either high calcium or magnesian. When fired a lime is produced which can set under water (hydraulic lime).

There are several other types of limestones (less common and of limited value) such as coral limestones, shell limestones, marl, cherty
limestones and stalagmites and stalactites.

1.5 Chemical reactions in the production of lime

Calcination
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A. High calcium limestones:

CaCO3 + heat ® CaO + CO2Â

B. Magnesian limestones:

CaMg (CO3)2 + heat ® CaCO3 + MgO + CO2 (at around 750 °C)

CaCO3 + heat ® CaO + CO2 (at around 1100 °C)

Hydration

CaO + H2O ® Ca(OH)2 (water)

MgO + H2O ® Mg(OH)2 (water)

Simply stated, limestone plus heat produces quicklime and quicklime plus water produces lime hydrate.

1.6 Common uses of lime in developing countries

1.6.1 Use of lime in building construction

1.6.2 Soil stabilization in road construction

1.6.3 Lime in agriculture

1.6.1 Use of lime in building construction

Lime is used in buildings in one of two forms, either as dry slaked lime powder or as putty. The choice of whether to use one or the other form
depends on the preference of the builders, the availability of water at the production site and the available means of transport. There is little
difference in terms of quality between the two.

The properties which make lime an excellent cementitious building material are the shape and fineness of the particles, which provide the
plasticity necessary for a good workable mortar or plaster, and its chemical properties which are the mechanical, strength giving
characteristics.

Historically, lime was used for building in such places as ancient China and Greece and, although since the discovery of portland cement its
relative use has decreased. it is used in mortars and plasters in combination with cement in most countries of the world.

Good mixing proportions are:

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lime cement sand

1 1 6

1 2 9

The first mix is used where greater strength and resistance to weather are required and the second where these properties are unnecessary.

In situations where the sand to be used is very fine and/or not well graded, a mix of 1:1:7 can be used. Where the use of cement is limited in
one way or another a small proportion of cement will suffice or none need be used at all. The use of such mortars or plasters is however
limited since they are susceptible to weathering. They are best used on internal walls, external walls which are well protected from the rain,
and in dry climates. The mix suitable under such circumstances is 1:2/3, i. e. 1 part lime to 2 or 3 parts sand. The same mix proportions are
used for mortars and plasters. Special care must be taken where the' lime is of low quality (relatively low hydroxide content) and the sand
badly graded and fine.

Limewash as an external and sometimes internal wall coating is used in many countries today. Its advantages are that it is relatively cheap,
easy to apply and gives a clean white finish, whilst its disadvantage is that it rubs off easily.

The durability of limewashes can be improved by adding small amounts of common salts or stearates. The recipes given by Bessey are:

"Quicklime 1 kg

Tallow 60 g

Water 2.5
Iitres"

Quicklime is broken into small lumps and tallow is placed in shreds over it. Enough water is then added to slake the quicklime. Once slaking
is complete the remaining water is added and then the slurry is screened to remove any lumps and remaining shreds of tallow.
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If only hydrated lime is available, powdered calcium stearate and water are added to it to produce a slurry. The recipe is:

"Hydrated lim 1 kg

powdered calcium 50 g
stearate

Water as required"

Lime in combination with pozzolanic material can be used as an alternative cementitious material to portland cement. This type of cement
can be used successfully for most purposes other than structural concrete work, i.e. in plaster, mortar, production of building blocks, screeds
etc. Some types of pozzolanic materials are: pulverized fuel ash, blastfurnace slag, volcanic ash, diatomatious earth, under-fired clay bricks,
porcellanite and others. Each has a particular form in which it is most effective as a pozzolana.

1.6.2 Soil stabilization in road construction

The construction of roads in tropical and sub-tropical regions in areas where the soil is clay or laterite will require the use of a soil stabilizer.
Lime, like portland cement, reacts chemically with certain constituents of the clay and acts as a binder. The effectiveness of lime as a soil
stabilizer is increased in warm climates where its rate of strength development will be faster than in cooler areas. 2 - 5 % hydrated lime is
mixed with soil from the road and spread over the road surface for compaction. The quantities required will depend on the compaction
density, width and thickness of sub-base or base designed, and also on the proportion of available lime in the lime hydrate. For a road 11 m
wide, sub-base 200 mm thick and a compaction density of 1500 kg/m3, where 4 % lime is to be added, 130 tonnes lime per kilometer of road
will be required.

For an existing limework with a low output (up to 15 tonnes), the implications of such a demand are:

-A long period of warning will be required to develop stockpiles, the development of which will require special financing arrangements since
the stockpiling will cause excessive strain on cashflow.

- The accent will be placed on the quantity rather than the quality produced. It should be noted however, that the higher the quality the lower
the quantities of lime required. The economic effects on transport cost, sales prices, etc. need to be carefully considered.

-A dry hydrate needs to be produced.

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The possibility of installing a small limeworks near the road works, if possible in a situation where its operation will be continued after the
completion of the road, must be considered as it may be more economic than transporting large quantities over long distances.

1.6.3 Lime in agriculture

Lime and limestone are used in agriculture to neutralize the acidity of the soil and to promote effective use of added fertilizers. Crushed
limestone, dolomite, chalk, etc. are preferred as they are slower acting than lime and therefore last longer.

Other uses are:

-water purification,

-sugar refining,

-tanning,

-neutralizing acid mine water,

-oil well drilling,

-wire drawing,

-paper and pulp production,

-sewage treatment,

-metallurgical processing,

-petroleum refining,

-calcium silicate brick production,

-pains production

and others.

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