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UPTEC Q10 001
Examensarbete 30 hp
Mars 2010
The lime industry, a potential

business area for Kanthal
Jesper Ejenstam
Abstract
The lime industry, a potential business area for
Kanthal
Jesper Ejenstam
Teknisk- naturvetenskaplig fakultet

UTH-enheten The subject of this M.Sc. thesis is to find out whether the lime industry is a possible
business area for Kanthal AB. The lime industry is one of the biggest chemical
Besöksadress: industries in the world and it is very energy demanding. In the process of making
Ångströmlaboratoriet
Lägerhyddsvägen 1 quicklime, calcium oxide, a lot of energy is needed as the dissociation of limestone,
Hus 4, Plan 0 which consists mainly of calcium carbonate, takes place in the temperature span
between 900°C and 1300°C. The total production of quicklime was in 2009 about
Postadress: 280 million tonnes, and the selling price was about $100 per ton. Today, all limekilns
Box 536
751 21 Uppsala are driven by fossil fuels, i.e. oil, coal and gas. The increasing demand on lowering the
emissions of carbon dioxide strongly affects the industry, as it is responsible for about
Telefon: 2 % of the total emissions of carbon dioxide. The industry itself claims that the
018 – 471 30 03 emissions may only be reduced about 10 %, although at very high costs. Kanthal AB
Telefax: produces electric heating solutions that may be suitable for lime production.
018 – 471 30 00 However, the lime industry is conservative and the use of electricity for lime
production is not economically feasible today. Most of the electricity comes from coal
Hemsida: power plants and therefore the use of electricity would not be more environmentally
http://www.teknat.uu.se/student
friendly in most countries. New limekilns, which are more environmentally friendly,
are on the way. These kilns do not necessarily have to use fossil fuels, provides a
purer end product and the emission of carbon dioxide is minimized. The size of the
production is also much lower, but the end products might be used in more
demanding areas, e.g. the pharmaceutical industry, and be sold at a higher price. It is
this area Kanthal has to focus on if going to enter the lime industry at this point.
Handledare: Gustaf Lorenzson

Ämnesgranskare: Håkan Engqvist
Examinator: Åsa Kassman Rudolphi
ISSN: 1401-5773, UPTEC Q10 001
Sponsor: Kanthal AB
Kalkindustrin, en möjlig marknad för Kanthal
Jesper Ejenstam
Bakgrund och syfte
Kalkindustrin är en av världens största kemikalieindustrier, näst störst efter

svavelsyraindustrin. Tekniken som används är ungefär densamma som för 100 år sedan, dock
har den optimerats en hel del. Industrin hävdar att metoderna är så pass utvecklade de kan bli,
vilket är ett problem eftersom effektiviteten ligger mellan 30 och 80 %. 2009 producerades ca
280 miljoner ton bränd kalk, varav Kina stod för ca 180 miljoner ton, och det ungefärliga
priset ligger på 100 dollar per ton.
Kanthal AB vill med det här examensarbetet få svar på frågan om kalkindustrin kan vara ett
möjligt affärsområde. Därför syftar examensarbetet till att vara kunskapsbyggande och ska
kunna ligga som underlag vid ett eventuellt ”business case” om Kanthal bestämmer sig för att
satsa på kalkindustrin.
Bränd kalk
Kalksten har används av människan i tusentals år. Ett exempel på det är pyramiderna i
Egypten som består av kalksten. Kalksten består i huvudsak av kalciumkarbonat och det finns
mycket god tillgång till mineralen över hela världen.
När kalciumkarbonat upphettas till ca 900°C sönderdelas det till ungefär lika stora delar
kalciumoxid och koldioxid . Kalciumoxid, även kallat bränd kalk, är en viktig ingrediens i
många andra processer, till exempel stålframställning där det används som slaggbildare. Idag
används framförallt två typer av ugnar för framställning av bränd kalk, roterugnar och
schaktugnar. En roterugn består av en enorm lätt sluttande cylinder med en längd på ca 100 m
och en diameter på ca 3-4 m. I ena änden finns en brännare som drivs med fossila bränslen
såsom olja eller kol. I andra änden matas kalksten in i cylindern och när cylindern sätts i
rotation transporteras kalkstenen mot brännaren där bränd kalk bildas. En schaktugn består av
ett högt torn på ca 30 m, med en diameter på 4-5 m. Kalksten matas in i toppen av schaktet, i
mitten bränns den och i botten plockas den brända kalken ut. I och med att brännarens låga är
i direkt kontakt med kalkstenen i bägge dessa kalkugnar är en viss förorening av
slutprodukten oundviklig. Detta medför att kvalitén på den brända kalken blir något sämre,
vilket påverkar priset.
Energi och miljöaspekter
Eftersom det går åt mycket energi att framställa bränd kalk, och att fossila bränslen används
som energikälla, är stora utsläpp av koldioxid oundvikligt. Kalkindustrin står för ca 2 % av
världens totala koldioxidutsläpp, där upp till 40 % kan kopplas till förbränningen av fossila
bränslen. Miljöskatter, såsom koldioxidskatt, påverkar industrins resultat kraftigt. Enligt
representanter från kalkindustrin skulle utsläppen kunna minskas med 7 till 10 %, fast till
mycket höga kostnader. Detta är långt ifrån tillräckligt och nya produktionsmetoder måste till.
I dagsläget skulle en kalkugn inte kunna drivas av elektricitet eftersom elpriset är så högt i
förhållande till fossila bränslen. Dessutom produceras stora delar av världens elektricitet idag
genom förbränning av fossila bränslen, framförallt kol. Detta medför att elanvändning inte
skulle vara mer miljövänlig i dagsläget, utan endast flytta problemet till den
energiproducerande sektorn. Dock tar koldioxidneutrala energikällor, såsom kärnkraft,
vindkraft, vattenkraft och solenergi, hela tiden nya marknadsandelar. Detta faktum,
kombinerat med ett ökat pris på fossila bränslen, gör att många vetenskapsmän tror att el som
energikälla kan vara konkurrenskraftig runt 2050.
Ny teknik
På senare år har nya förslag på kalkugnar presenterats av forskarlag och kalkföretag.

Gemensamt för alla dessa prototyper är att slutprodukten ska bli mycket renare och därför
kunna användas inom nischade produktområden, till exempel inom läkemedelsindustrin.
Detta beror framför allt på att den brända kalken aldrig förorenas av en öppen låga, vilket är
ett av problemen idag. Stort fokus ligger även på energifrågan, och ett forskarlag har tagit
fram en idé där koncentrerade solstrålar är värmekälla.
Gemensamt för de nya teknikerna är att slutprodukten blir dyrare än den är i dagsläget,
storleken på produktionen blir mindre men slutprodukten blir mycket renare.
Slutsats
I dagsläget är det inte ekonomisk lönsamt att storskaligt producera bränd kalk med elektricitet
som energikälla. Det skulle heller inte bidra till minskade utsläpp av växthusgaser. Däremot
kan produktion av bränd kalk i mindre skala kunna vara ett intressant område för Kanthal.
Flera forskargrupper har presenterat goda resultat och ett intresse från bland annat
läkemedelsindustrin finns. Detta är det område som Kanthal idag bör satsa på, vilket även ger
större inblick i industrin. Förslagsvis ska Kanthal delta på internationella kalkkonferenser där
kontakter med kalkföretag och ugnsbyggare kan skapas. Dessutom diskuteras energiproblem
och ny teknik vilket är områden där Kanthal kommer in i bilden.
Examensarbete 30 hp på civilingenjörsprogrammet
Teknisk fysik med materialvetenskap
Uppsala universitet, mars 2010
The lime industry, a potential business area for Kanthal
Contents
1 Introduction 1
1.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Basic definitions and notifications . . . . . . . . . . . . . . . . . . . . 3
1.3 Purpose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Methodology 4
3 Limestone 5
3.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2 Formation of limestone . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.4 Quarrying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.5 Limestone preparation . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.6 Environmental aspects of limestone quarrying . . . . . . . . . . . . . 7
4 Quicklime 9
4.1 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2 Theory of calcination . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2.1 Calcitic quicklime . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2.2 Dolomitic quicklime . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2.3 Stages of calcination . . . . . . . . . . . . . . . . . . . . . . . 11
4.2.4 Dissociation of calcite . . . . . . . . . . . . . . . . . . . . . . . 11
4.2.5 Sintering of high calcium quicklime . . . . . . . . . . . . . . . 14
4.3 Production of quicklime . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.3.1 Shaft kiln . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.3.2 Rotary kiln . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.3.3 Distribution of kiln types . . . . . . . . . . . . . . . . . . . . . 18
4.3.4 Environmental aspects of lime burning . . . . . . . . . . . . . 18
4.4 Slaked lime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.5 Largest quicklime producing countries . . . . . . . . . . . . . . . . . . 20
4.6 Uses of quicklime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6.1 Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6.2 Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.6.3 Metal refining . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.6.4 Pulp and Paper . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.6.5 Caustic soda . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.6.6 Soil stabilization . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.6.7 Steelmaking . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.6.8 Sugar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.6.9 Water treatment . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.6.10 Flue gas desulphuration . . . . . . . . . . . . . . . . . . . . . 25
The lime industry, a potential business area for Kanthal
5 Research and Development 26

5.1 Solar reactors for quicklime production . . . . . . . . . . . . . . . . . 26
5.2 Indirect fired limekiln . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.3 Energy source outlook . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.3.1 Fossil fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.3.2 Renewable energy sources and Nuclear energy . . . . . . . . . 31
6 Idea for an alternative heating solutions for lime-burning 32

6.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.2 Kanthal APMT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.3 Radiant tubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.3.1 Tubothal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
6.3.2 Ecothal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
6.4 Prototype proposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
7 Investigation of the impact of the calcination process on Kanthal

APMT 37
7.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
7.3.1 Visual observations . . . . . . . . . . . . . . . . . . . . . . . . 38
7.3.2 Light Optic Microscopy . . . . . . . . . . . . . . . . . . . . . 38
7.3.3 Scanning Electron Microscopy . . . . . . . . . . . . . . . . . . 39
7.3.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8 Discussion 43
8.1 Quicklime production . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
8.2 The market potential . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
8.3 Energy sources and environmental aspects . . . . . . . . . . . . . . . 43
8.4 Effects of limestone calcination on Kanthal APMT . . . . . . . . . . 44
8.5 The alternative limekiln prototype . . . . . . . . . . . . . . . . . . . . 44
8.6 Other proposed prototypes . . . . . . . . . . . . . . . . . . . . . . . . 45
9 Conclusions 46
10 Future work 47
10.1 Porcupine heating cassettes as pre-heaters in cement production . . . 47
10.2 Alloys as construction material in lime and cement facilities . . . . . 47
10.3 Lance tubes for quicklime shaft kilns . . . . . . . . . . . . . . . . . . 47
11 Acknowledgments 49
References 50
The lime industry, a potential business area for Kanthal 1
1 Introduction
1.1 Background
The lime industry is one of the largest chemical industries in the world. Every year,
about 280 million tons of quicklime (calcium oxide) is produced. The lime products
are very versatile, whereas many areas of usage have been defined. Quicklime is pro-
duced in large kilns, which often have poor efficiency. The kilns also use fossil fuel
and are one of the largest contributors of green house gases, such as carbon dioxide.
The burner in conventional limekilns does also affect the product. The flame of the
burner is in direct contact with limestone and therefore the end product will be
polluted. This reduces the selling price of the product, which is already low from
the beginning. It also decreases the areas of use of quicklime. Because quicklime
is a fairly cheap chemical, about $ 100 per ton, many producers are struggling to
survive. Thus, long range exporting of the products is just not economically fea-
sible. Therefore a lime plant often only supplies the local industries near by. The
high fuel prices, emission-taxes and low efficiency of the kilns force the producers
to find new ways of lime production. A lot of work has been done in small exper-
imental setups, but as the lime industry is very conservative the development of
new solutions is progressing slowly. The whole lime production cycle is very large
and therefore the main focus in this report will be at the calcining processes, figure 1.
Quicklime is produced by dissociation of calcium carbonate (CaCO3 ) to calcium

oxide (CaO) and carbon dioxide (CO2 ). The process takes place at high tempera-
tures, about 900◦ C to 1300◦ C depending on which properties are requested. Some
of the processes that are common today have large energy and heat losses and this
problem may be solved by modifications or using other heating techniques.
Kanthal AB is producing and selling heating solutions and is constantly looking

for new market areas where their products may fit in. The lime industry is new
ground for Kanthal AB that are hoping their products can make a difference in this
area.
Figure 1: Schematic figure of the lime production process. This report focuses on
the calcining process, which is illustrated in the square [1].
1.2 Basic definitions and notifications

The phrase lime is often used rashly by representatives and people connected to
the lime industry. This may lead to misunderstandings, as the word lime implicates
both quicklime and slaked lime. However, this does not mean that these products
have the same properties. Unfortunately this misleading phrase is commonly used
and the reader has to know the differences. Beneath, the common words are listed
together with a short explanation [2].
• Limestone is a mineral that occurs naturally in the nature, and consists mostly
of calcium carbonate (CaCO3 ). It occurs all over the world and is one of the
most important minerals known to mankind.
• Quicklime consists almost entirely of calcium oxide (CaO), and is produced

by thermal dissociation of limestone.
• Slaked lime is produced by adding water to quicklime. This is an endothermal

reaction where calcium hydroxide (Ca(OH)2) is the end product.
1.3 Purpose
Kanthal AB wants to know whether quicklime processing can strengthen its busi-
ness, and if the company can contribute to the industry. There is a need to know
more about lime and lime production, what furnace types are used, energy usage
and research done in the area, and also to get an estimate of how big the market
potential is.
Kanthal also wants to find new systems for quicklime processing, by renewable
energy or with higher efficiency. If it turns out to be possible for Kanthal to enter
this industry, ideas of a prototype limekiln, using Kanthal products are wanted.
This M.Sc. thesis is supposed to be the base for an upcoming business case.
2 Methodology
This M.Sc. thesis is mainly a literature study of the lime industry and information
has been gathered from scientific reports, books and web pages. To further un-
derstand the processes, technology and important factors of lime production, lime
facilities were visited. Experts in interesting areas, who had great importance to the
conclusions in this report, have been interviewed and cited. The literature study is
presented in Chapters 3-5.
A prototype proposal, using Kanthal heating system, is presented in Chapter 6.
A small experimental work was carried out to examine whether a Kanthal alloy
was affected by the calcination when getting in direct contact with quicklime. This
work is presented in Chapter 7.
3 Limestone
3.1 History
Limestone has been used for thousands of years. One proof is the pyramids in Giza,
figure 2 [3], which are about 5000 years old. Also the ancient Greeks and Romans
used limestone as construction material long time before the birth of Christ (BC) [2].
Moreover, in Yugoslavia, excavations have found limestone constructions that have
been dated to 5-6000 years BC. In addition to limestone, excavations have shown
that quicklime was also used in mortar to strengthen buildings. During the 19th
and 20th century several cities in USA and Canada were built in pure limestone.
An example is Kingston in Canada, where several buildings consist of limestone.
Hence, the city is known as the ”Limestone City”. These are just a few examples
of how important limestone has been to mankind throughout the years, and even
today limestone is an essential part of construction materials [2, 4].
Figure 2: Cheops pyramid in Giza, an early example that limestone has been used
as a construction material a long time.
3.2 Formation of limestone

Limestone is formed mainly in warm, shallow and still waters. It is in these envi-
ronments where organisms, which form shells and skeletons, flourish. The limestone
is in fact formed when these organisms die and accumulate onto the seabed. What
kind of organisms that flourishes in a certain area highly affects the composition of
the limestone. Apart from the organism, the environment itself at a certain area
affects the formation of limestone as well. This is why there are different types of
limestone at different places throughout the world. The formation is a very slow
process, which takes several million years to complete [2, 4].
Limestone is also formed when water evaporates. Water often consists of some
amount calcium, which is transferred to the ground when water either absorbs to
the ground or evaporates.
3.3 Properties
Limestone is a sedimentary rock that consists primarily of CaCO3 , but MgCO3 and
several other minerals are also to be found within the rock. It can be both crystalline
and amorphous, but the structure mainly depends on the age of the rock. Very old
limestone, typically more than 600 million years old, tends to be crystalline whereas
younger limestone often is amorphous. This property, among others, is the reason
that a classification system for different limestone types has been invented. The
limestone classification depends on microstructure, texture, impurities, age, grain
size and CaCO3 -content. This system has been constructed because of the wide
use of limestone and different uses have different demands. For example, when
burning limestone the temperature of the process depends of the composition of the
limestone. Further on, the temperature affects the resulting product. The amount
of a certain impurity can be crucial to one process, but is devastating to another.
The properties of limestone therefore depend very much on where, when and how it
was formed [2].
The color varies from white to grey, but can be slightly red or yellow depending
of what kind of impurities are present at a certain quarry. The crystal structure
can be orthorhombic (aragonite), hexagonal (vaterite) or rhombohedral (calcite).
Aragonite is semi stable, which means that it slowly converts to calcite in presence
of water or at temperatures above 400◦ C. The same implies for vaterite, although
it is even less stable than the aragonite and converts into calcite at temperatures
above 60◦ C [2, 4].
CaCO3 has a molar mass of 100.09g/mole. The density varies from about
1.5g/cm3 to 2, 9g/cm3, depending of the composition of the limestone. Limestone
has a hardness of about 2-4 Mohs, a scale from 1 to 10 where diamond has the
highest value. Specific heat capacity is about 0.22cal/g, and the pH is about 9 [2].
3.4 Quarrying
Limestone is one of the most common minerals in the crust of the earth, and can
be found all over the world as it covers about 10 % of the surface of the earth.
It is a relatively young mineral and therefore it can be found near the surface.
Limestone quarries are often open quarries, i.e. it is deposited from the surface and
down. Limestone mines are not feasible from an economic point of view, as walls of
limestone would have to be left behind.
The quarrying can be divided into five steps; overburden removal, drilling, blast-
ing and transportation. First of all, the limestone has to be exposed. It can be found
less than 1 m to tens of meters down in the ground. This is done by conventional
excavators and is considered to be the most demanding part of the quarrying. When
this is done, blasting holes are drilled. They are drilled with a twenty-degree angle,
which has been shown to be most effective. Further on, the limestone is loaded onto
lorries using excavators or rolling hoops. All steps in the quarrying have over the
years been accurately developed to ensure as high profit as possible [2].
In Sweden, limestone is quarried at several places but the largest quarry is found
near Slite, Gotland. The largest limestone quarry in the world is found near Roger’s
city in USA, and is owned by Michigan Limestone and Chemical company [2].
3.5 Limestone preparation

Before the limestone can be transported to the lime facilities for processing, it has
to be crushed and screened in different fractions. In some cases washing is necessary
as well. When crushing limestone, two different methods are used, impact crushers
and compression crushers. Impact crushers have the advantage of producing cubical
fractions, although a lot of powder is obtained as well. The compression crushing
obtains a more even fraction distribution, but the limestone tends to be slightly
rounded. Washing of limestone is often not necessary, as most limestone quarries
have very clean limestone that is not contaminated by clay and dirt. However,
for some areas, which demand extra clean limestone, washing is needed to achieve
required purity. Washing in rotating barrels is also used to reduce fractions size,
when fractions smaller than 10 mm are necessary [2].
3.6 Environmental aspects of limestone quarrying

The environmental effects of lime production start with the limestone quarrying.
The limestone quarries are large areas, which looks like giant craters. This results
in a disturbance in the wildlife of the area. The quarrying companies have a big
responsibility to ensure that the wildlife is not disturbed too much in the area, and a
plan has to be made how to restore the area when the quarry has served its purpose.
Another environmental effect of quarrying is the dust, which the process creates.
The dust mainly originates from crushing of the quarried limestone. There is always
a risk that the dust is spread by the wind and causes over-fertilization of lakes,
forests and agricultural land. The dust is unhealthy when inhaled as well.
Huge industrial machinery is used in the process and these generate noise, vi-
brations and exhaust gases. Although noise is mainly from the explosives that are
used when large pieces of limestone are being quarried. This is the main source of
vibrations as well, which may cause damage to near-by buildings [2, 4].
4 Quicklime
4.1 Properties
Quicklime is a porous rock, which often appears white or slightly discolored due to
impurities. Impurities may be found naturally within the limestone or may come
from the burning of fossil fuels while burning the limestone [4].
To the naked eye, CaO appears like an amorphous material, although this is
not the case. It consists of many small crystals in NaCl structure with the lattice
constant of 4.81Å. The melting point is about 2850◦ C.
Quicklime is a very reactive substance that reacts strongly with water, thus gen-
erating a large amount of heat, about 1140kJ/kg, and calcium hydroxide (Ca(OH)2)
[2, 4, 5].
4.2 Theory of calcination

To produce quicklime, limestone is heated to a temperature over the dissociation
temperature. The dissociation temperature depends on the type of limestone that
is used, and cannot be generally defined. This is because the limestone differs from
quarry to quarry, and experiments have to be carried out to find the optimal calcining
temperature for each limestone. Limestone can be divided in two subgroups, calcite
and dolomite.
4.2.1 Calcitic quicklime

Calcite consists mostly of CaCO3 and is the type of limestone that is most widely
used in the lime industry. This is because of the fact that most customers want a
high level of pure CaO as possible in their processes. The decomposition of high
calcium limestone is expressed in reaction 1 [2, 4, 5].
CaCO3 + heat ! CaO + CO2 (1)

100g 56g 44g
At atmospheric pressure, it has been shown that CaCO3 decomposes to CaO

around 900◦C. The amount of heat that is needed for the reaction has been closely
investigated through the years and values from 695 kcal/kg of CaO to 834 kcal/kg
of CaO have been reported. These values have been calculated relative an ambient
temperature of 25◦ C. This is not entirely correct due to the fact that heat, which
is needed to raise the temperature from 25◦ C to 900◦C, has to be taken into con-
sideration. Furthermore, when CaO and CO2 are cooled from 900◦ C to 25◦ C, some
energy is gained by exothermic reactions. The net sum of the total required heat
is therefore a little lower than for the heat required for the decomposition. With
respect to this, values from 698 kcal/kg of CaO to 723 kcal/kg of CaO have been
reported [2, 4, 5].
4.2.2 Dolomitic quicklime

Dolomite is a magnesian limestone, which consists of both CaCO3 and MgCO3 .
When dolomite decomposes, it can be done in a two-stage decomposition, a direct
decomposition or by a mix of these reactions [2, 4, 5].
MgCO3 · CaCO3 + heat ! CaCO3 · MgO + CO2 (2)

184g 140g 44g
CaCO3 · MgO + heat ! CaO · MgO + CO2 (3)

140g 96g 44g
MgCO3 · CaCO3 + heat ! CaO · MgO + 2CO2 (4)

184g 96g 88g
The different reaction stages depend on the starting temperature of the calcina-
tion. At low temperatures, the two-stage reaction, 2 + 3, has been reported whereas
reaction 4 has been reported for temperatures around 900◦ C. The heat of dissoci-
ation of dolomite has been reported to be about 700 kcal/kg of (CaO · MgO), i.e.
about the same as for calcitic limestone [2, 4, 5].
4.2.3 Stages of calcination

Throughout the years, the calcination process has been closely studied. The process
can be divided in five steps [2].
1. Limestone is preheated to about 800◦ C by using exhaust gases from the main
process.
2. When the limestone reaches 800◦C, the pressure from the dissociated CO2
equals the pressure of the hot gases in the limekiln. The surface of the lime-
stone starts to dissociate even faster and when the temperature reaches about
900◦C, the layer of quicklime is about 0.5 mm thick for a limestone lump of
about 25 mm radius.
3. When the temperature rises above 900◦C, which is about the optimal dissoci-
ation temperature, the partial pressure within the lump surpasses the atmo-
spheric pressure and the dissociation proceeds beneath the surface layer.
4. The dissociated limestone begins to sinter after some time, which corresponds
to the temperature in the furnace. A higher temperature implies a faster
sintering. The sintering process results in less reactive quicklime due to a
smaller surface area.
5. The quicklime leaves the calcination zone and is cooled by air.
4.2.4 Dissociation of calcite

The disassociation of high calcium limestone, calcite, always starts from the surface
of the limestone and proceeds gradually into the core. As earlier mentioned, the
dissociation process starts at the surface of the limestone at temperatures slightly
below the calcining temperature, whereas a quicklime shell encapsulates it. At
temperatures higher than the calcining temperature, the CO2 -pressure is higher
inside the limestone than outside that forces CO2 to escape. This implies that
greater radius of the limestone will require a higher temperature to fully calcine it.
For some types of limestone the dissociation temperature can vary 150◦ C to 350◦ C
from the surface to the center of the limestone. In addition to higher temperatures,
there is often a longer calcining time for larger fractions of limestone. The variation
of the calcining time with respect to the temperature and radius is shown in figure
3 [5].
Figure 3: The variation in calcining time with temperature and lump diameter. a.)
150 mm, b.) 125 mm, c.) 100 mm, d.) 75 mm and e.) 50 mm.
The dissociation of calcitic limestone, illustrated in figure 4 [5], can be summa-

rized as:
(a) Heat is transferred from the hot ambient to the surface of the limestone
(b) Heat is conducted through the decomposed layer into material, which is yet to
be dissociated.
(c) CaCO3 dissociates into CaO and CO2 .
(d) CO2 migrates from the inside of the limestone through the decomposed layer.
(e) CO2 migrates from the surface limestone.

Figure 4: A schematic of the calcination process of high calcium limestone.
The processes (a), (b) and (c) are well known as they are relatively straight for-
ward. However, (d) and (e) are more complex as the properties of the decomposed
layers will change due to sintering of CaO, slagging of the surface and absorption
of sulfur dioxide [2, 5].
The following list roughly rates the most important factors of limestone calcina-
tion [2, 5].
1. Characteristics of the limestone.
2. Particle size distribution.
3. Shape of particles.
4. Temperature profile of the calcining zone.
5. Rate of heat exchange between the gases and the particles.
Because different limestone types have slightly different properties, each type
must be properly investigated. The optimum temperature cycle may vary between
types, whereas it is important to characterize the limestone type properties individ-
ually, with respect to the optimal calcining temperature cycle. The heating cycle
have great impact on lime quality, shrinkage and reactivity. Experiments have shown
that a gradual increase of temperature, rather than shock heating, gives the best
quicklime quality. However, little is investigated in this area and perhaps even bet-
ter quicklime could be produced with better understanding of the impact of the
temperature cycle [5].
4.2.5 Sintering of high calcium quicklime

One process that may disturb the calcining process is sintering. When high cal-
cium limestone is heated, the volume increases due to thermal expansion. At, and
above, the calcining temperature small crystals of CaO are formed. This process
proceeds until the whole limestone has been converted into CaO, which consists of
several small crystals at this point. This leads to an extremely large surface area,
and therefore highly reactive quicklime, due to the large amount of small crystals.
When the furnace temperature is higher than the calcining temperature, these small
crystals starts to unitize and larger crystals are formed. This leads to shrinkage of
the material due to the settle up of the CaO-crystals. Another effect of to high
calcining temperature is when the surface of the material has been severed sintered
it may disrupt the continuous dissociation of limestone core, and stops it. When
this happens, so called dead burned quicklime is formed. On the other hand, the
sintering process that occurs after completion of the calcination is very common and
useful. Soft, medium and hard burnt quicklime are common products, and refers to
the level of sintering of the material. Soft burnt quicklime is very reactive but may
contain small amounts of CaCO3 , as the calcination process was stopped to ensure
small crystal sizes in the material. Therefore a full calcination of the core has to be
sacrificed. Hard burnt lime has a high CaO-content but is not as reactive as soft
burnt quicklime due smaller total surface area because of fewer grains. What type
of quicklime is requested depends on the buyer’s processes. Some processes require
highly reactive lime, while others require not so reactive lime [2].
4.3 Production of quicklime

4.3.1 Shaft kiln
The shaft kiln, figure 5 [6], is a vertical furnace, in which the limestone is inserted
from the top, and passes down through the kiln during the process. The top of the
kiln works as a preheating stage where the limestone is heated and partly calcined.
This is due to the hot exhaust gases created by the calcining burners. In the middle
of the kiln, the calcining zone is found. The limestone is heated with a flame, which
is led into the limestone through pipes. The bottom of the kiln is the cooling area.
Cooled air is blown into the kiln, which help cooling the limestone. The air is then
heated in the calcining zone and travels upwards in the kiln and helps preheating
the incoming limestone.
Figure 5: Schematic of shaft kiln.
A typical shaft kiln is about 30 meters high and has a diameter of 2 to 7 me-
ters. Firebricks build up the walls, which have a thickness of about 400 mm. The
most common shaft kiln has two shafts connected to each other, called parallel flow
regenerative (PFR), to acquire as high efficiency as possible. The idea is to let hot
exhaust gases travel through as much limestone as possible before leaving the fur-
nace, figure 6. As there are two shafts in a PFR, the hot exhaust gases from the
active shaft are used to heat the limestone in the passive shaft. In the next cycle, the
active and passive shaft shifts. This solution makes the shaft kiln the most efficient
limekiln today. The down side is that a maximum temperature in the furnace is
about 1000◦C, due to the thick limestone mass. The ”low” temperature implies to
a high sulphur content in the quicklime as the temperature is to low for formation
of SO2 . This fact reduces the number of possible users, e.g. stainless steel produc-
ers. On the other hand, the low temperature leads to a low level of sintering and
therefore highly reactive quicklime is obtained. The production capacity of modern
PFR shaft kilns is about 100 to 600 tones per day. Today the shaft kiln is the most
common lime-burning furnace, mainly because of the high efficiency. The efficiency
of a PFR shaft kiln is about 80 % [7], and the consumed heat is about 4 MJ per kg
quicklime [2, 6].
Figure 6: The heat flow in a PFR shaft kiln.

4.3.2 Rotary kiln

The rotary kiln, figure 7, is the other major type of lime-burning furnaces. It was
invented in the beginning of the 20th century, and at that time the rotary kiln
was superior all other kilns. The reason to the success was because wider range of
limestone fractions could be calcined, from very fine fractions and upwards. Another
advantage of the rotary kiln was the possibility to remove sulphur from the quicklime.
Quicklime is used in the metallurgical process as a slag remover. If high levels of
sulphur contaminate the stainless steel, the corrosion resistance is affected as the
sulphur makes passivation of the steel surface difficult [8]. The reason that sulphur
can be removed is because of the high operating temperatures, which is possible to
achieve in the kiln. At these temperatures, sulphur complexes dissociate and leave
the limestone as sulphur dioxide is transported out of the kiln with the exhaust
gases. A typical rotary kiln produces about 1000 tones of quicklime per day.
The theoretical heat requirement for dissociation of CaCO3 is about 3,15 MJ
per kg of lime. The rotary kiln consumes about 8 MJ per kg of lime, which gives
an approximate efficiency of 40 % [7]. The burners is often of flexible fuel type, i.e.
gas, coal, oil or waste can be burnt individually or simultaneously. The power of the
burner is decided by the heat exchange of the fuel that is burnt, but has an average
power of 50 to 100 MW [7].
In contrast to shaft kilns, the rotary kiln has a much higher operating costs.
This is mainly due to the higher fuel cost due to poor heat exchange. Some modern
rotary kilns have a pre-heating system that uses the heat from the exhaust gases to
heat the limestone before it enters the kiln. The loss of heat in the rotary kiln system
is another problem. The shell is built up of firebricks and a thin steel mantle, which
have the combined thickness of about 250 mm. There are rotary kilns of all sizes,
longer with smaller diameter as well as shorter with greater diameter. A modern
kiln is about 100 m long with a diameter and about 4-5 meters. The weight varies
between models, but is often greater than 1000 tonnes. The rotary kiln also has a
small gradient, which is needed for transportation of limestone through the kiln.
Rotary kilns have a few support points, called riding rings, which also are the
points where the rotating motion is created. The rotating motion is needed to move
the limestone through the kiln during the process. The length of the kiln decides
the number of support points that are needed. Riding rings are machined to obtain
as smooth surface as possible. This is to ensure that the friction is low between
the riding rings and the kiln. The rotation speed of the kiln is typically 4 to 5 rpm
and a drive gear creates the motion. To start the rotating motion a strong electric
engine, of about 800 kW, is used. The engine has a variable speed drive, which is
needed, as the rotation speed of the kiln is proportional to the flow of lime trough
the furnace.
These days the rotary kiln is the standard furnace type in many applications,
not only for lime burning. Other products made by rotary kilns are; cement, iron
ore pellets, alumina silicate, titan dioxide, vermiculite. Rotary kilns are also used
for roasting sulfide ores [2, 9].
Figure 7: Schematic figure of a typical rotary kiln. The limestone is transported

through the kiln due to the rotating motion and the small gradient of the kiln.
4.3.3 Distribution of kiln types

Because of the higher efficiency of PFR-kilns, they have become the most common
kiln type, figure 8 [10]. In China, which is the largest lime producing country, there
are lots of unknown types of limekilns. This is due to many locally constructed
kilns and a rapid expansion of the lime industry within China. In Japan, several
smaller alternative limekilns have been developed during the past years, mainly for
experimental work [7, 10].
Figure 8: Chart showing the distribution of limekilns used in the world.
4.3.4 Environmental aspects of lime burning

During the calcining process, a lot of greenhouse gases are emitted, especially nitrous
gases and carbon dioxide. The chemical process itself gives rise to carbon dioxide,
which constitute about half the mass of CaCO3 . This part of the CO2 -emission
should not be calculated as a true emission of carbon dioxide as CaO want to
convert into CaCO3 again, and for this process CO2 is needed.
During the process of making quicklime, a large amount of CO2 is created. The
industry is responsible for almost 2% of the global CO2 emissions. Up to 40% of
these emissions is derived from the fuel, burnt in the process. The total sum of
the emitted CO2 by mankind is about 29 billion tons per year. Up to about 220
million tons are directly derived from the usage of fossil fuels [5], figure 9. The global
warming rate is estimated to about 0.2◦ C every 10 year, and during the 20th century
the mean temperature in Europe have risen about 0.95◦ C. Reports are showing that
in about 100 years the mean temperature will rise about 2.0 - 6.3◦ C, due to global
warming [11]. However, this is lively debated and some scientists claims that the
global mean temperature actually are decreasing.
Figure 9: Distribution of CO2 -emissions within the lime industry (in million tonnes).
4.4 Slaked lime

Slaked lime consists of calcium hydroxide (Ca(OH)2) and is obtained when CaO
reacts with water in an exothermal reaction; see reaction 5. Slaked lime is often
used for several lime products consisting Ca(OH)2 such as hydrated lime, milk of
lime and lime putty. In this section, only hydrated lime will be considered. The
other products are basically variations of the hydrated lime.
At temperatures lower than 350◦ C, CaO reacts with water, and heat is released.
About 276 kcal/kg of CaO have been reported for this process [2]. However, if the
temperature exceeds 350◦ C, the counter-reaction occurs.
CaO + H2 O ! Ca(OH)2 + Heat (5)

56.1g 18g 74.1g
For dolomitic lime, with high magnesium content, the process is done slightly
different. The reaction is similar to the reaction of CaO and water; see reaction 6,
although under steam pressure at temperatures above 100◦ C. The released heat has
been reported to 211 kcal/kg of CaO [2].
MgO · CaO + 2(H2 O) ! Ca(OH)2 · Mg(OH)2 + Heat (6)

96.4g 36g 132.4g
An interesting thing to notice is the low solubility of Ca(OH)2 in water, which

is 1.28 g/l at 50◦ C and 0.71 g/l at 100◦C. Magnesium hydroxide hardly solute in
water, only 0.01 g/l has been reported [2].
4.5 Largest quicklime producing countries

In 2009, the world production of lime was estimated to about 280 million tonnes.
This was a decrease in production from 2008 with about 5 %, due to the world wide
financial crisis. However, the price of quicklime continued to increase, which it has
done every year. In 2009, the quicklime price increased with about $11 per ton to $
101 per ton. The increasing price is mainly because of increasing production costs.
Earlier years the increasing fuel costs, and taxes, strongly influenced the price of
quicklime. In 2009, the fuel prices decreased dramatically but the lime companies
still struggled with increasing production costs. China is today, by far, the largest
lime-producing country in the world with more than 50 % of the total production,
see figure 10 [12].
Figure 10: Countries with 90 % of the total world lime production (in million
tonnes).
4.6 Uses of quicklime

Quicklime is one of the most versatile chemicals known to man and the areas of use
are almost countless. It is also one of the largest chemical industries in the world
[4].
The areas that consume the most tonnage of lime will be presented in this section,
but remember that there are other areas of use as well. Many areas of use may not
even have seen the light of the day at this point.
4.6.1 Agriculture
Agricultural lime, mostly slaked lime, is mainly used to neutralize the pH-value of
soil to improve vegetation. It also improves the stability of the soil by decreasing
crusting of the surface and therefore reducing soil erosion. Another effect is that
the water penetration, of the soil, is improved. Other important minerals, such as
magnesium, phosphorous, nitrogen and potassium, can be added to the agricultural
lime to improve the fertility of the soil. If the soil has high levels of iron and
aluminum, the lime helps to neutralize those elements. Agricultural lime can also
be used to prevent spreading of diseases among plants and animals. By increasing
the pH-value of the treated soil, spreading of bacteria is prevented [2, 13].
4.6.2 Glass
Soda-Lime glass is one of the most common types of glass. It is mostly used for
glass containers, such as coca cola bottles, and windowpanes. The glass is made
by melting and mixing of quicklime, limestone, sodium carbonate, silicon dioxide,
aluminum dioxide, and fining agents at a temperature of about 1700◦ C. For glass
containers, limestone is mainly used, but for windowpanes high calcium quicklime
is used. This is because high calcium quicklime improves the transparency of the
glass within the wavelengths of visual light [2, 13].
4.6.3 Metal refining

Quicklime is a very important ingredient when refining non-ferrous metal ores. The
quicklime controls the pH value of the solution and acts depressant that is neces-
sary to extract pure metals, such as gold, silver and nickel from cyanide extraction.
Quicklime also enables copper pyrites (Cu2 S) to be separated from arsenopyrite
(As2 S5 ).
When producing magnesium, dolomitic quicklime is used to reduce magnesium ox-

ide with ferrosilicon (F eSi). The process takes place at temperatures above 1200◦ C
and at low pressures, about 13 to 670 KPa. When the magnesium oxide has been
reduced, gaseous magnesium is obtained that condensates at about 450◦C.
2CaO + 2MgO + Si → 2Mg + Ca2 SiO4 (7)
Pure calcium is another metal that is produced by thermal reduction. High

calcium quicklime is mixed with aluminum, and heated to about 1200◦ at about 0,1
Pa.
3CaO + 2Al → Al2 O3 + Ca (8)
Mercury is produced by a similar process and the mineral that is used is cinnabarite
(HgS). Cinnabarite is reduced in presence of oxygen, but can be reduced in absence
of oxygen as well, see reaction 9 and reaction 10. There are two ways of reducing
cinnabarite, with or without presence of oxygen. Both processes take place at about
300◦C [2, 13].
4HgS + 4CaO → 3CaS + CaSO4 + 4Hg (9)
HgS + CaO + 1, 5O2 → CaSO4 + Hg (10)

4.6.4 Pulp and Paper

In the paper industry, slaked lime is used in the sulfate process or the Kraft-process
as it is called. In this process, wood is converted into wood pulp that consists
mostly of cellulose fibers. Kraft is called ”black liquor” and is dehydrated and burnt
to produce a mix of sodium carbonate and sodium sulfide. This smelt is then mixed
with slaked lime, which has a caustic effect, and calcium carbonate and sodium
hydroxide liquor is obtained. The calcium carbonate is filtered from the solution
and is later re-calcined in a kiln and can therefore be recycled. The same implies
for the sodium hydroxide. About 250 kg of slaked lime is used in this process.
A lot of slaked lime was earlier used in the sulfite pulp process as well, but has
now been exchanged for other alkalis that are easier to handle than lime products
[2].
4.6.5 Caustic soda

Slaked lime and soda ash converts into caustic soda and calcium carbonate, when
mixed. Caustic soda is an essential ingredient in many products such as soap and
detergents, bleach, aluminum, petroleum products and in several chemical processes
[13].
4.6.6 Soil stabilization

Quicklime and slaked lime are commonly used at building sites to dry wet soil and
increase the stability of the ground. This is necessary when heavy machinery is used
at these sites. By stabilizing the soil, building time is reduced and money is saved.
The soil is stabilized because quicklime modifies clay, due to the exchange of
cations from the calcium and the minerals the clay consists of. The result is swelling,
hardening and drying of the clay.
Because both quicklime and slaked lime are relatively cheap chemicals, this area
of use has been very popular as it is very cost effective [2, 13].
4.6.7 Steelmaking
There are two different methods commonly used in steel production today, the
method of Basic Oxygen Steelmaking (BOS) or re-melting steel scrap. When pro-
ducing steel with BOS, oxygen are blown through the melted pig iron to reduce
the high level of coal in the melt. At the same time, quicklime is mixed into the
melt. This is done to remove impurities, such as phosphor, sulphur and silica, by
forming slag. Typically 30 to 50 kg CaO is used per ton produced steel. About
30 to 50 % of the lime is dolomitic lime, high magnesium content, which is added
for two reasons. First of all, magnesium oxide help produce certain slag products
that calcium oxide is unable to elaborate. Secondly, magnesium oxide slag products
protect the furnace, increasing refractory lining lifetime. Steel can also be produced
by scrap melting. This is very common today, whereas lots of steel is recycled. The
steel-scrap is often melted in blast furnaces, and lime is once again used for impurity
removal through slag forming. The used quicklime is often in form of lumps, but
some modern steel plants uses quicklime powder as it has shown to be more effective
in modern refractories.
When producing ultra pure steel, a secondary refining is often necessary. In this
production step, quicklime is used for further impurity removal, but also to adjust
the temperature and the chemistry of the steel-melt [14, 15].
4.6.8 Sugar
Sugar can be produced from either sugarcanes or sugar beets. When using sugar-
canes, slaked lime is used in both the production and refining of the sugar. When
the canes are harvested they are treated with water, which lowers the pH to about
4 to 5. Slaked lime is added to raise the pH, which is needed to destroy enzymes,
e.g. invertase. Further on, slaked lime is also used to remove inorganic and organic
compounds by forming insoluble calcium salts. These salts are then filtered from
the solution.
When producing sugar from sugar beets, quicklime is used instead of slaked lime.
The sugar beet is washed in hot water to extract the sugar, which also contains col-
loidal, suspended and dissolved compounds. At this point the extract is treated
with quicklime to raise pH and to create deposits of calcium salts and ”carbonation
sludge” that are filtered from the solution.
When producing sugar from canes, about 3 kg of slaked lime is used to produce
1 ton of sugar. Sugar from sugar beets requires about 200 kg of quicklime per ton
produced sugar. The latter industry often has its own quicklime production close
to the sugar refinery [2, 13].
4.6.9 Water treatment

Lime is essential in water treatment. In municipal wastewater treatment, lime is
used to remove nitrogen and phosphor. This is because of the high pH caused by
lime. The result is that nitrogen and phosphor are precipitated and can be removed
from the wastewater. Due to this, algae growth can be prevented. Lime also acts as
a filter, in which sludge is removed. In industrial water treatment, lime is used to
neutralize acids and to remove heavy metals by precipitation. For drinking water
treatment, lime is used for softening, pH adjustment, removal of impurities (e.g.
arsenic) and to kill bacteria and viruses. The latter is done by raising the pH of the
water to about 11 for about 1 to 3 days [2, 13].
4.6.10 Flue gas desulphuration

When fossil fuels and waste are burnt, sulphur dioxide (SO2) is formed. SO2 is
responsible for the formation of acid rain, which affects the environment negatively
due to acidifying of lakes and grounds. Use of lime prevents large emissions of SO2 .
Exhaust gases, which consist partly of SO2 is filtered through lime and calcium
sulfite (CaSO3 ). This can be achieved through wet or dry filtering. Wet filtering of
SO2 is done by using slaked lime, reaction 11, and dry filtering, reaction 12, by using
quicklime. The resulting product, CaSO3 , is commonly used as a preservative. It is
also used to produce gypsum, which is done by adding water and oxygen to CaSO3 ,
see reaction 13. Then the solution is dried and gypsum plates are formed, which are
used in constructions etc [2].
SO2 + Ca(OH)2 → CaSO3 + H2 O (11)
SO2 + CaO → CaSO3 (12)
2CaSO3 + 4H2 O + O2 → 2(CaSO4 · H2 O) (13)

5 Research and Development

5.1 Solar reactors for quicklime production
Anton Meier, doctor at the Solar Technology Laboratory at the Paul Scherrer In-
stitute, has during the last years been working, together with his team, on a solar
reactor for quicklime production. The idea is to use mirrors to concentrate solar
beams to calcine limestone. This would generate highly pure quicklime for special
sectors, such as the chemical and pharmaceutical industry because no exhaust gases
are polluting the end product. However, this is true for any indirect heated limekiln.
Another advantage is the huge reduction of emitted CO2 . This solution is entirely
CO2 -free, in contrast to conventional limekilns that emit about 2 % of the total
global emissions. A solar lime reactor plant would therefore be able to reduce emis-
sions up to 20 %. The fraction of limestone that the group focused on is in the range
of 1 to 5 mm, and results showed that over 98% of the limestone were calcined. This
was done in a laboratory kiln of about 10 kW, which managed to produce about
15 tones per day. Concentrated solar beams were not used in the experiment, but
silicon carbide (SiC) elements from Kanthal AB, figure 11. The heat source itself
does not influence the resulting quicklime, and therefore electric heating was used
to produce reference samples of quicklime [1, 16].
Figure 11: SiC element from Kanthal AB was used to produce reference quicklime.
For industrial use A. Meier et. al., proposed three different solutions for solar
beam lime burning [1, 16]. All of these solutions use mirrors to concentrate the
solar beams, but some minor differences were introduced as all of them had their
advantaged. The ”Top Tower” (TT), figure 12a, uses heliostat mirrors to focus the
solar beam into the reactor, which is located in the top of a tower. The ”Beam down”
(BD), figure 12b, is very similar but instead of having the reactor in the top of the
tower, it is located in the bottom. In the top of the tower, a parabolic concentrator
is mounted that collects the solar beams from the heliostat mirrors and focus the
beam into the reactor. The reason for having two solutions is because of how much
areal available at a certain location. The TT-solution may be the best solution if the
areal is limited, although as the reactor is located in the top of the tower handling
of the quicklime is an issue. The BT-solution makes quicklime handling easier, but
tends to be more expensive due to the extra parabolic concentrator [1, 16].
Figure 12: a.) Illustration of a tower top system (TT), b.) Illustration of a beam
down system (BD).
The third solution, figure 13, is supposed to be applied at areas that are moun-
tainous or where land area is limited. Heliostat mirrors are mounted on a south
facing hill, natural of artificial, and the solar beams are concentrated into a vertical
lime reactor [1, 16].
Figure 13: Illustration of a mountainside mounted solar lime plant.
A disadvantage of this lime burning solution is the geographic areas, figure 14,
where it can be applied, as the minimum solar insolation is 2000 kW h/m2 . Solar
beam produced lime have higher production costs than conventional lime, due to
more expensive production equipment. The capacity of the plants is calculated to
about 50 tones per day, which is notably less than a conventional kiln such as the
shaft kiln. This leads to a cost of about $ 128 per ton to $ 157 per ton, for solar
beam produced lime. The selling price for conventional lime is about $ 100 per ton,
about 1 to 1.5 times less than solar produced lime. However, solar produced lime
has far greater purity and therefore may be interesting in special sectors such as the
pharmaceutical industry [1, 16].
Figure 14: Regions with annual solar irradiation of at least 2000 kW h/m2 .
5.2 Indirect fired limekiln

At the international lime association congress in 2002, H.E. Willis of Merichem
Company, USA presented an idea of an indirect fired limekiln [17]. He had been
sketching on a horizontal limekiln, consisting of a ceramic tube, in which a ceramic
screw was inserted. The screw was supposed to rotate slowly, and therefore move
the limestone through the kiln while being calcined, see figure 15 [17]. The kiln is
supposed to have three main advantages over conventional limekilns:
1. Possibility to calcine very fine limestone lumps and powder.

2. CO2 decomposed from the calcination can be separated from exhaust gasses,
and be recovered.
3. Any heat source can be used.
Figure 15: Schematic view of the indirect fired limekiln.
H.E Willis, Yoshizawa lime industry, JP Steel Plantech and Haldenwanger started
collaboration and a prototype kiln was constructed. The prototype was of semi-
industrialized size and was finished in 2003. The total length of the kiln was 5.4
m, in which the ceramic tube, consisting of six sections, with length of 0.9 m and
diameter of 0.3 m, was mounted. Inside the ceramic tube, the ceramic screw was
inserted. In figure 16, a cross section sketch of the prototype can be observed. Early
in the project they were able to produce quicklime with quality equal to conven-
tional quicklime. However, some problems occurred. The limestone had ambient
temperature when entered the kiln. This caused thermal stress to the first ceramic
tubes, which broke. There was not enough room for a limestone pre-heater so the
solution was to change the first two ceramic tubes to metallic tubes. Further testing
showed that the prototype were able to calcine very fine limestone powder with good
results. This cannot be done in conventional limekilns today. However, fine lime
powder tended to aggregate and adhered to the ceramic screw. This caused the
rotation torque to increase and less limestone could be calcined due to less space in
the kiln. The result was that the calcination capacity of the kiln decreased from 150
kg per hour, to about 100 to 120 kg per hour [17].
Figure 16: Cross sectional view of the indirect fired limekiln.
The conclusion was that the indirect limekiln prototype is very successful. Fur-
ther work is to be carried out with a goal to commercialize the prototype kiln. The
ceramic tube is very sensitive to thermal stress whereas other materials were con-
sidered, such as aluminum oxide, which can withstand higher temperatures. This
would also open for other high temperature applications, such as high temperature
treatment of inorganic materials etc [17].
5.3 Energy source outlook

5.3.1 Fossil fuels
Fossil fuels have been the major energy source the last centuries, but now new energy
sources must be invented. There are two major reasons for this, the environmental
impact and the fact that oil fields and natural gas resources are starting to peter.
Coal findings, however, do not show signs of declination [18]. Fossil fuels have
lately become the topic of conversation all over the world, due to the environmental
aspects. The majority of emitted CO2 originates from burning of fossil fuels, and
scientists claims that this is one of the reasons why the temperature of the earth
is rising. One attempt to reduce the use of fossil fuels has been to introduce the
CO2 -tax, where companies, which emit large amounts of CO2 , have to pay a certain
fee. However, companies have been allocated a certain amount of CO2 that they
can emit without being charged with any taxes. Companies, which have reduced
their emissions, can sell emission rights to other companies that have exceeded
their amount of allocated CO2 . Due to this, these companies gets lower CO2 -tax.
However, every year the allocated amount of ”free” CO2 is reduced and the CO2-
tax increases [19]. The reason for this system is to force the companies that use
fossil fuels, as their main energy source, to find other more environmentally friendly
solutions. However, the associates of the lime industry claims that the processes
used today are as optimal as they can be. The emissions can only be reduced about
10 %, but this would cost a lot [20].
5.3.2 Renewable energy sources and Nuclear energy

Renewable energy sources, such as wind, solar, wave, and hydroelectric power have
been increasing their market shares the last decades. Today, electricity from re-
newable energy sources have about 15 % of the total energy market but is rapidly
increasing 17 [21]. Nuclear energy has always been controversial due to the security
issues because of the accidents in Harrisburg 1979 and in Chernobyl 1986. The
threat of nuclear weapons and the issue of handling of nuclear waste products have
also infected the debate around nuclear energy. The need of CO2 -free energy, and
the highly effective nuclear energy have overcome many obstacles and today the de-
velopment of nuclear power is very intense. New reactors are invented, which aims
at reducing the half-life of the nuclear waste from some hundred thousand years to
about 500 years [22]. Today, about 30 % of the produced electricity in the world
comes from nuclear energy and this figure is increasing every year [21].
Figure 17: Distribution of energy sources for electricity production, within the Kyoto
member countries.
6 Idea for an alternative heating solutions for lime-

burning
6.1 Background
One part of this M.Sc. thesis was to propose a prototype lime-burning kiln, using a
Kanthal heating system. The design, which is presented in this section, was chosen
after a company visit where a similar furnace was studied. The company, HASopor,
produces foam glass for ground stabilization in a furnace where their product is
applied on a rolling hoop and is heated as the hoop slowly moves through the
furnace. Electric radiant tubes are used, beneath and over the hoop, to heat the
product to about 900◦ C.
The glass foam that HASopor produces has no resemblance with quicklime what-
soever but the heating solution may be used successfully in both processes.
6.2 Kanthal APMT

Kanthal APMT (Advanced Powder Metallurgical Tube) is an alloy consisting mostly
of iron, chromium and aluminum. It offers high strength and corrosion resistance,
together with a long working life. In contrast to nickel-chromium alloys, Kanthal
APMT withstands higher temperatures. Kanthal APMT also offers high creep re-
sistance, a property that can be derived to the high corrosion resistance. Corrosion
reduces strength, due to local or general undermining of the material. Another as-
pect of the creep resistance of Kanthal APMT is the linear deformation behavior
over time and temperature. The high corrosion resistance of Kanthal APMT is due
to the protective aluminum oxide (Al2 O3 ), which is formed on the surface when the
alloy is heated. This oxide is thermodynamically stable, has good adhesion to the
bulk material and has a slow growth rate. The slow growth rate is important to
ensure a long-term protection of the material. Due to the protective oxide, Kanthal
APMT can be used in troublesome environments such as high carbon atmospheres
and sulphur atmospheres. Kanthal APMT is recommended in temperatures from
600◦C up to 1250◦C to ensure even and good performance, however it can withstand
even higher temperatures [23].
6.3 Radiant tubes

Radiant tubes, figure 18 are extruded from a powder metallurgical (PM) base mate-
rial, which gives benefits over traditional tubes, e.g. higher mechanical strength due
to dispersion strengthening. Kanthal offers two PM materials, Kanthal APM and
Kanthal APMT. Kanthal APMT is a further development of Kanthal APM, with
higher strength [23].
Figure 18: Kanthal radiant tubes.
6.3.1 Tubothal
Tubothal, figure 19, is an electric heating solution from Kanthal, which offers high
power, low weight and long lifetime. The heating elements that are made from a
Kanthal alloy are inserted into a radiant tube. The system has an operating tem-
perature interval of 600◦ C to 1250◦C, and the temperature can be easily controlled.
Ability to fine tune the temperature in the furnace gives Tubothal a big advantage
in processes where temperature cycling is of great importance. Another advantage
is that the elements can easily be replaced, without having to remove the radiant
tubes and therefore the process does not have to be interrupted [23].
Figure 19: Kanthal Tubothal.
6.3.2 Ecothal
The Ecothal Single-Ended Recuperative burner (SER), figure 20, was designed for
high efficiency, reliability and low emissions. It has an efficiency of about 80 % and
has been shown to be about 10 % more effective than other commercial burners.
The design of the Ecothal makes it the cleanest burner on the market, due to the
well-defined combustion. This leads to lower emissions of green house gases and
lower operating costs. The high efficiency and low emissions are obtained when the
exhaust gases heat the gas at the inlet, and therefore a more effective burning of
the gases is achieved. The Ecothal is mounted into a Kanthal APMT radiant tube,
and therefore the burner offers indirect heating through the radiant tube [23].
Figure 20: Kanthal Ecothal.
6.4 Prototype proposal

The prototype, figure 211 , proposal that was discussed during this M.Sc. thesis
has some advantages. The magnitude of the lime production can easily be decided,
and the amount of power needed depends on how many radiant tubes are fitted
inside the furnace. Tubothal or Ecothal heaters could be used, which gives the user
the ability to use either electricity or gas as energy source. Other Kanthal heating
solutions may be of interest as well, but these two options seem to be the most
appropriate at the time. The throughput of lime also depends on the width of the
conveyor belt, and for large quantities this may be a problem as the hoops often are
around 1 m in width. However, in such case several parallel systems may be used
to increase quicklime output. The system can also be divided into different heating
zones, as each radiant tube is individually controlled. This gives the producer the
opportunity to fine-tune the optimal heating cycle for their process. The prototype
is designed for temperatures of about 900◦ C to 1000◦C, as this temperature is used
in about 60 % of the conventional limekilns today. For higher temperatures, other
heating elements may be of use. However, problems with the rolling hoop may also
occur at higher temperature as the common materials does not withstand those
1
Figure by Per Kruse, Kanthal AB
temperatures.
Figure 21: Prototype sketch, using Kanthal radiant tubes.

7 Investigation of the impact of the calcination

process on Kanthal APMT
7.1 Background
If used in the lime industry, the Kanthal alloy may be exposed to highly reactive
quicklime. In theory this would not happen, as the heating system would never
be in contact with lime or limestone. However, if direct contact would occur, the
heating system must not be severely damaged.
7.2 Experimental
Test samples of Kanthal APMT (Advanced Powder Metallurgical Tube), an alloy
consisting of mostly iron, chromium and aluminum, were exposed to a powder con-
sisting of crushed calcitic limestone, which has high calcium content greater than 95
%. The limestone powder was applied on the test samples, which then were placed
inside an electric furnace for about one hour. During this hour, the limestone pow-
der calcined, and quicklime was obtained. After one hour, the test samples were
taken out of the furnace, the quicklime was removed and new limestone powder was
applied. This was repeated eight times for every test sample.
Four experiments were conducted, table 1. Two test pieces were pre-oxidized
in 1050◦ C for 8 hours, to ensure that they were protected with a covering layer of
aluminum oxide when exposed to the lime. The other two test pieces were not pre-
oxidized. Two different temperatures were chosen, 950◦C and 1250◦ C. These two
temperatures were chosen, as they are about the same temperatures that are used
in conventional kilns. The working temperature in a shaft kiln is around 900◦ C to
1000◦C, and around 1200◦C to 1300◦ C in a rotary kiln.
A final furnace cycling test was preformed to find out whether the alloy would
heal if affected to lime, and form a protective aluminum oxide. The test was pre-
formed in a special furnace where the samples were kept in the furnace chamber for
1 hour at 1200◦ C and where then kept in room temperature for 1 hour. This cycle
was all automatic, and was repeated 24 times. The total cycle time was therefore
48 hours.
Table 1: Overview of the test samples and their conditions
APMT sample Temperature Pre-oxidized

1 950◦ C Yes
2 950◦ C No
3 1250◦ C Yes
4 1250◦ C No
7.3 Results
7.3.1 Visual observations
The non-oxidized samples 2 and 4 were severely affected by the calcination process,
figure 22. Visual inspection of the pre-oxidized samples 1 and 3 did not show any
signs of being affected.
Figure 22: Visual observation of sample 4 after eight calcination cycles.
7.3.2 Light Optic Microscopy

Using a Leica stereomicroscope, it could be seen that the non-oxidized samples 2
and 4 were affected by the calcination, figure 23. Sample 2 was less affected than
sample 4, probably due to lower temperature during the calcination.
(a) Sample 2 (b) Sample 4
Figure 23: Close-up on the damaged areas of sample 2 and sample 4.

7.3.3 Scanning Electron Microscopy

The pre-oxidized samples, 1 and 3, did not show any signs of being affected even at
very high resolutions, when examined with the Zeiss Scanning Electron Microscope
(SEM). The protective aluminum oxide was all there, and no aluminum nitrides had
been formed. The lighter areas, figure 24, were identified as aluminum oxide, using
Energy-Dispersive x-ray Spectroscopy (EDS).
Figure 24: SEM-picture showing lighter and darker areas of aluminum oxide on
sample 1.
The non-oxidized sample 4 was also examined. EDS-analysis identified the com-
position of the damages areas as aluminum oxide, iron oxide, chromium oxide and
bulk alloy, figure 25.
Figure 25: The surface of sample 4. 1.) Iron oxide, 2.) Bulk alloy, 3.) Chromium
oxide, 4.) Aluminium oxide.
Cross-sectional analysis of the pre-oxidized samples 1 and 3 did not show any
signs of influence of the calcination, while in the non-oxidized samples 2 and 4,
aluminum nitrides were found, figure 26. The number of aluminum nitrides in
sample 4 was far greater than in sample 2.
Figure 26: Cross-sectional view, showing aluminum nitrides under the surface of
sample 4.
7.3.4 Summary
The results of the experimental work are summarized in table 2. The importance of
pre-oxidation of the alloy is clearly noticed.
Table 2: Overview of the results of the experimental work
Sample Temperature Pre-oxidized Iron oxides Aluminum nitrides

1 950◦C Yes No No
2 950◦C No Yes Yes
3 1250◦C Yes No No
4 1250◦C No Yes Yes
The final furnace cycling test did give a positive result. The healing effect of
Kanthal APMT had rebuilt the aluminum oxide, and the samples were at this point
covered with an aluminum oxide. No further growth of aluminum nitrides was
noticed.
8 Discussion
8.1 Quicklime production
Future limekilns do not have to look like the kilns used today. To produce quicklime,
heat is needed and only heat. However, to produce quicklime of really good quality
one has to be able to control the heat very carefully. The most suitable temperature
cycle should be investigated very carefully as the calcination of limestone is sensitive
to correct heat treatment. There are some different quicklime qualities, which have
different properties depending on at what temperature they have been processed.
This is desirable as some customers are looking for qualities that are formed at
higher temperatures, and others are looking for qualities that are formed at lower
temperatures. It is also important to minimize the energy losses in the process.
Quicklime is a relatively cheap product, about $ 100 per ton, and therefore energy
losses are directly affecting the profit.
8.2 The market potential

The market potential for lime products is huge. There are endless of areas where
lime is used or may be used in the future. The production has increased over the
years, and China is the main lime producing country today. The market is over
heated as it is, and it is very tough to introduce a new type of limekilns, as it would
be too costly. The economy of the producers is not good enough to let them try
new solutions. In 2009, a lot of producers had to shut down their businesses due
to high production costs that undermined most of the profits. The use of lime in
pharmaceutical areas or as a part of a biomaterial could be a future market where
new types of kiln may flourish. In these areas the need for extremely pure lime is
increasing. The tonnages are and will be very small, but the price of the extremely
pure lime is a lot higher than of conventional lime. Another view of the market
potential is to look at the amount of consumed energy, which is about 2.4 TWh per
year based on an annual production of 280 million tonnes of lime. This gives an
indication of the potential market for future electrical limekilns.
8.3 Energy sources and environmental aspects

The debate on future energy sources and environmental effects of using fossil fuels
has greatly influenced the lime industry, as it is one of the largest users of fossil
fuel and therefore one of the largest emitters of CO2. The CO2 -tax was introduced
in Europe as a result of the Kyoto protocol, which aims to lower the emissions of
green house gases such as CO2 . This was also the beginning of the emission trading
experiment. The cost of exceeding the amount of emitted CO2 was about 40 Euro
per ton CO2 2 . If one plays with the thought that all no allocations were given
2
According to the Swedish environmental protection agency, 2006
to the lime companies, their total amount of about 560 million tonnes of emitted
CO2 would be charged for. In such a case, with the above-mentioned CO2 -tax fee,
about 22,5 billion Euros would be the final fine. This is more than the total profit
for all produced quicklime in the world. The industry would not survive such a
scenario. However, this is not going to be realized but is an indicator of how brittle
the industry is. The natural step to take is to move towards ”green” energy in this
industry as well. The world is seeing a big expansion of renewable energy sources
and even in the nuclear power sector, which will provide CO2 -free energy in the
future. However, producing electricity from fossil fuels is still the major source in
production of electricity and will probably be in the near future. If renewable energy
and nuclear power will be the main energy sources in 50 to 100 years nobody knows,
but it is a time of change so it is not impossible as reports are showing decreasing
oil and gas production and increasing development of ”green” energy.
8.4 Effects of limestone calcination on Kanthal APMT

The radiant tubes in the prototype will not be in direct contact with limestone
during the calcining process, although the experimental work showed the outcome if
this would occur. The pre-oxidized APMT samples showed good resistance against
the quicklime, which is very good as the radiant tubes are always delivered in this
state. However, the oxide may spall off and in such case the bulk material would
not be protected. A non pre-oxidized APMT sample that had been in direct contact
with limestone, during eight calcination cycles, was severely affected. Brown-orange
points could be seen where the quicklime had been lying. These dots were identified
as iron oxide (F e2 O 3 ). This oxide is porous and has not the protective properties,
which aluminum oxide has, and therefore this was not very good from a material
perspective. SEM-analysis discovered aluminum nitrides beneath the iron oxide,
which partly explains why no aluminum oxide had been formed. It is also interesting
to notice that even though the non pre-oxidized samples were severe affected by lime,
they were able to heal when not exposed to lime. These results are interesting, but to
further investigate the effects of limestone calcination on APMT more experiments
are needed. For example, the APMT samples must be exposed to lime during the
calcination process for a longer time.
8.5 The alternative limekiln prototype

The limekiln prototype, which is proposed in this report, has some advantages and
disadvantages. First of all, the prototype will be able to be used whatever the size
of the lime production. It is just a matter of how many radiant tubes that are fitted
inside the kiln. This makes the kiln very versatile, and a growing lime company
could easily expand their furnace. However, this is only in theory. Today it is too
expensive to produce conventional lime, e.g. for the steel industry, in this way. The
furnace may be suitable for lime companies that focus on special areas such as the
pharmaceutical market. The fact that the kiln could be driven with both Tubothal
and Ecothal makes it even more versatile. In areas where natural gas is cheap, the
Ecothal solution may be more preferable. However, this is not the most environ-
mentally friendly solution, which would be the Tubothal fed with ”green” energy,
but the most environmentally friendly when it comes to gas solutions. The width of
the rolling hoop is a disadvantage as it is often not more than about 1 m. To walk
around this problem several prototypes could be installed side by side.
8.6 Other proposed prototypes

There are several other prototypes, which have been developed at research institutes
and at lime companies. Their purposes are to find alternative ways to produce lime,
and to be able to produce purer lime. In this report two prototypes, which are
very interesting, have been presented. The solar reactor has been shown to be
very successful, in theory. However, this solution could be usable for larger lime
productions, as very large land area would be used. For applications, which require
smaller amounts of lime than e.g. the steel industry, this method may be successfully
used. Another drawback is that the solar reactors only can be used at some areas in
the world, where the sunlight contains enough energy. The other kiln, which uses
a silicon carbide pipe with an internal silicon carbide screw, is also very interesting.
Their purpose is the same as for the prototype proposed in this report. They do not
say anything about a specific heat source, and Kanthal elements may be suitable.
The kiln had a drawback with limestone sticking to the screw and with thermal
induced stresses in the tube, but a part from that it is a very good solution. Both of
these prototypes are interesting models, and will hopefully be noticed by associates
of the lime industry.
9 Conclusions
The purpose of this M.Sc. thesis was to find out whether the lime industry is
a potential business area for Kanthal or not. Twenty weeks have passed since the
investigation started, and a lot of information has been gathered. However, a straight
answer cannot be given because it depends on where in the lime industry the focus
lies. If Kanthal wants to focus on the large producers and short-term profits, it
is probably not a potential business area today. It is simply too expensive for the
producers to change their furnaces and to use electricity as energy source. If Kanthal
decides to focus on smaller areas, such as the special chemical industry that provide
the pharmaceutical industry with lime, it could very much be a potential business
area for Kanthal in the future. However, this would probably not generate profit for
some time, as the focus would be at experimental setups in the beginning. Due to
the complexity of the lime industry, a suggestion is that Kanthal should:
• Focus on small scaled lime production for special areas of lime, such as the
pharmaceutical area (5 - 10 years)
• Extend the presence in the lime industry by starting to look at more conven-
tional lime products (10 - 20 years)
• Develop a full-scaled lime kiln that has the potential of becoming the new
conventional lime kiln (20 - 40 years)
To start with, Kanthal has to make business contacts within the lime industry,
preferably at lime conferences held by lime associations such as European Lime
Association (ELA), International Lime Association (ILA) or Svenska Kalkinstitutet.
This is probably the best way to integrate with the lime industry and to find out
what is going on in the industry.
10 Future work
During this investigation, some additional business areas have been found. If these
areas could be improved with help from Kanthal, they would most certainly generate
profit in shorter terms than an introduction of Kanthal in the lime industry would
do.
10.1 Porcupine heating cassettes as pre-heaters in cement

production
Producing cement has little resemblance with lime production, aside from rotary
kilns as clinker burners. Clinker is a product, which is obtained when limestone and
clay are heated to temperatures around 1450◦ C. Then the clinker is crushed and
gypsum is added to form cement. In this process, exhaust gases from the furnace
process is used to heat ingoing material in a pre-heating tower. This tower consists
of some stages, so called cyclones, in which the limestone clay is heated in different
steps. When the clinker burners are using fuel with low energy value, for example
some biogases, a separate burner is needed to add heat to the pre-heating process.
Instead adding a separate burner, a Kanthal porcupine heating cassette may be
useful. The porcupine works like a large hair dryer, which heats air to about 900◦C.
It is a very versatile product, which can be built after the customer’s demands.
10.2 Alloys as construction material in lime and cement fa-

cilities
Rotary kilns for cement production uses a cooling system to cool the clinker and
the gases in the end of the production lime. The gases are led from the kiln through
a cooling system before it is used in the pre-heating system. These gases are hot
and contain a lot of corrosive elements such as sulphur. Kanthal alloys have good
resistance to sulphur attacks due to the protective aluminum oxide, and may be
useful as construction material in a cement facility.
10.3 Lance tubes for quicklime shaft kilns

In shaft kilns the heat source is several flames, which comes from so-called lace tubes,
figure 27 [10]. In these lances, fuel (often oil) is transported into the kiln and ignites
in the nozzle of the lances. As the lances are in direct contact of limestone, some
problems occur. First of all, the lance tubes are exposed to a lot of wear as they are
in direct contact to limestone that continuously flows through the kiln. However, in
modern shaft kilns the lances are often protected to minimize wear. Secondly, the
environment inside is crude. Quicklime is very reactive and attacks the material of
the lance tubes. In this harsh environment, Kanthal alloys may be useful.
Figure 27: Lance tubes in a shaft kiln

11 Acknowledgments
First of all I would like to thank Kanthal AB for giving me the opportunity to
work with this project. I would like to thank my supervisor, Gustaf Lorenzson, who
assisted me in my work from day one. Your positive attitude to the progress of
my work has been very encouraging. I would also like to thank Fernando Rave for
showing great interest in my work and providing assistance whenever I needed it.
During my work, I have met many friendly people as well that assisted me. I would
like to thank you all for making my time at Kanthal memorable and pleasant.
Beside Kanthal AB, I would like to thank Nordkalk and SMA Mineral for helping
me understand the lime industry and the processes involved by patient answer my
questions and showing me the conventional production methods used today.
References
[1] A. Meier, N. Gremaud, and A. Steinfeld, “Economic evaluation of the industrial
solar production of lime,” Energy Conversion and Management, vol. 46, no. 6,
pp. 905 – 926, 2005.
[2] J. A. H. Oates, Lime and Limestone: Chemistry and Technology, Production

and Uses. John Wiley and Sons Inc, 1998.
[3] http://en.wikipedia.org/wiki/File:Kheops-Pyramid.jpg, 25th of february 2010

at 11.02.
[4] R. S. Boynton, Chemistry and Technology of Lime and Limestone. John Wiley
and Sons Inc, 1980.
[5] Y.-T. H. Lawrence K. Wang and N. K. Shammas, eds., Handbook of Environ-

mental Engineering, vol. 5, ch. 14, pp. 611–633. Humana Press, 2007.
[6] http://en.wikipedia.org/wiki/Lime kiln, 25th of february 2010 at 16.53.
[7] Personal contact with Mikael Wendell at Nordkalk.
[8] Personal contact with Matti Grönvall at Nordkalk.
[9] http://en.wikipedia.org/wiki/Rotary kiln, 25th of february 2010 at 15.17.
[10] I. Quintar and M. Okuma, “High temperature project.” Sandvik report, 2009.
[11] J. Petrel, “Policies to reduce climate change impacts,” in 11th ILA-Congress,

Prague, May 16-19, International Lime Association, 2006.
[12] U. G. Survey, “Mineral commodity summaries 2010.”
[13] http://www.graymont.com/applications.shtml, 25th of february 2010 at 17.57.
[14] http://www.britishlime.org/tech iron01.php, 25th of february 2010 at 18.10.
[15] http://www.lime.org/ENV02/Metal802.htm#IS, 25th of february 2010 at

18.09.
[16] A. Meier, E. Bonaldi, G. M. Cella, W. Lipinski, and D. Wuillemin, “Solar

chemical reactor technology for industrial production of lime,” Solar Energy,
vol. 80, no. 10, pp. 1355 – 1362, 2006.
[17] K. Tsurunaga, “Progress in development of a new indirect fired lime kiln,” in

11th ILA-Congress, Prague, May 16-19, 2006.
[18] K. Aleklett, “Fossil motor fules around 2050,” in Energy 2050, Stockholm, oc-
tober 19-20, 2009.
[19] http://www.naturvardsverket.se/sv/Lagar-och-andra-styrmedel/Ekonomiska-
styrmedel/Handel-med-utslappsratter/, 25th of february 2010 at 19.33.
[20] G. Flament and T. Schlegel, “Potential reduction of co2 emissions & associated
abatement costs in the european lime industry,” in 11th ILA-Congress, Prague,
May 16-19, 2006.
[21] I. E. Agency, “Co2 emissions from fuel combustion,” 2009.
[22] M. S. Kazimi, “The future of nuclear energy,” in Energy 2050, Stockholm, 19-20
october, 2009.
[23] Kanthal, “Radiant tubes and heating systems.” Product description booklet.

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UPTEC Q10 001

The lime industry, a potential

Teknisk- naturvetenskaplig fakultet

Handledare: Gustaf Lorenzson

Bakgrund och syfte

Kalkindustrin är en av världens största kemikalieindustrier, näst störst efter

Energi och miljöaspekter

På senare år har nya förslag på kalkugnar presenterats av forskarlag och kalkföretag.

5 Research and Development 26

6 Idea for an alternative heating solutions for lime-burning 32

7 Investigation of the impact of the calcination process on Kanthal

Quicklime is produced by dissociation of calcium carbonate (CaCO3 ) to calcium

Kanthal AB is producing and selling heating solutions and is constantly looking

1.2 Basic definitions and notifications

• Quicklime consists almost entirely of calcium oxide (CaO), and is produced

• Slaked lime is produced by adding water to quicklime. This is an endothermal

3.2 Formation of limestone

3.5 Limestone preparation

3.6 Environmental aspects of limestone quarrying

4.2 Theory of calcination

4.2.1 Calcitic quicklime

CaCO3 + heat ! CaO + CO2 (1)

At atmospheric pressure, it has been shown that CaCO3 decomposes to CaO

4.2.2 Dolomitic quicklime

MgCO3 · CaCO3 + heat ! CaCO3 · MgO + CO2 (2)

CaCO3 · MgO + heat ! CaO · MgO + CO2 (3)

MgCO3 · CaCO3 + heat ! CaO · MgO + 2CO2 (4)

4.2.3 Stages of calcination

5. The quicklime leaves the calcination zone and is cooled by air.

4.2.4 Dissociation of calcite

The dissociation of calcitic limestone, illustrated in figure 4 [5], can be summa-

(c) CaCO3 dissociates into CaO and CO2 .

(e) CO2 migrates from the surface limestone.

Figure 4: A schematic of the calcination process of high calcium limestone.

4.2.5 Sintering of high calcium quicklime

4.3 Production of quicklime

Figure 5: Schematic of shaft kiln.

Figure 6: The heat flow in a PFR shaft kiln.

4.3.2 Rotary kiln

Figure 7: Schematic figure of a typical rotary kiln. The limestone is transported

4.3.3 Distribution of kiln types

Figure 8: Chart showing the distribution of limekilns used in the world.

4.3.4 Environmental aspects of lime burning

4.4 Slaked lime

CaO + H2 O ! Ca(OH)2 + Heat (5)

MgO · CaO + 2(H2 O) ! Ca(OH)2 · Mg(OH)2 + Heat (6)

An interesting thing to notice is the low solubility of Ca(OH)2 in water, which

4.5 Largest quicklime producing countries

4.6 Uses of quicklime

4.6.3 Metal refining

When producing magnesium, dolomitic quicklime is used to reduce magnesium ox-

2CaO + 2MgO + Si → 2Mg + Ca2 SiO4 (7)

Pure calcium is another metal that is produced by thermal reduction. High

3CaO + 2Al → Al2 O3 + Ca (8)

4HgS + 4CaO → 3CaS + CaSO4 + 4Hg (9)

HgS + CaO + 1, 5O2 → CaSO4 + Hg (10)

4.6.4 Pulp and Paper

4.6.5 Caustic soda

4.6.6 Soil stabilization

4.6.9 Water treatment

4.6.10 Flue gas desulphuration

SO2 + Ca(OH)2 → CaSO3 + H2 O (11)

SO2 + CaO → CaSO3 (12)