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Examensarbete 30 hp
Mars 2010
Jesper Ejenstam
Abstract
The lime industry, a potential business area for
Kanthal
Jesper Ejenstam
Jesper Ejenstam
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.
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
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
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.
Figure 1: Schematic figure of the lime production process. This report focuses on
the calcining process, which is illustrated in the square [1].
The lime industry, a potential business area for Kanthal 3
• 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.
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.
The lime industry, a potential business area for Kanthal 4
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.
The lime industry, a potential business area for Kanthal 5
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.
The lime industry, a potential business area for Kanthal 6
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].
The lime industry, a potential business area for Kanthal 7
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].
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].
The lime industry, a potential business area for Kanthal 9
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].
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].
The lime industry, a potential business area for Kanthal 11
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.
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.
(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.
(d) CO2 migrates from the inside of the limestone through the decomposed layer.
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].
The lime industry, a potential business area for Kanthal 14
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
The lime industry, a potential business area for Kanthal 16
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].
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).
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].
Figure 10: Countries with 90 % of the total world lime production (in million
tonnes).
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].
The lime industry, a potential business area for Kanthal 22
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].
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].
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
The lime industry, a potential business area for Kanthal 24
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].
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
The lime industry, a potential business area for Kanthal 27
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].
The lime industry, a potential business area for Kanthal 28
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 .
The lime industry, a potential business area for Kanthal 29
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].
The lime industry, a potential business area for Kanthal 30
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].
used today are as optimal as they can be. The emissions can only be reduced about
10 %, but this would cost a lot [20].
Figure 17: Distribution of energy sources for electricity production, within the Kyoto
member countries.
The lime industry, a potential business area for Kanthal 32
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].
The lime industry, a potential business area for Kanthal 34
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].
The lime industry, a potential business area for Kanthal 35
temperatures.
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.
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 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.
The lime industry, a potential business area for Kanthal 40
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.
The lime industry, a potential business area for Kanthal 41
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.
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.
The lime industry, a potential business area for Kanthal 43
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.
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.
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.
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.
The lime industry, a potential business area for Kanthal 47
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.
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.
The lime industry, a potential business area for Kanthal 50
References
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solar production of lime,” Energy Conversion and Management, vol. 46, no. 6,
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[4] R. S. Boynton, Chemistry and Technology of Lime and Limestone. John Wiley
and Sons Inc, 1980.
[10] I. Quintar and M. Okuma, “High temperature project.” Sandvik report, 2009.
[18] K. Aleklett, “Fossil motor fules around 2050,” in Energy 2050, Stockholm, oc-
tober 19-20, 2009.
The lime industry, a potential business area for Kanthal 51
[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.
[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.