Home / Coating, rings and balls - Dr Michael Clark, Whitehopleman

Coating, rings and balls - Dr Michael

Clark, Whitehopleman
Dr Clark reviews the well worn topic of the formation of coating, rings and clinker
balls in cement kilns. A recent flrr! of en"iries prompts Dr Clark to review the
literatre on the topics to provide a reappraisal of the possible cases and, of corse,
their soltion when the! case interrptions in kiln operation. Dr Clark wold
welcome contribtions from readers who are encontering sch problems.
#his month$s #echnical %orm concerns the related topics of the formation of coating,
rings and clinker balls in cement kilns. #his is not a new topic. We have had man!
"estions abot these topics over the !ears, bt dring the last few months there have
been a new flrr! of "estions, particlarl! relating to the formation of large clinker
balls. &ver the !ears the standard answer to these "estions has been that all these
phenomena are related to the properties of the li"id phase in the charge in a cement
kiln.
#he final conversion of kiln feed raw meal into cement clinker is a sintering reaction
becase the principle reactants, the lime liberated from calcim carbonate and the
dicalcim silicate initiall! formed from the combination of that lime with silica, and
the final prodct the tricalcim silicate remain solids throghot the conversion
process. However, this solid to solid conversion is greatl! enhanced b! the presence
of '( to )(* li"id phase formed from the calcim almina ferrite and tricalcim
alminate phases pls the alkalis and slphates and p to '* of the magnesia present
in the clinker.
While the C'+ and Ca& reactants and the C)+ prodct are solids, the! each dissolve
to some e,tent in the li"id. #he C)+ combination reaction proceeds towards the
phase e"ilibrim between the reactants and prodct in both the solid and li"id
phases at the temperatre at the particlar position in the kiln. #he li"id fl, pla!s a
vital transport role in dissolving and bringing together the solid reactants to allow the
solid prodct to be formed and cr!stallise from the melt.
#he effectiveness of the li"id fl, in accelerating the reaction between C'+ and Ca&
to form C)+ depends on- .i/ the amont of li"id at a given temperatre, .ii/ the
viscosit! of the li"id and .iii/ the srface tension of the li"id.
0n the "aternar! Ca&-+i&'-Al'&)-%e'&) .C+A%/ s!stem the minimm etectic
temperatre, when melting will take place and li"id be formed, is at 1))23C. 0n the
presence of Mg& and the alkalis, 4a'& and 5'&, as is the case in an indstrial raw
mi,, the minimm etectic temperatre, when melting will take place and li"id be
formed, is at 1'2(3C. #he amont of li"id then increases as the temperatre rises and
more of the minerals melt.
#he first consideration is the amont of this li"id phase, or fl,, that is present in the
different 6ones of a cement kiln. #here are well established e"ations, based on the
o,ide content of the clinker, that allow the fl, content at different temperatres to be
estimated-
%l,1))23C 7 8.1,*%e'&) 9 *Mg& 9 *4a'& 9 *5'&
%l,1:((3C 7 '.;<,* Al'&) 9 '.',*%e'&) 9 *Mg& 9 *4a'& 9 *5'&
%l,1:<(3C 7 ).((,* Al'&) 9 '.'<,*%e'&) 9 *Mg& 9 *4a'& 9 *5'&
#hese formlae can be sed p to a ma,imm Mg& content of '*, arising from the
ma,imm < to 8* solbilit! of Mg& in the fl,, and a t!pical fl, content for cement
clinker of )(*. #he formla for the fl, present at 1))23C applies to raw mi,es of
almina modls greater than 1.)2.
#his then leads to the concept of the =clinkering range> of a particlar mi,, or clinker
composition. #he =clinkering range> is the temperatre range starting from the
temperatre when sfficient li"id is formed to case shrinkage and nodle formation,
and ending when so mch li"id is formed that serios balling of the mi, takes place.
Mi,es or clinkers with a wide =clinkering range> create less operational problems
sch a ball or ring formation, than those with a narrow =clinkering range>. High
%e'&) mi,es tend to have a narrower clinkering range. With a narrow =clinkering
range> an! flctations in temperatre can case ball or ring formation to occr and
flctations in temperatre are inevitable with an indstrial cement kiln.
?nfortnatel! it is not possible to define the e,act =clinkering range> for a particlar
mi, or kiln. #he minimm fl, content for shrinkage and nodle formation and the
ma,imm fl, content to avoid ball and ring formation are also dependent on the
viscosit! and srface tension of the li"id fl,.
#he viscosit! and srface tension of the fl, are dependent on the relative proportions
of %e'&) and Al'&) in the clinker. #he viscosit! of the fl, is important as its
effectiveness depends on =wetting> the srface of the solid C'+ in the kiln. A mobile,
low viscosit! fl, is more effective in wetting the C'+ and promoting reaction with
lime via diffsion across the solid state phase bondar!. #errier, @ndell and Hendrick
have condcted some stdies into the viscosit! of the fl, and fond that viscosit! is
significantl! increased with rising +i&' content and to a lesser e,tent Al'&).
All these considerations point to the ferric o,ide, %e'&), being a more effective fl,
than the almina, Al'&). #he almina does not contribte to the fl, at the lower
temperatres and also increases the viscosit! of the fl,. Aoth factors shold be
detrimental to the fl,ing of the kiln, increasing the temperatre re"ired for clinker
formation and fel consmption of the kiln. However, cement companies in fact
e,perience the opposite effect, with a fall in the almina content at the e,pense of
ferric o,ide reslting in lower kiln otpts and higher fel consmption. Dr +tanislav
Chrom!, the renowned clinker mineralogist from the C6ech Bepblic has a read!
e,planation for this. De to the lower moleclar weight of almina in comparison
with ferric o,ide, li"id phases rich in almina are mch less dense than those richer
in ferric o,ide. #he lower densit! means these fl,es occp! a mch greater volme
in the kiln and are mch more effective in wetting the clinker and promoting C)+
formation. Mass percentage and viscosit! are not the overriding considerations.
Colme percentage isD
Est as =wetting> of the C'+ srface is important to promote the conversion of the
C'+ into C)+ so the =wetting> of the refractor! lining b! the fl, is an important
contribtor to coating formation on the lining in a cement kiln. ?ntil there is sfficient
li"id phase present to =wet> the lining there will be no coating formation. #his
e,plains wh! coating is onl! present in the pper transition and brning 6one of
cement kilns.
#his then is the chemistr! nderl!ing the formation of coating in the rotar! section of
cement kilns. Wh! then does this coating sometimes locall! thicken into rings to
constrict the flow of e,hast gases throgh the kiln and the passage of the clinker
down the kilnF Wh! does the kiln feed sometimes ball p into clinker bolders which
can be more than 'm in diameterF 0n terms of the formation of rings or sal answer
in the #ech %orm is that it is cased b! a local cooling of the charge reslting in the
viscosit! of the fl, changing at a particlar point in the kiln. #his local cooling might
be e,ternal throgh the kiln shell or broght abot b! a phase change at a particlar
point. We have not offered an! e,planations for the formation of clinker balls other
than that the! are often associated with heav! slphr recirclation in the kiln and this
affects the "antit! and properties of the fl,.
At this stage we shold perhaps highlight that slphate, +&), is not inclded in the
e"ations for calclation of the amont of fl, present at different temperatres in a
cement kilnD Alkali slphates certainl! melt contribting the fl, and affecting its
properties. Ciscosit! and srface tension are redced making the formation of clinker
nodles more difficlt and leading to a finer clinker si6e distribtion with large
proportions of clinker dst. #hat provides no e,planation as to wh! sometimes this
cases the opposite effect of the formation of large clinker ballsD
#hese short comings in or standard answers to sch en"iries have prompted a
reappraisal of the topics of coating, ring and clinker ball formation. #hat reappraisal
began with a literatre search to see what has been pblished on the topic. +earching
back throgh 1< !ears of 0nternational Cement Beview back-isses reveals that
remarkabl! little has been pblished on the topics. #he following is a review of the
literatre starting with the topic of coating formation.
#he first point to make is that there are different t!pes of coating that form in a
cement kiln s!stem. #here are coatings that form on the impellor of the preheater
indced draft fan. #here are coatings that bild-p in the preheaters and kiln inlet
chamber of cement kilns. #here are =snowmen> that bild-p on the first grate of a
clinker cooler. #here are =rhino horns> that bild p on the top of the main brner of
the kiln. #hese are not the sbGect of this discssion. Here we are talking abot the
clinker-like coatings that form on the refractor! lining in the rotar! section of the kiln.
#hese coatings on the refractor! lining of a cement kiln are desirable becase the!
protect the refractor! lining from thermal shocks, abrasion b! the kiln charge and
chemical infiltration b! the gases in the cement kiln. #he neven srface of the
coating assists in transferring heat into the kiln charge b! casing the charge to climb
and tmble with the rotation of the kiln. #he coatings also thickens the effective
refractor! wall in the kiln, increases the inslation of the kiln shell from the high
temperatres of the process and redces radiation losses from the kiln and therefore
overall thermal energ! consmption.
#he formation of this stable, desirable coating is dependent on the kiln feed and
clinker properties, the refractor! lining material and the operating regime in the kiln.
#he principle means of coating formation is b! the clinker fl, wetting and
penetrating into the refractor! lining to the depth in the lining where the fl, stiffens
and free6es. #he wetted srface of the lining then gles solid particles to the lining
bilding p into a coating. Clearl! the amont and properties of the fl, at different
points in the kiln will affect its abilit! to form coating b! this mechanism. 0ncreasing
almina to iron o,ide ratio makes formation of coating more difficlt, as does
increasing silica to almina ratio. #he optimm almina modls for stable coating
formation is reckoned to be between 1.2 and '.). #he optimm silica to almina
modls is reckoned to be between '.< and ).).
4o dobt the t!pe of refractor! lining has an effect of the ease and stabilit! of the
coating formed. Magnesite chrome based lining provided for good, stable coating
formation bt these are increasingl! not being installed de to the potential for
he,avalent chromim formation, contamination of the clinker and the problems in
disposal of the spent refractor! lining. Magnesia spinel linings form coating less
easil! and of a more nstable natre. #he most stable coating is formed on dolomite
brning 6one linings, bt these re"ire long ninterrpted campaigns de to
atmospheric h!dration and destrction of the lining if the kiln is stopped after the
lining has been broght into service.
%inall! a stable operating regime is critical for maintaining a stable coating on the
refractor! lining in the kiln. An! changes in the feed and fel deliver! rates,
brnabilit! of the kiln feed, or the combstion of the fel in the main brner of the
kiln will affect the temperatre profile and the amont and properties of the fl, at
different points in the kiln. With these changes in the amont and properties of the
fl, the coating will bild in different places and might be destro!ed after it has
formed. +table operation is critical for maintaining a stable coating on the refractor!
lining and obtaining long campaigns of service from the refractor! lining.
+o formation of a coating is a good thing and dependent on the amont and properties
of the fl, at different points in the cement rotar! kiln. Wh! does this coating
sometimes grow to a thickness of more than (.<m, becoming a ring and presenting
problems for the operation of the kilnF 0n a d!namic, high temperatre process sch
as a cement kiln there is a balance between the accretion, or growth, of the coating at
a particlar point and the erosion, or destrction, of the coating at a particlar point.
What are the conditions that case the accretive, or growth, tendencies to far otweigh
the erosion, or destrction, tendencies at a particlar point and for the coating to grow
into a ringF What does a literatre search tell sF
0n the +eptember '((' isse of 0CB Hinda Hills$ article stated that- =Changes in
brnabilit! and/or clinker formation can have important practical impact on what
happens in the kiln, the mill, and the prodct. 0f the mi, is hard to brn, the operator
will be obliged to increase the brning 6one temperatre to achieve the desired free
lime level. Hard brning will tend to case low clinker porosit!, large cr!stals of alite,
and often contribtes to generation of dst and/or large clinker balls, instead of good,
nodlar clinker.>
0n the El! '((8 isse of 0CB Holcim$s alternative switch article stated that- =I..
previosl! e,perienced problems with slphr rings in the kiln and e,cessive slphr
content in the raw meal had been eliminated, thanks to the narrow flame prodced b!
the Dofle, brner, which prevents the flame from impinging pon the kiln charge.>
0n the March '((J isse of 0CB Argos$s optimising coolers article stated that-
=0nstalling a new static front end or a complete grate sing the original casing shold
be anal!sed in detail from a process point of view. When the cooler throat is small or
the cooler roof is low, static grates redce the available area for gases going into the
kiln, this is compensated either with higher gas velocities or restrictions of the gas
flow into the kiln. #he first sitation sall! generates clinker dst which is carried
back from the cooler to the kiln casing rings and flame deformation. With the second
method, redcing conditions are ver! probable with the known conse"ences.>
0n the +eptember '((J isse of 0CB Ashgrove$s article on their Montana cooler
investment stated that- =#he plant has also seen an improvement in the handling of
snowmen and large chnks of coating within the new cooler. Bnning a high
secondar! air temperatre sall! reslted in nstable kiln operations, with fine
clinker and the formation of rings in the kiln and snowmen in the cooler. #he original
cooler cold not address these isses, re"iring plant personnel to fre"entl! shoot ot
the bild-ps. As the plant has become comfortable with the new cooler and its abilit!
to handle the chnks coming from the kiln and the air blasters$ abilit! to prevent the
formation of snowmen on the inlet of the cooler, shooting in the cooler is no longer
necessar!.>
0n the +eptember '((2 isse of 0CB +tewart +ervice$s article on petcoke related
refractor! problems stated that- =#he reslts of flame flctations can be readil! seen
in kilns as mltiple slphr rings, slphr balls, brnt-ot brick in the 4o ' t!re
neighborhood and nose ring brick problems.>
#here are certainl! cles in these articles bt no definitive anal!sis of case and
effect. 5iln feed chemistr!, slphr recirclation, kiln main brner adGstment and
cooler operation all have an effect on ring and ball formation. At which one in a
particlar instanceF
Aefore we can answer the "estion of wh! the accretive, or growth, tendencies far
otweigh the erosion, or destrction, tendencies at a particlar point for the coating to
grow into a ring we also have to recogni6e that different t!pes of coatings and rings
occr at different positions in the rotar! section of a cement kiln. 0n the calcining 6one
of a long kiln, or sspension preheater kiln, rings can form de to the formation of the
sprrite, 'C'+.CaC&), intermediate mineral. #his mineral is reported to have a
monoclinic, needle-like strctre casing the material to bind together. 0t$s formation
re"ires that partiall! combined C'+ be present in combination with ncalcined
calcim carbonate, CaC&). %or this reason it is not normall! encontered with
modern, precalciner kilns where the CaC&) is almost fll! calcined to Ca& in the
precalciner before entering the rotar! section of the kiln.
However, there is an analoge of the sprrite mineral, slphate sprrite, 'C'+.Ca+&:,
where the calcim carbonate, CaC&) is replaced b! calcim slphate, Ca+&:. #his
mineral can certainl! be present at the inlet of modern, precalciner kilns where there
is an e,cess of slphate over alkalis in the hot meal. +ch a sitation might arise from
redctive brning at some point in the kiln s!stem and attendant heav! recirclation
of slphate. #his is thoght to be a common case of kiln inlet rings in some modern,
precalciner kilns.
+ch sprrite and slphate sprrite based rings are particlarl! problematic. #he!
form too far back from the kiln otlet to be effectivel! shot ot b! an indstrial gn
firing throgh the kiln hood. +ometimes the! can be addressed b! C&' charges fired
throgh the shell of the kiln is ports for the firing of sch charges are provided. As
the! form so close to the kiln inlet the! can dam the calcining feed, casing it to spill
back throgh the kiln inlet seals presenting a significant ha6ard to personnel and
e"ipment. #he kiln has to be fre"entl! stopped to cool down and ph!sicall! remove
the ring. #he onl! satisfactor! soltion to sch ring problems is to adGst the process
to prevent the slphate bilding p in e,cess of the alkalis in the hot meal. #his might
involve changing the raw material or fel inpts and most importantl! avoiding
redcing brning conditions at an! point in the kiln.
%rther down the kiln an! coating and rings are formed b! sintered material, i.e. all
the C&' has driven off the calcim carbonate and the liberated lime has begn to
combine with the acidic +i&', Al'&) and %e'&). &nce the temperatre is high
enogh for significant fl, formation then coating begins to form on the refractor!
lining, bt an! local cooling can case the fl, to free6e and the coating to grow into a
ring at that point. At the beginning of the brning 6one where the fl, is first forming
the refractor! is sccessivel! cooled as the kiln rotates and the lining is e,posed to the
hot kiln atmosphere and then cooled as it trns into the cooler charge. #he fl,
adhering to the lining softens as it is e,posed to the kiln atmosphere and then stiffens
as it is cooled b! trning into the charge. #he weight of the charge cases solid
particles to adhere to the stiffening fl, la!er and a ring can rapidl! grow. +ch rings
can sall! be combated b! minor adGstments to the kiln main brner, slightl!
shifting the brning 6one and the position in the kiln where fl, is first formed, with
this shifting casing the ring to break awa! and reform at a different point.
More problematic are longer, middle rings cased b! recirclation of clinker dst in
the combstion prodct gases from the main brner. Dst! clinker leads to a heav!
dst brden in the secondar! combstion air drawn into kiln and flame from the
cooler. At the temperatres in the flame the fl, in the clinker particles re melts and is
carried back to the point in the kiln where the fl, stiffens again and sticks to the
refractor! lining. An elongated ring bilds p in la!ers with a fine strctre showing
the crvatre of the kiln. #hese rings can be shot ot with an indstrial gn bt their
elongated natre means that man! ronds and significant downtime can be re"ired.
#he soltion to problem is to eliminate the dst recirclation from the cooler. #his is
often best achieved b! adGstment of the main brner to prodce a short, dense flame.
Hong, la6! flames tend to prodce dst! clinker de to higher slphate recirclation
and/or slow heating and cooling of the clinker.
#he final rings we shold mention are kiln otlet or nose ring rings. #he secondar!
combstion air drawn into the kiln leads to cooling of the clinker falling over the nose
ring. #his can case stiffening of the fl, in the clinker and its prononced adhesion
to the refractor! lining at the nose ring. #his tends to dam the combined clinker in the
kiln at high temperatre and can lead to clinker "alit! problems. #hese kiln otlet
rings can be combated b! pshing the brner into the kiln creating a clinker cooling
6one within the kiln itself. AdGstment of the insertion distance of the brner into the
kiln will significantl! psh the brning 6one p the kiln and can lengthen the brning
6one re"iring other adGstments to maintain a short, intense flame.
%inall! we come to the "estion of clinker ball formation. Hinda Hills talked of =Hard
brning will tend to case low clinker porosit!, large cr!stals of alite, and often
contribtes to generation of dst and/or large clinker balls, instead of good, nodlar
clinker.> +tewart +ervices talked of- =flame flctations can be readil! seen in kilns as
mltiple slphr rings, slphr ballsII>. Aack in December 1;;J %lo!d Hamilton
talked abot =a long flame, directed along the a,is of the kiln, casing the formation
of a material ball. +ome of these growing to 8 to 2 feet in diameter, and brning with
a shorter flame preventing their formation nless cased b! alkalis, slphr and
chloride.>
Again cles, bt no definitive case and effect. @lsewhere it is stated that balls tend to
form where there is alread! a tendenc! to form meal or sinter rings. #here needs to be
a core, or seed formed and then the bild-p into a ball is cased b! the weight of the
ball itself as it trns with the rotation of the kiln, compressing material and sticking it
to the srface. #hose of s who made snowmen or had snow ball fights in or !oth
will nderstand how that mechanism wold work.
#his is where the #ech %orm needs to be thrown open for contribtions from reglar
readers encontering sch problems with clinker ball formation .or indeed e,cessive
coating and rings/. 0 know that clinker ball formation can certainl! be associated with
e,cessive slphr recirclation cased b! redcing brning at one or other point in the
kiln. #hese slphr balls sinter to a hard shell as the! pass throgh the kiln, bt
contain nsintered material when broken open. Anecdotall! and also from distant
e,perience 0 know that changes in the Mg& content of the kiln feed and clinker can
lead to clinker ball formation. #hese Mg& related balls are hard and fll! sintered
right throgh to their core. Has an!one got an! contribtions the! can makeF 0f so
send them to mccKwhitehopleman.com.
Also anecdotall! these isses with clinker balls tend to come and go. #o m! mind this
means that some kilns are ssceptible to clinker ball formation. #here is an nderl!ing
=latch> condition that makes the kiln ssceptible. #hen at certain times a =trigger>
condition arises which cases clinker balls to start to be formed. An! thoghts on
what those =latch> and =trigger> conditions might be wold be of maGor interest.
#ech 0mage-
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