NTNU Institutt for petroleumsteknologi og anvendt

geofysikk
An Introduction to Scaling
causes, problems and solutions
Margrethe Nergaard hriss !rimholt
Trondheim, november "#$#
Term paper for the course% T&! '$'# Natural !as
i
Abstract
Scale occurrence, formation and prevention have been investigated( In a natural gas
reservoir, )ater )ith dissolved ions )ill al)ays be present( *hen parameters as tem+
perature, pressure, concentration or p, are changed, the e-uilibrium of the system is
shifted( This can push the system into a state )here the dissolved ions precipitate out,
causing a deposition of scale(
orrosion protection of pipelines )ill lead to increased scaling of calcium carbonate(
Mono ethylene glycol .M/!0 used as antifree1e, )ill also impact the scaling( 2arious
mechanisms can lead to scale formation in the natural gas )ell, the )ellbore and in the
production e-uipment( In processing systems, especially heated surfaces are targets of
scale( 3egeneration of M/! is also connected to scale formation, as the process )ith
lo)est operating costs has higher risk of scale formation and contamination(
After formation, some scales can be removed( This can either be done by physical pro+
cesses or chemically( &revention of scale is conventionally done )ith chemical inhibitors(
This can create large amounts of )aste( *e claim that increased kno)ledge on the
chemical background of scale formation, can also contribute to scale prevention(
ii
ontents
$ Introduction $
" hemical background of scale formation "
"($ Solubility product ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( "
"(" hemical potential and supersaturation ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( "
"(4 Nucleation and particle gro)th ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 4
4
' Scale in production systems 5
6 Scaling in processing systems $#
6($ Scale at heated surfaces ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( $#
6(" M/! regeneration systems ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( $$
7
8 9iscussion $'
5 onclusion $6
Scale formation '
4($ ,ydrate prevention ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( '
4(" orrosion prevention ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 6
4(4 ombating one problem by creating another ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 7
4(' :ormation )ater ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 7
4(6 alcium carbonate scale mechanism ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 7
3emoval and prevention of scaling $"
7($ hemical removal ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( $"
7(" Mechanical removal ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( $4
7(4 &revention of scale ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( $4
4
$ Introduction
Scaling can be a serious problem for the oil and gas industry, but it is hard to find a good
comprehensive introduction to the sub;ect( The aim of this report is to give an easy
introduction to the scaling phenomena, going though crystalli1ation and e-uilibrium
theory, the cause of scaling, problems caused by scaling and ending )ith strategies for
fighting scales(
Scaling is the deposition of a mineral salt on processing e-uipment( Scaling is a result
of supersaturation of mineral ions in the process fluid( The theory behind scaling is
e<plained in section " )ith important topics like solubility, nucleation and supersatura+
tion(
This supersaturation of ions are caused by several factors( An important contributor
is the production of high salt content )ater like formation )ater from the )ell( This
increases the ionic concentrations, possibly leading to deposition of scales, as e<plained
in section 4( This section also discuss ho) other preventive actions against
hydrate
formation and corrosion increase the risk for scale deposition, and ho) scaling is aected
by changes in physical variables such as concentration .also including p,0, pressure and
temperature(
Scale deposition can cause problems several places in production and processing of nat+
ural gas( A summary of the most common problems associated )ith scaling is given
in section ' and 6( This includes high risk areas )here large temperature and pressure
changes occur, like heat e<changers and pipes(
There are several )ays of fighting scales, as discussed in section 7( There are preemptive
methods like chemical inhibitors that hinder the scale gro)th( These methods are limited
in there use, because a inhibitors )orks best for specific scale types and crystal structure(
A more versatile methods for scale fighting are removal after deposition( hemical
removal is a cheap method for scale removal, but it is eectiveness depends on the
porosity and the type of scale( Mechanical removal is another method for removing
scales after scale deposition, and usually involves scraping, drilling or inducing
vibrations to pipes and e-uipment( Theres a )ast amount of mechanical systems, and
only a fe) are discussed(
*e summari1e the report by discussing ho) scaling can impact economy, health, security
and environment .,S/0 and alter the choice of technical solutions(
" hemical background of scale formation
"($ Solubility product
A salt is a neutral substance formed by combining positive and negative ions(
*hen a salt is dissolved in a solvent, for most cases )ater, the salt )ill separate
into its constituent ions, so+called solute molecules( These ions )ill interact in various
degrees
)ith the solvent= )e say they have dierent ionic activity( The product of the salt>s
ion
activities gives the solubility product, ?
sp
( If the solution .of solvent and solute0 is close
to an ideal solution, one can substitute ionic activity )ith the concentration of each ion(
The solubility product is a measure of ho) many moles of ions per unit volume of solvent
there can bein a system before a salt precipitates out( ?
sp
can vary )ith solvent, but
)ater is often used as reference( A lo) ?
sp
value means that little salt )ill be dissolved
in )ater and this salt )ill be referred to sparingly soluble salts(
*hen a salt is dissolved in )ater, the resulting solution can be acidic, neutral or basic(
The negative ion can )ork as a base or the positive ion as an acid( If either of
them have such properties, the result is a neutral solution( This also implies that
solvent>s p, impacts the solubility product( In the case of calcium carbonate, the
carbonate ion can attract a proton from )ater, resulting in a basic solution( *hen
reducing the p, by adding additional acid, the e-uilibrium )ill be shifted favoring
dissolution of calcium carbonate into carbon dio<ide .@
"
0 and calcium ions(
"(" hemical potential and supersaturation
hemical potential is a measure of the reactivity of a component in a solution( More
accurate, it is a measure of ho) much the free energy, A!, of a system changes )hen
changing the number of moles in this system at constant temperature and pressure( It
can be compared to gravitational potential= like a ball is minimi1ing its gravitational
potential by rolling do)n a hill, a system of molecules )ould try to reach a state of
lo)er chemical potential to minimi1e its free energy(
*ithout going into too many thermodynamic details, )e here limit ourselves by stating
that chemical potential is both temperature and pressure dependent( ,ence, by chang+
ing these parameters, the solubility of a system )ill be influenced( :or most
systems,
increasing temperature )ill increase the solubility( &ressure dependence is usually )eak
for systems of dissolved solids, but in oil+ and gas )ells the pressure can be so high that
this dependency has to be taken into account B$C( Also, for the ease of the discussion,
)e hereby look at an ideal system )here activities can be replaced by concentrations(
Dy )hat )e have stated so far, concentrations greater than the ones dictated by the
solubility product ?
sp
)ould give precipitation( ,o)ever, this is not al)ays the case(
This is most easily e<plained by an illustration, see figure $( ,ere, the solubility prod+
uct is represented as the solid black line line( This curve is also called the saturation
line, referring to a solution saturated by dissolved ions( EStable regionF refers to the re+
gion )here ions are dissolved .meaning% in solution0 and ElabileF to )here precipitation
)ill occur spontaneously and solids form( The metastable region is further e<plained
belo)B"C(
Dehind every chemical process, there must be a thermodynamic driving force( :or
precipitation, this is given by the dierence bet)een the chemical potential of a
given
substance in the stable and metastableGlabile region( To represent this driving force,
the term supersaturation is often used( Supersaturation refers to the dierence in con+
centration bet)een the bulk concentration ./, in the figure, but can be any)here in
the metastable and labile region0 and the corresponding concentration at the solubility
curve .D, 90 for a given temperature(
At point A, the solution is not supersaturated, there is no thermodynamic driving force
and therefore no precipitation( Dy changing either the temperature or the concentration
.e(g( by evaporation some solute0 one can e<ceed the solubility concentration .point D
and 90 and cross into the supersaturated regime( No), a thermodynamic driving force
for precipitation is established and formation of solids may take place(
"(4 Nucleation and particle gro)th
Although a driving force is established, a solution can be supersaturated )ithout solid
formation occurring( The short e<planation to this is that the supersaturation has
to
be suciently high= )e have to be in the labile regime of figure $( A more e<tensive
e<planation re-uires understanding ho) particles appear in a solution( This kno)ledge
is also crucial in order to understand and design scale inhibitors(
In a supersaturated solution, unstable clusters of atoms develop( Hocal fluctuations in
the e-uilibrium concentration can trigger these clusters to form seed crystals( :urther,
these crystals gro) by adsorbing ions, preferably at defects in the surface( After reaching
a critical si1e, the crystal )ill e<hibit a reduction of free energy )hen e<panding it
surface, favoring gro)th to)ards a larger crystal( Harge crystals can also redissolve
smaller seed crystals if this lo)ers the overall free energy of the system( This
implies that formation of seed crystals in regimes )here the supersaturation is large,
catalyses the gro)th of e<isting crystalsB"C(
In the metastable region of figure $, the driving force is not large enough to overcome the
energy amount re-uired to form a surface= a solid particle( Spontaneous precipitation
like the one described above, )ill therefore not take place( ,o)ever, )hen a surface is
present, already e<isting defects at the surface can act as nucleation sites( Dy this, the
surface free energy re-uired is lo)erd, allo)ing solid particles to form and gro) even in
the metastabile regime( This formation of precipitate at a surface is often referred to as
precipitation fouling or scaling(
4 Scale formation
A natural gas )ell )ill, besides producing natural gas, also produce )ater and carbon
dio<ide .@
"
0( The produced )ater can come from t)o sources% )ater vapor in the gas
that condenses into li-uid )ater and formation )ater containing salts( This )ater is the
source of hydrate formation and, in combination )ith @
"
, corrosion( Scaling is caused
by salts and can occur )hen the produced )ater contains formation )ater(
4($ ,ydrate prevention
A hydrate is a solid structure )here a gas molecule is surrounded by a cage of )ater
moleculesB4C( It is formed at high pressures and lo) temperatures( ,ydrates are very
similar to sno) and ice and can form plugs in pipelines leading to blockage( To prevent
such hydrates, in;ecting a substance like mono ethylene glycol .M/!0 )ill lo)er the
free1ing point of )ater by diluting the system, ;ust like an anti free1e agent( A lo)er
free1ing point ensures that solid structures of )ater cannot form and hence there )ill be
no formation of hydrates(
M/! is transported in a so+called M/! loop( ,ere, M/! is in;ected into the natural gas
pipeline at the )ellhead and flo)s )ith the natural gas to processing site onshore( M/!
is then separated from the )ater, regenerated and sent back to the oshore production
facilitie( The M/! transported from the reservoir and from the production site onshore
is called rich M/! and lean M/! respectively(
4(" orrosion prevention
9ue to temperature drop, )ater in the pipeline )ill at some point condensate( Since
M/! has lo)ered the free1ing point, this )ater )ill be in li-uid form( &resents of li-uid
)ater leads to a problem )ith corrosion( The cause of this is the presence of @
"
, )hich
in contact )ith )ater forms a )eak carbonic acid .,
"
@
4
0, as sho)n in reaction $(
@
"
.g0 I ,
"
@ .l0 ,
"
@
4
.a-0 .$0
Hong pipelines are constructed of carbon steelB'C( arbonic acid )ill corrode the iron
in the pipeline )all, producing iron carbonate( See reaction "( This iron carbonate can
precipitate in the production fluid and follo) the gas and li-uid flo), causing problems
do)nstream(
:e I ,
"
@
4
:e@
4
I ,
"
."0
To combat this problem, p,+stabili1ing is implemented( ,ere, p, is increased from the
sour condition of the reservoir into more neutral conditions( This is done by in;ect+
ing an alkaline chemical, sodium hydro<ide .Na@,0, together )ith the M/!( Neutral
conditions decrease the solubility of the corrosion product iron carbonate( *hen the
solubility is suciently decreased )ithout corresponding decrease in concentration, the
system crosses into the metastable and eventually labile region of figure $( This results
in a supersaturated system and precipitation of iron carbonate -uickly takes place(
The precipitation occur often directly on the pipeline )all, because the energy barrier
for formation of solid particles is lo)er on solid surfaces( After some time there )ill be
formed a thin iron carbonate film that covers the iron surface of the pipeline, protecting
it from contact )ith carbonic acid and )ater( orrosion protection is then established
and further corrosion is only possible by eroding a)ay this film(
4(4 ombating one problem by creating
another
@ne problem )ith p, stabili1ing is that it does not only decrease the solubility of iron
carbonate, but also other salt like calcium carbonate( This means that if calcium is
present in the pipeline, )hich it often is, it )ill also precipitate on the )alls of the
pipeline( ompared to iron carbonate precipitation, scaling of calcium carbonate is
usually not limited to a fe) millimeters( Decause there is a protective film over the iron
surface , there is no longer a source of iron and no precipitation can occur(
In contrast, calcium carbonate gets its reactants from the reservoir( A further discussion
of this reactant supply follo)s beneath( &recipitation )ill therefore continue as long as
the reservoir produces )ater and this result in a thick layer of scale( At some point, the
calcium carbonate scale can be so thick that the pipeline flo) is completely restricted(
4(' :ormation )ater
In most hydrocarbon reservoirs, )ater is also present( It is believed that the reservoir
)as completely saturated )ith )ater before the hydrocarbons appeared, and )ater is
therefore usually present )ith hydrocarbons in the reservoirsB6C( This )ater is called
formation )ater and usually has a high salt content around three to five percentB7C(
omposition of the formation )ater varies greatly )ith the reservoirs, but the usual
constituents are Na
I
, a
"I
, ?
I
, Mg
"I
, :e
"I
, l
J
, S@
"J
and ,@
J
(
' 4
:ormation )ater )hich flo)s out )ith the hydrocarbon production is called produced
)ater( The amount depends on the reservoir characteristics and ho) the )ells are
positioned compared to the reservoir phases( Since hydrocarbons are less dense than
)ater, they )ill be in the top phase inside the reservoir( As hydrocarbons are drained
from the reservoir, )ater level in the reservoir )ill rise( The amount of produced )ater is
therefore likely to rise during the production lifetime( &roduced )ater can also suddenly
occur in fields )here there used to be little or no produced )ater(
4(6 alcium carbonate scale mechanism
Scale can form by various reasons depending on a number of factors( Scale formation )ill
be treated in details later in this report )hen scale in production systems is discussed(
:or no), a simple e-uilibrium approach is used to e<plain ho) dierent parameters
impact solubility and thus scale formation( To limit the e<tent of this report, )e focus
on the formation of calcium carbonate(
The reactions that lead to formation of solid calcium carbonate are as follo)sB8C% :irst,
carbon dio<ide reacts )ith )ater to produce carbonic acid as seen by reaction 4(
@
"
.g 0 I ,
"
@ .l 0 ,
"
@
4
.a- 0 .40
This carbonic acid )ill continue to dissociate hydrogen, creating ne) deprotonated
species of carbonic acid, as seen in reaction ' and 6(
,
"
@
4
.a- 0 I ,
"
@ .l0 ,
4
@
I
.a- 0 I ,@
J
.a- 0 .'0
,@
J
.a- 0 I ,
"
@ .l0 ,
4
@
I
.a- 0 I @
"J
.a- 0 .60
4 4
In the )ater mi<ture there )ill be a mi<ture of the species ,
"
@
4
, ,@
J
and @
"J
(
4 4
:inally, in the presence of calcium and carbonic acid, calcium carbonate )ill precipitate
out as seen by reaction 7(
4
.a- 0 I a
"I
.a- 0 a@
4
.s 0 .70
Since produced )ater usually contains a carbonic acid and calcium ions, a recombination
of these reactions )ill give a better representation of the situation, as seen by reaction
8(
a .,@
4
0
"
.a- 0 @
"
.g0 I ,
"
@ .l 0 I a@
4
.s 0 .80
alcium and carbonic acid together in li-uid form )ill be in e-uilibrium )ith )ater,
solid calcium carbonate and @
"
gas(
Most behaviors of the calcium carbonate e-uilibrium can be predicted from He hKte+
lier>s e-uilibrium principle( This principle states that a chemical system at e-uilibrium
4
@
"J
)ill al)ays try to counteract any imposed change in pressure, temperature, volume and
composition( All these variables can be changed during gas production and therefore,
aecting the e-uilibrium and scale formation( A brief discussion of each parameters
follo)s beneath(
&ressure dependance % *hen pressure is decreased in a chemical system, the e-uilibrium
)ill try compensate by increasing the pressure( Decause @
"
is the only gaseous specie,
the only )ay to increase pressure is by shifting the e-uilibrium to)ards producing more
@
"
( A decrease in pressure )ill then result in more precipitation of calcium carbonate(
oncentration dependance% If the concentration of calcium or carbonic acid is increased
or the partial pressure of @
"
is decreased, then there )ould be an e-uilibrium shift
to)ards the right and more precipitation of calcium carbonate( Increasing the p, by
addition of an alkaline chemical such as Na@, )ould result in a naturali1ation of the
,
4
@
I
comple<( This )ill shift the reactions ' and 6 to the right, yielding more carbonic
acid( More carbonic acid )ill shift the e-uilibrium in reaction 8 to)ards the right and
more calcium carbonate )ill precipitate out(
Temperature dependance% The solubility of calcium carbonate )ill decrease as the tem+
perature increases( This is an interesting phenomena, because most solubilities increase
)ith increasing temperature and therefor one gets less precipitation( @ne of the reasons
for this behavior is the fact that the precipitation of calcium carbonate re-uire energy
.endothermic0( This can be )ritten into the e-uilibrium e-uation as follo)s%
energy I a .,@
4
0
"
.a- 0 @
"
.g0 I ,
"
@ .l 0 I a@
4
.s 0 .50
*hen the temperature increases, the energy also increases, and the e-uilibrium )ill try
to counteract this by consuming energy( The e-uilibrium is then shifted to)ards right,
favoring precipitation of calcium carbonate(
' Scale in production systems
Scale can occur in all parts of a gas production system and due to several dierent
mechanisms( ommon for them are that the system is )ithin, or brought into, a super+
saturated regime( ,ere, precipitation can occur( See figure $(
Inside the )ell, )ater is naturally present( As the )ater e<periences changes in temper+
ature or pressure during production, the system )ill shift the e-uilibrium in order to
combat these changes( This shift can bring the system from the stable to the metastable
and labile region of figure $ and scale can be formed( Species that originally )ere dis+
solved precipitate out and scale is formed in perforations in the near )ellbore matri<(
Such scale depositions reduce the formation porosity and permeability and thus the
hydrocarbon flo)( As scale is formed, pressure drops even further, giving more scale
formation( An illustration of this is found in the right part of figure " belo)( This
process is kno)n as autoscaling and in )orst case, pores can be completely blocked(
*hen the )ell is drilled and later completed, fluids .mud0 are used to, among others,
stabili1e the drill hole and provide hydrostatic pressure to prevent formation fluids from
entering the )ell bore( :ormation )ater and drilling fluids are said to be incompatible=
meaning, chemical reactions )ill take place upon mi<ing( This can also lead to scale in
the near+)ellbore environmentB', 5C( Incompatible mi<ing can also occur )hen sea)ater
is in;ected to enhance production( Sea)ater is often rich in dierent ions than the
production )ater and upon mi<ing, sparingly soluble salts precipitate out, as illustrated
to the left in figure "(
As already mentioned= imperfections in surfaces can act as nucleation sites and initiate
precipitation and scale formation( A high degree of turbulence is found to cataly1e
depositions of scale( Turbulence increases mi<ing and mass transfer in the 1one close to
the surfaceBLC( *hen a fluid passes a hinderance, a pressure drop is often e<perienced(
These factors can e<plain )hy scale often occurs in do)nhole completion e-uipment(
This can cause severe problems if devices such as safety valves and gas lifts are put out
of action due to scale( In production pipes, scale may build up as a thick layer inside
the tubing( These depositions can be so thick that flo) is severely restricted as seen in
figure 4(
If the gas produced has acidic gases associated )ith it, such as ,
"
S and @
"
, another
mechanism cause problems( As pressure is reduced during production, less acidic gas is
dissolved( This raises the p,, )hich again lo)er the solubility and causes precipitation
of carbonates( Scale of this type can e<tend from the near+)ellbore matri< along tubing
and to surface e-uipment, since the temperature and pressure of the produced )ater
continuously changes and thus also changes the p,( A similar type of scaling can occur
)hen using @
"
for secondary recovery( As )ater turns acidic )hen @
"
is dissolved,
calcium carbonate )ill dissolve from the limestone )ell( *hen production leads to
pressure drop, @
"
is released from the )ater and calcium carbonate precipitate out
again in the near+)ellbore pores( Hike autoscale, these processes are self+generating and
can completely seal )ells and boreholes in fe) daysBLC(
In )et gas production, evaporation+induced scaling can also occur( 9uring production,
lo)ered pressure e<pands the hydrocarbon gas( This leads to evaporation of the for+
mation )ater and thus increased concentration of dissolved species( As enough solvent
is evaporated, the system crosses the solubility curve as seen in figure $ and scale is
formedBLC(
6 Scaling in processing systems
/ven if little or no formation )ater is produced, there )ill still be some ions and impu+
rities present in the )ater( These can origin from corrosion, p,+stabili1ation, minerals
in the reservoir or from sea)ater and cause precipitation and scale in the processing
systems( To ease the follo)ing discussion, )e only look at the processing systems )ithin
the M/!+loop(
6($ Scale at heated surfaces
alcium carbonate belongs to a group of salts often called inverse soluble( These salts
do not follo) the general trend on increasing solubility )ith increasing temperature(
Instead, )hen temperature increases, the solubility goes do)n and favors precipitationB"C(
This can cause trouble in systems )here heated surfaces are present(
Since calcium carbonate is inverse soluble, a heated surface )ill have a greater tendency
to)ards nucleation than a lo) temperature surface( At this elevated temperature, the
solubility is lo)ered and a local regime favoring precipitation can occur( If the system
already is )ithin the metastable region, the temperature gradient from the heated surface
may impact the chemical potential and thus the driving force for precipitation( Unit
operations like heat e<changers and reboilers, )here surfaces at elevated temperatures
e<ist, are therefore potential sites for scale formation( Scale at such surfaces )ill lo)er
the
heat transfer and reduce the unit>s eciency( Also, studies sho) that prescaled surfaces
have a higher tendency of further scaling, as nucleation sites already is establishedB$#C(
alcium carbonate has three dierent crystal structures, socalled polymorphs( /ach
polymorph gro)s )ith dierent rates( Also, dierent supersaturations )ill favor dier+
ent polymorphs( The same applies to temperature regionsB$$C( To understand )hich
polymorph that )ill cause scale at the current processing conditions, is therefore impor+
tant(
In a current research pro;ect, scaling at heated surfaces for a continuous system is
studied( A scanning electron microscope picture from this pro;ect is sho)n in figure '(
At the conditions of this e<act e<periment, the fast+gro)ing needle+like crystal structure
dominates fully over the slo) gro)ing cube like structure( In the )orst case scenario, the
scaling can be so e<tensive that that heat transfer is reduced to almost 1ero( 9epending
on the dimensions of the unit operation, this can happen in a short time .hours or days0
and can put the )hole unit out of action( Understanding )hich crystal structure occurs
)hen, can therefore be crucial( It is to be hoped that research )ill give more kno)ledge
on ho) to avoid such scenariosB'C(
6(" M/! regeneration systems
M/! dries the gas by absorbing )ater and thereby also absorbing dissolved ions( After
removal of the absorbed )ater, the M/! is said to be regenerated and can again be used
to inhibit hydrates and dry the natural gas( 9epending on the regeneration process,
impurities is either carried )ith the M/! or separated o in the regenerating process(
Since )ater has a lo)er boiling point than M/!, )ater may be removed by simple boil+
ing( A sketch of the reboiler unit from ?ollsnes is sho)n in figure 6( Since calcium
and carbonate cannot carried by the )ater vapor, these are left in the M/!( As time
proceeds, the concentration of ions in the M/!+loop increases( If concentrations corre+
sponding to supersaturated regimes are reached, scaling can occur( The reboiler is, as
)e have seen, especially e<posed( Dut, if concentrations are high enough for spontaneous
nucleation .labile region0, crystal gro)th can occur in the bulk fluid( The )hole loop can
be contaminated by crystals and in )orst case, the )hole M/! mass must be changed(
A process kno)n as M/! reclamation solves the problem )ith upconcentrated contam+
inations( ,ere, both M/! and )ater are boiled o and later separate into t)o phases(
This re-uires more energy and increase operating costs, but allo)s impurities to be
removed( The illustration in figure 7 is from SnMhvit )here this techni-ue is in use(
Solid removal is illustrated by a black bo< in figure 7, but is usually done in a sedi+
mentation tank or in a centrifugation( M/! addition influences both the solubility and
crystal structure of calcium carbonate( As stated earlier, solubility of calcium carbonate
decreases )ith increasing M/! concentration( It is also found that the particle si1e
of calcium carbonate precipitate is reduced at high M/!+levelsB$$C( This can have an
impact on the removal of solids in the reclamation process, as the particles can be too
small and light for both conventional separation techni-ues(
7 3emoval and prevention of scaling
As discussed by rabtree et al(BLC, scale can be removed chemically or mechanically after
deposition( Also, scale formation can be prevented before deposition occurs(
7($ hemical removal
Scales can be divided into t)o ma;or categoriesB$"C% the acid soluble scales consisting
mainly of carbonates .M
<
@
4
0 and sulfides .M
<
S
y
0 and the acid insoluble scales con+
sisting mainly of sulphates .M
<
S@
'
0( The M refers to a metal ion, for e<ample calcium,
and <Gy refers to stoichiometric ratios( Acid soluble scales, the use of a strong acid
can dissolve the precipitated scales( :or calcium carbonate, hydrochloric acid may be
used( Scales that cannot be solved by acids re-uire other treatments( These scales can
removed by using a strong chelating agent( A chelating agent is a comple< molecule
)hich breaks up the scale by isolating and tying up the metallic ions in the scaleBLC(
hemical scale removal is usually a cheap and easy )ay to remove scales, but the eec+
tiveness of the removal depends on surface to volume ratio of the scale( If the scale has
a large surface area compared to the volume, like porous materials, the scale )ill be bro+
ken do)n -uickly( This is due to the large contact area bet)een the chemical agent and
the scale( If a scale has a lo) surface to volume ratio, like a non+porous material, only
the e<terior surface )ill be in contact )ith the chemical agent( Decause a non+porous
scale )ill be broken do)n only from the e<terior surface, )hile a porous material )ill be
broken do)n from the e<terior and interior surface, the removal of a non+porous scale
)ill be much slo)er(
7(" Mechanical removal
There are many dierent )ays of removing scales mechanically( @ne can use simple
milling or impact techni-ues( Scales rarely forms evenly along tubules, and therefore
the energy re-uired to remove the scales vary greatly( If the speed of the milling device
is not set at a suciently high speed, there is a risk of stalling( Impact techni-ues
)orks much like a ;ack hammer, hammering the scales until they break( These impact
techni-ues )ork best for brittle scales( Another techni-ue is to use e<plosives induce
shock vibrations to the pipe, causing brittle scales to break o( This method is eective
against thin layers( Thick layers are usually too strong for a safe removal by e<plosives(
Net blasting techni-ues involve using an high velocity ;et stream to remove scales( This
)orks best for soft scales( The ;et techni-ue can be combined )ith a hard particle
substance to remove hard scales( This is very similar to sand blasting, and removes the
scales by erosion( The particles used have to be selected carefully since the ;et blasting
)ith particles can erode pipe )all as easily as scales( 3ound particles are good for
removing scales, and reduce the damage to the pipes(
7(4 &revention of scale
The cost of scales removal can be -uite costly( Therefore it is sensible to prevent
the formation of scales( @ne of the easiest )ays is to dilute ion rich )aters )ith fresh
)ater, reducing the concentration of ions and thus the saturation of the system( Another
)ay is to use a scale inhibitor( Scale inhibitors can hinder scale gro)th in several )ays,
)here some of them are% Absorption onto the surface of the scale nuclei to make
combination
)ith other crystals dicult, absorption on a surface defect of a crystal preventing further
gro)th or use a chelating agent(
@ne problem )ith chelating inhibitors is that a stoichiometric ratio often is
re-uired( This both creates large amounts of )aste and are costly( These kind of
inhibitors are also sensitive to e-uilibrium changes( Absorption inhibitors attack the
crystalline structures and not ions themselves( Therefore, an amount $### times lo)er
than the stoichiometric ratio is needed, resulting in reduced treatment cost(
Another problem )ith chemical inhibitors is the calcium carbonate itself( As stated pre+
viously, calcium carbonate has three dierent crystal structures( The variation is crystal
structures demands dierent inhibition mechanisms for dierent crystal structures( This
can e<plain )hy certain inhibitors after some time apparently stop )orking( Than, scale
formation occur and some times even more aggressive than before inhibitionB$4C(
8 9iscussion
In all businesses, time is money( /<tra time used to deal )ith scale problems represents
both a loss of incoming money( :or )ells completely blocked after a -uick autoscale
process, the economic losses can be tremendous as a ne) )ellbore might be needed( Scale
removal by either mechanical processes or chemical additives represents e<tra e<penses in
addition to the time used( And, as already seen, )hen recycling M/!, a choice bet)een
e<tra operating costs or potential costs related to scale and polluted M/! must
be taken( :or scale at heated surfaces in processing systems, e<tra energy may be
re-uired to obtain the desired heat transfer(
,ealth, security and environment .,S/0 is important for all industries( Some of the
scales that can form .phosphorous scales0 can be poisonous and represent a health risk(
Scaling at safety valves can cause huge safety problem if these valves are covered by so
much scale that they are put out of action( *hen looking at environmental impact,
)aste formation, use of environmental unfriendly chemicals and energy use must be
taken into the discussion( The scale itself might be treated as a )aste after removal( As
stated in section 7, )hen preventing scale chemically, the result can be large amounts
of created )aste( *aste products )ill also be formed in a M/!+loop, either directly in
the reclamation process or potentially indirectly in the regeneration process(
Some of the chemicals used previously for inhibition of scale have no) been banned
due to un)anted environmental impacts( Ne) chemicals are developed, but some of
these are not as ecient and therefore, larger amounts are needed( The environmental
conse-uences of ne) chemicals in large amounts are often unclear until after some time
in useB$'C( /conomical aspects of increased energy use has already been discussed(
,o)ever, increased energy use has also environmental impact and minimi1ed energy use
is desirable(
The choice of technical solutions can be altered by scale formation( An e<ample of this
can be )hen scale in the near )ellbore region result in lo)er permeability( A potential
solution can be to perforate further into the )ell by using a more eective perforation
gun(
5 onclusion
Scaling is precipitation of sparingly soluble salts at surfaces( This can occur )hen a
supersaturated regime is established( :ormation of scale can occur and cause problems
both do)n in the )ell, along the pipelines and in the processing units on the platform or
onshore( If scale is left untreated, the )orst case can be blocked )ells, blocked pipelines
and blocked processing e-uipment( Since this is highly un)anted, prevention of scale is
important(
In order to prevent scale in an as environmentally friendly )ay as possible, a good
understanding of the chemical background for scale formation is necessary( There are
fundamental dierences bet)een dierent scales that can lead to more scaling if the
)rong choices are made(
To avoid all e<tra costs related to scaling is unrealistic( Dut the costs can be minimi1ed
by thoroughly risk analyses and a focus on scale prevention(
3eferences
B$C ,elbOk M, ?;elstrup S( :ysikalsk ?;emi( :agbokforlaget= "##7(
B"C Mullin N*( rystalli1ation( 'th ed( Dutter)orth+,einemann= "##$(
B4C Sandengen ?( &rediction of Mineral Scale :ormation in *et !as
ondensate &ipelines and in M/! .Mono /thylene !lycol0 3egeneration &lants
B&h9 ThesisC( NTNU= "##7(
B'C Sandengen ?( ,ydrates and !lycols( h tt p %GG )))( ip t(n tn u(n o GP ;s g Gund e r v is n in g Gn a tu r g a ss G
lysarkGHysarkSandengen"#$#(pdf= november "#$#(
B6C Noel @:, Ama;ouoyi A, N)okoye U( haracteri1ation of :ormation *ater on+
stituents and the /ect of :resh *ater 9ilution from Hand 3ig Hocation of
the
Niger 9elta, Nigeria( N Appl Sci /nviron Manage( "#$# Nune=$'."0%48'$(
B7C ?o;en !&( Statoil ASA &rincipal 3esearcher 3Q9 !as &rocessing and HN! Statoil
ASA B&ersonal correspondence by e+mailC= "#$#(
B8C hilingar !2, Mourhatch 3, Al+Rahtani !9( :undamentals of orrosion and Scal+
ing + :or &etroleum and /nvironmental /ngineers( !ulf &ublishing ompany= "##5(
B5C Nahn :, ook M, !raham M( ,ydrocarbon /<ploration and &roduction( "nd ed(
/lsevier= "##5(
BLC rabtree M, /slinger 9, :letcher &, Miller M, Nohnson A, ?ing !( :ighting Scale
3emoval and &revention( @ilfield 3evie)( $LLL autumn=(
B$#C 2atneberg S( Scaling of alcium arbonate on Metal Surfaces in Mi<tures of Mono
/thylene !lycol and *ater BMaster ThesisC( NTNU= "##5(
B$$C :laten /M, Seiersten M, Andreassen N&( &olymorphism and morphology of calcium
carbonate precipitated in mi<ed solvents of ethylene glycol and )ater( Nournal of
rystal !ro)th( "##L=44$%46444645(
B$"C Salami A3A, Monem AA( 9o)nhole and Topside Scale hallenge E3emoval, &re+
vention and Inhibition StrategyF( Society of &etroleum /ngineers( "#$#=(
B$4C Andreassen N&( Associate professor in rystalli1ation, 9epartment of hemical
/ngineering, NTNU B&ersonal contact, oral informationC= "#$#(
B$'C h tt p %GG )))( u is (n o Gr e s e a r c h Gn a tu r a lS s cie n ce s Gc h e m is tr y S a nd S e n v ir o n m e n tG
oilSfieldSproductionSchemicalsG= november "#$#(
B$6C Andreassen N&( Supersaturation B&resentation given in the course T?& '646 rys+
talli1ationC( NTNU= "#$#(
B$7C h tt p %GG )))(s ta toil (co m Ge n Gte c hn olog y inn o v a tio n Gfi el dd e v elo p m e n tGfl o) a ss u r a n ce
GscaleGpagesGdefault(asp<= "#$#(
B$8C Nergaard M( Master Student, NTNU= "#$#(
:igure $% Solubility diagramB$6C
:igure "% Scaling due to mi<ing of incompatible fluids .left0 and autoscaling .right0 BLC
:igure 4% &icture of Scale deposition in a pipeB$7C
:igure '% S/M picture of dierent types of calcium carbonate crystalsB$8C
:igure 6% A sketch of the reboiler unit from ?ollsnesB'C
:igure 7% Sketch of the reclamation unit at SnMhvitB'C