Documente Academic
Documente Profesional
Documente Cultură
geofysikk
An Introduction to Scaling
causes, problems and solutions
Margrethe Nergaard
Chriss Grimholt
Abstract
Scale occurrence, formation and prevention have been investigated. In a natural gas
reservoir, water with dissolved ions will always be present. When parameters as temperature, pressure, concentration or pH are changed, the equilibrium of the system is
shifted. This can push the system into a state where the dissolved ions precipitate out,
causing a deposition of scale.
Corrosion protection of pipelines will lead to increased scaling of calcium carbonate.
Mono ethylene glycol (MEG) used as antifreeze, will also impact the scaling. Various
mechanisms can lead to scale formation in the natural gas well, the wellbore and in the
production equipment. In processing systems, especially heated surfaces are targets of
scale. Regeneration of MEG is also connected to scale formation, as the process with
lowest operating costs has higher risk of scale formation and contamination.
After formation, some scales can be removed. This can either be done by physical processes or chemically. Prevention of scale is conventionally done with chemical inhibitors.
This can create large amounts of waste. We claim that increased knowledge on the
chemical background of scale formation, can also contribute to scale prevention.
Contents
1 Introduction
2
2
2
3
3 Scale formation
3.1 Hydrate prevention . . . . . . . . . . . . . .
3.2 Corrosion prevention . . . . . . . . . . . . .
3.3 Combating one problem by creating another
3.4 Formation water . . . . . . . . . . . . . . .
3.5 Calcium carbonate scale mechanism . . . . .
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8 Conclusion
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ii
1 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 subject. The aim of this report is to give an easy
introduction to the scaling phenomena, going though crystallization and equilibrium
theory, the cause of scaling, problems caused by scaling and ending with strategies for
fighting scales.
Scaling is the deposition of a mineral salt on processing equipment. Scaling is a result
of supersaturation of mineral ions in the process fluid. The theory behind scaling is
explained in section 2 with important topics like solubility, nucleation and supersaturation.
This supersaturation of ions are caused by several factors. An important contributor
is the production of high salt content water like formation water from the well. This
increases the ionic concentrations, possibly leading to deposition of scales, as explained
in section 3. This section also discuss how other preventive actions against hydrate
formation and corrosion increase the risk for scale deposition, and how scaling is aected
by changes in physical variables such as concentration (also including pH), pressure and
temperature.
Scale deposition can cause problems several places in production and processing of natural gas. A summary of the most common problems associated with scaling is given
in section 4 and 5. This includes high risk areas where large temperature and pressure
changes occur, like heat exchangers and pipes.
There are several ways of fighting scales, as discussed in section 6. There are preemptive
methods like chemical inhibitors that hinder the scale growth. These methods are limited
in there use, because a inhibitors works best for specific scale types and crystal structure.
A more versatile methods for scale fighting are removal after deposition. Chemical
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 equipment. Theres a wast amount of mechanical systems, and only a few are
discussed.
We summarize the report by discussing how scaling can impact economy, health, security
and environment (HSE) and alter the choice of technical solutions.
increasing temperature will increase the solubility. Pressure dependence is usually weak
for systems of dissolved solids, but in oil- and gas wells the pressure can be so high that
this dependency has to be taken into account [1]. Also, for the ease of the discussion,
we hereby look at an ideal system where activities can be replaced by concentrations.
By what we have stated so far, concentrations greater than the ones dictated by the
solubility product Ksp would give precipitation. However, this is not always the case.
This is most easily explained by an illustration, see figure 1. Here, the solubility product is represented as the solid black line line. This curve is also called the saturation
line, referring to a solution saturated by dissolved ions. Stable region refers to the region where ions are dissolved (meaning: in solution) and labile to where precipitation
will occur spontaneously and solids form. The metastable region is further explained
below[2].
Behind every chemical process, there must be a thermodynamic driving force. For
precipitation, this is given by the dierence between the chemical potential of a given
substance in the stable and metastable/labile region. To represent this driving force,
the term supersaturation is often used. Supersaturation refers to the dierence in concentration between the bulk concentration (E, C in the figure, but can be anywhere in
the metastable and labile region) and the corresponding concentration at the solubility
curve (B, D) for a given temperature.
At point A, the solution is not supersaturated, there is no thermodynamic driving force
and therefore no precipitation. By changing either the temperature or the concentration
(e.g. by evaporation some solute) one can exceed the solubility concentration (point B
and D) and cross into the supersaturated regime. Now, a thermodynamic driving force
for precipitation is established and formation of solids may take place.
3 Scale formation
A natural gas well will, besides producing natural gas, also produce water and carbon
dioxide (CO2 ). The produced water can come from two sources: water vapor in the gas
that condenses into liquid water and formation water containing salts. This water is the
source of hydrate formation and, in combination with CO2 , corrosion. Scaling is caused
by salts and can occur when the produced water contains formation water.
MEG is transported in a so-called MEG loop. Here, MEG is injected into the natural gas
pipeline at the wellhead and flows with the natural gas to processing site onshore. MEG
is then separated from the water, regenerated and sent back to the oshore production
facilitie. The MEG transported from the reservoir and from the production site onshore
is called rich MEG and lean MEG respectively.
(1)
Long pipelines are constructed of carbon steel[4]. Carbonic acid will corrode the iron
in the pipeline wall, producing iron carbonate. See reaction 2. This iron carbonate can
precipitate in the production fluid and follow the gas and liquid flow, causing problems
downstream.
Fe + H2 CO3 FeCO3 + H2
(2)
For now, a simple equilibrium approach is used to explain how dierent parameters
impact solubility and thus scale formation. To limit the extent of this report, we focus
on the formation of calcium carbonate.
The reactions that lead to formation of solid calcium carbonate are as follows[7]: First,
carbon dioxide reacts with water to produce carbonic acid as seen by reaction 3.
(3)
This carbonic acid will continue to dissociate hydrogen, creating new deprotonated
species of carbonic acid, as seen in reaction 4 and 5.
(4)
+
2
HCO
3 (aq) + H2 O (l) H3 O (aq) + CO3 (aq)
(5)
2
In the water mixture there will be a mixture of the species H2 CO3 , HCO
3 and CO3 .
Finally, in the presence of calcium and carbonic acid, calcium carbonate will precipitate
out as seen by reaction 6.
2+
CO2
(aq) CaCO3 (s)
3 (aq) + Ca
(6)
Since produced water usually contains a carbonic acid and calcium ions, a recombination
of these reactions will give a better representation of the situation, as seen by reaction
7.
(7)
Calcium and carbonic acid together in liquid form will be in equilibrium with water,
solid calcium carbonate and CO2 gas.
Most behaviors of the calcium carbonate equilibrium can be predicted from Le Chteliers equilibrium principle. This principle states that a chemical system at equilibrium
will always 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 equilibrium and scale formation. A brief discussion of each parameters
follows beneath.
Pressure dependance: When pressure is decreased in a chemical system, the equilibrium
will try compensate by increasing the pressure. Because CO2 is the only gaseous specie,
the only way to increase pressure is by shifting the equilibrium towards producing more
CO2 . A decrease in pressure will then result in more precipitation of calcium carbonate.
Concentration dependance: If the concentration of calcium or carbonic acid is increased
or the partial pressure of CO2 is decreased, then there would be an equilibrium shift
towards the right and more precipitation of calcium carbonate. Increasing the pH by
addition of an alkaline chemical such as NaOH would result in a naturalization of the
H3 O+ complex. This will shift the reactions 4 and 5 to the right, yielding more carbonic
acid. More carbonic acid will shift the equilibrium in reaction 7 towards the right and
more calcium carbonate will precipitate out.
Temperature dependance: The solubility of calcium carbonate will decrease as the temperature increases. This is an interesting phenomena, because most solubilities increase
with increasing temperature and therefor one gets less precipitation. One of the reasons
for this behavior is the fact that the precipitation of calcium carbonate require energy
(endothermic). This can be written into the equilibrium equation as follows:
(8)
When the temperature increases, the energy also increases, and the equilibrium will try
to counteract this by consuming energy. The equilibrium is then shifted towards right,
favoring precipitation of calcium carbonate.
Inside the well, water is naturally present. As the water experiences changes in temperature or pressure during production, the system will shift the equilibrium in order to
combat these changes. This shift can bring the system from the stable to the metastable
and labile region of figure 1 and scale can be formed. Species that originally were dissolved precipitate out and scale is formed in perforations in the near wellbore matrix.
Such scale depositions reduce the formation porosity and permeability and thus the
hydrocarbon flow. As scale is formed, pressure drops even further, giving more scale
formation. An illustration of this is found in the right part of figure 2 below. This
process is known as autoscaling and in worst case, pores can be completely blocked.
When the well is drilled and later completed, fluids (mud) are used to, among others,
stabilize the drill hole and provide hydrostatic pressure to prevent formation fluids from
entering the well bore. Formation water and drilling fluids are said to be incompatible;
meaning, chemical reactions will take place upon mixing. This can also lead to scale in
the near-wellbore environment[4, 8]. Incompatible mixing can also occur when seawater
is injected to enhance production. Seawater is often rich in dierent ions than the
production water and upon mixing, sparingly soluble salts precipitate out, as illustrated
to the left in figure 2.
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 catalyze
depositions of scale. Turbulence increases mixing and mass transfer in the zone close to
the surface[9]. When a fluid passes a hinderance, a pressure drop is often experienced.
These factors can explain why scale often occurs in downhole completion equipment.
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 flow is severely restricted as seen in
figure 3.
If the gas produced has acidic gases associated with it, such as H2 S and CO2 , another
mechanism cause problems. As pressure is reduced during production, less acidic gas is
dissolved. This raises the pH, which again lower the solubility and causes precipitation
of carbonates. Scale of this type can extend from the near-wellbore matrix along tubing
and to surface equipment, since the temperature and pressure of the produced water
continuously changes and thus also changes the pH. A similar type of scaling can occur
when using CO2 for secondary recovery. As water turns acidic when CO2 is dissolved,
calcium carbonate will dissolve from the limestone well. When production leads to
pressure drop, CO2 is released from the water and calcium carbonate precipitate out
again in the near-wellbore pores. Like autoscale, these processes are self-generating and
can completely seal wells and boreholes in few days[9].
In wet gas production, evaporation-induced scaling can also occur. During production,
lowered pressure expands the hydrocarbon gas. This leads to evaporation of the formation water and thus increased concentration of dissolved species. As enough solvent
is evaporated, the system crosses the solubility curve as seen in figure 1 and scale is
formed[9].
10
Calcium carbonate has three dierent crystal structures, socalled polymorphs. Each
polymorph grows with dierent rates. Also, dierent supersaturations will favor dierent polymorphs. The same applies to temperature regions[11]. To understand which
polymorph that will cause scale at the current processing conditions, is therefore important.
In a current research project, scaling at heated surfaces for a continuous system is
studied. A scanning electron microscope picture from this project is shown in figure 4.
At the conditions of this exact experiment, the fast-growing needle-like crystal structure
dominates fully over the slow growing cube like structure. In the worst case scenario, the
scaling can be so extensive that that heat transfer is reduced to almost zero. Depending
on the dimensions of the unit operation, this can happen in a short time (hours or days)
and can put the whole unit out of action. Understanding which crystal structure occurs
when, can therefore be crucial. It is to be hoped that research will give more knowledge
on how to avoid such scenarios[4].
11
Solid removal is illustrated by a black box in figure 6, but is usually done in a sedimentation tank or in a centrifugation. MEG addition influences both the solubility and
crystal structure of calcium carbonate. As stated earlier, solubility of calcium carbonate
decreases with increasing MEG concentration. It is also found that the particle size
of calcium carbonate precipitate is reduced at high MEG-levels[11]. 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 techniques.
12
13
structures demands dierent inhibition mechanisms for dierent crystal structures. This
can explain why certain inhibitors after some time apparently stop working. Than, scale
formation occur and some times even more aggressive than before inhibition[13].
7 Discussion
In all businesses, time is money. Extra time used to deal with scale problems represents
both a loss of incoming money. For wells completely blocked after a quick autoscale
process, the economic losses can be tremendous as a new wellbore might be needed. Scale
removal by either mechanical processes or chemical additives represents extra expenses in
addition to the time used. And, as already seen, when recycling MEG, a choice between
extra operating costs or potential costs related to scale and polluted MEG must be
taken. For scale at heated surfaces in processing systems, extra energy may be required
to obtain the desired heat transfer.
Health, security and environment (HSE) is important for all industries. Some of the
scales that can form (phosphorous scales) 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. When looking at environmental impact,
waste formation, use of environmental unfriendly chemicals and energy use must be
taken into the discussion. The scale itself might be treated as a waste after removal. As
stated in section 6, when preventing scale chemically, the result can be large amounts
of created waste. Waste products will also be formed in a MEG-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 now been banned
due to unwanted environmental impacts. New chemicals are developed, but some of
these are not as ecient and therefore, larger amounts are needed. The environmental
consequences of new chemicals in large amounts are often unclear until after some time
in use[14]. Economical aspects of increased energy use has already been discussed.
However, increased energy use has also environmental impact and minimized energy use
is desirable.
The choice of technical solutions can be altered by scale formation. An example of this
can be when scale in the near wellbore region result in lower permeability. A potential
14
solution can be to perforate further into the well by using a more eective perforation
gun.
8 Conclusion
Scaling is precipitation of sparingly soluble salts at surfaces. This can occur when a
supersaturated regime is established. Formation of scale can occur and cause problems
both down in the well, along the pipelines and in the processing units on the platform or
onshore. If scale is left untreated, the worst case can be blocked wells, blocked pipelines
and blocked processing equipment. Since this is highly unwanted, prevention of scale is
important.
In order to prevent scale in an as environmentally friendly way as possible, a good
understanding of the chemical background for scale formation is necessary. There are
fundamental dierences between dierent scales that can lead to more scaling if the
wrong choices are made.
To avoid all extra costs related to scaling is unrealistic. But the costs can be minimized
by thoroughly risk analyses and a focus on scale prevention.
15
References
[1] Helbk M, Kjelstrup S. Fysikalsk Kjemi. Fagbokforlaget; 2006.
[2] Mullin JW. Crystallization. 4th ed. Butterworth-Heinemann; 2001.
[3] Sandengen K. Prediction of Mineral Scale Formation in Wet Gas Condensate
Pipelines and in MEG (Mono Ethylene Glycol) Regeneration Plants [PhD Thesis].
NTNU; 2006.
[4] Sandengen K. Hydrates and Glycols. http://www.ipt.ntnu.no/~jsg/undervisning/naturgass/
lysark/LysarkSandengen2010.pdf; november 2010.
[5] Joel OF, Amajouoyi CA, Nwokoye CU. Characterization of Formation Water Constituents and the Eect of Fresh Water Dilution from Land Rig Location of the
Niger Delta, Nigeria. J Appl Sci Environ Manage. 2010 June;14(2):3741.
[6] Kojen GP. Statoil ASA Principal Researcher R&D Gas Processing and LNG Statoil
ASA [Personal correspondence by e-mail]; 2010.
[7] Chilingar GV, Mourhatch R, Al-Qahtani GD. Fundamentals of Corrosion and Scaling - For Petroleum and Environmental Engineers. Gulf Publishing Company; 2008.
[8] Jahn F, Cook M, Graham M. Hydrocarbon Exploration and Production. 2nd ed.
Elsevier; 2008.
[9] Crabtree M, Eslinger D, Fletcher P, Miller M, Johnson A, King G. Fighting Scale
Removal and Prevention. Oilfield Review. 1999 autumn;.
[10] Vatneberg S. Scaling of Calcium Carbonate on Metal Surfaces in Mixtures of Mono
Ethylene Glycol and Water [Master Thesis]. NTNU; 2008.
[11] Flaten EM, Seiersten M, Andreassen JP. Polymorphism and morphology of calcium
carbonate precipitated in mixed solvents of ethylene glycol and water. Journal of
Crystal Growth. 2009;331:35333538.
[12] Salami ARA, Monem AA. Downhole and Topside Scale Challenge Removal, Prevention and Inhibition Strategy. Society of Petroleum Engineers. 2010;.
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Figure 2: Scaling due to mixing of incompatible fluids (left) and autoscaling (right) [9]
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Figure 3: Picture of Scale deposition in a pipe[16]
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