Effect of temperature
calcium sulfate is less soluble
at higher temperatures.
Change of pressure on
solution- The sulfates of calcium, barium and strontium are more soluble at
higher pressures. Consequently, formation water will often precipitate a
sulfate scale when pressure is reduced during production. The scale may
deposit round the wellbore, at the perforations, or in the downhole pump (if
used).
Agitation
Source of Oil Field Scale: The chief source of oilfield scale is mixing of
incompatible waters. Two waters are called incompatible if they interact chemically
and precipitate minerals when mixed. A typical example of incompatible waters are
-2
+2
+2
+2
sea water with high concentration of SO4 and low concentrations of Ca , Ba /Sr ,
-2
and formation waters with very low concentrations of SO4 but high concentrations of
+2
+2
+2
Mechanism of scaling
1. Supersaturation: Behind every chemical process, there must be a
thermodynamic driving force. For precipitation, this is given by the difference
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. 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.
2. Nucleation sites: Although a driving force is established, a solution can be
supersaturated without solid formation occurring. The short explanation to this is
that the supersaturation has tobe sufficiently high; we have to be in the labile
regime of figure 1. In the metastable region of figure 1, the driving force is not
large enough to overcome the energy amount required to form a surface; a solid
particle. Spontaneous precipitation will therefore not take place. However, when
a surface is present, already existing defects at the surface can act as
nucleation sites. By this, the surface free energy required is lowered, allowing
solid particles to form and grow even in the metastable regime.
3. Precipitation nucleation is followed by precipitation and adherence.
(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, favouring precipitation of calcium carbonate.
Scaling decreases as total salt content (not counting Ca ions) of water increases
to a concentration of 1 20g N aCl/ 1 000g of water. Further increases in NaCI
concentration decrease CaC03 solubility and scaling increases
SI=H-K- AK where
H=actual H of water
= - log (moles of Ca++/litre)
2. Sulfates
i) CaS04.2H2O or anhydrite or hemihydrate - Calcium sulfate can
crystallize from aqueous solution in three forms: gypsum (CaSO4.2H2O),
hemihydrate (CaSO4.1/2H2O) and anhydrate (CaSO4).
Gypsum, the most common scale occurs at relatively low temperature. At
higher temperature (above 100 C), the stable phase predicted is anhydrite
(CaSO4). Many parameters are affecting this problem. Temperature,
pressure, fluid concentration, ratio of brine to hydrogen, fluid dynamic and
type of porous media are among these parameters.
Causes
Mixing of two waters, one containing calcium ions and the other
containing sulfate ions, often causes gyp scaling, particularly in
water flooding.
ii) BaS04 and SrS04 - Both BaS04 and SrS04 scales are usually caused
by mingling of two unlike waters, one containing soluble salts of barium or
strontium and the other containing sulfate ions. Barium sulfate is often
precipitated in gas wells as hydrates are evaporated.
3. NaCl
4. Iron salts- iron salts are precipitated during simulation if pyrite, siderite, iron
rich in clays are present in rocks. Scales do not consist of one salt but mixtures
of barium, strontium, calcium and iron salts along with wax if present in oil.
Iron sulfide scale is present in oil and gas producing wells, sour wells and
water injectors where the injected water has high sulfate content.
The disposal water contains dissolved H2S, whereas the aquifer water
contains dissolved iron. When these two waters are mixed together, H2S
reacts with the iron ions and precipitates iron sulfide species, as shown in
Equation (2.7).
Iron scales are frequently the result of corrosion products such as various
iron oxides and iron sulfide. Sulfate-reducing bacteria can be a source of
hydrogen sulfide , which then reacts with iron in solution or with steel
surfaces to form iron sulfide . If oxygen is introduced to a system , it can
react with iron to form a precipitate and with steel surfaces to form an
oxide coating.
The first step is to determine which scales are forming and where they are forming.
manner which permits its identification. It is the fastest method and requires
least amount of sample.
Chemical analysis may also be used for scale identification. Samples of scales
are decomposed and then dissolved in chemical solution. Scale compounds
are then analysed by standard techniques of titration or precipitation.
Scale compounds will usually not be identified unless the analysis is made for
each specific chemical compound, By comparison, all chemical compound can
readily be identified form an x-ray analysis.
(1) After adding HCI to the scale
sample, effervescence
usually
indicates CaC03, especially if the
sample does not contain iron
sulfide or iron carbonate. The odour
of H2S will indicate the presence of
sulphide scale. Table 9-5 is a
summary of easily run laboratory or
field tests to determine type of scale
(2) Analysis of field brine can show scaling tendencies. Table 9-6 shows an
example of BaS04 scale caused by mixing of Bartlesville and Arbuckle
brines from wells in the Boston Pool, Oklahoma .
(3) Table
9-7 shows
an
example of predictable
CaC03 precipitation due to
pressure drop and release
of CO2 from HC03 1,in
the Grayburg formation,
Hobbs field, New Mexico
SCALE REMOVAL
Scale remediation techniques must be quick and nondamaging to the wellbore,
tubing, and the reservoir. If the scale is in the wellbore, it can be removed
mechanically or dissolved chemically. Selecting the best scale removal technique for
a particular well depends on knowing the type and quantity of scale, its physical
composition, and its texture. Mechanical methods are among the most successful
methods of scale removal in tubulars. When pulling costs are low (e.g., readily
accessible and shallow land locations), the least expensive approach to scaling is
often to pull the tubing and drill out the scale deposit.
Chemically inert scales are not soluble in chemicals. Chemically reactive scales may
be classified as water soluble, acid soluble and soluble in chemicals other than water
or acids.
1. Mechanical methods
I.
II.
III.
IV.
Field
II.
No. of wells
III.
Well production(production/Status)
IV.
Perforated interval
V.
Petro-physics
VI.
Tubing id and od
VII.
Wireline observation
VIII.
Types of scales
IX.
X.
Treatment procedure
Carry out production test, build up if well is not in conformity with
reservoir engineer prediction
Prepare the well for injection
Demulsifier spearhead: inject a slug containing 0.1% solution of
demusifier in deoxygenated seawater along with scale inhibitor (70100 gal/ft.) of perforation +wellbore volume below packer
Inject a spacer containing (4-6 %) EDTA/Erythorbic acid in
deoxygenated seawater with 2%KCl -(70-100 gal /ft. of perforation)
Inject a more concentrate on scale dissolver solution 20-25% w/w in
deoxygenated seawater +2%KCl
Calculate the injection volume to perforate 4ft. around wellbore and
bottom of tubing. Add foaming agent if gas lift is not available.
Scale dissolver over flush solution- depending upon reservoir
pressure inject tubing volume of diesel or liquid nitrogen or seawater
with foaming agent.
Scale dissolver shut in for 24 hr. to assist the scale dissolver, agitate
after 4 to 1 hr. 4 ft. involves flowing of 5 bbl of fluid out of well (in most
cases) so that unreacted solution is moved to the scale surface.
A three stage treatment may be planned. Each may be separated
after chemical analysis of produced fluid and well performance.
Water-Soluble Scale-The most common water-soluble scale is sodium chloride
which can be readily dissolved with relatively fresh water. Acid should not be used to
remove NaCI scale. If gyp scale is newly formed and porous, it may be dissolved by
circulating water containing about 55,000 mg/liter NaCl past the scale. At 100 deg. F,
55,000 mg/liter NaCl will dissolve three times as much gypsum as fresh water.
Acid-Soluble Scalei.
ii.
iii.
iv.
The most prevalent of all scale compounds, Calcium carbonate (CaCO 3), is
acid soluble. HCl or Acetic acid can be used to remove calcium carbonate.
Formic acid and sulphonic acids have been used effectively to remove such
scales.
Acetic acid has special application down the hole in pumping wells when it
is desired to leave chrome plated or alloy pumps in a well during acid
treatment. Acetic acid will not damage chrome plated surfaces at
temperature below 200 deg. F, However HCl may severely damage the
chrome plated surfaces.
Acid soluble scales also include iron carbonate (FeCO3), iron sulphide
(FeS), and iron oxide (Fe 2O3).
HCl plus a sequestering agent is normally used to remove iron scale. The
sequestering agents holds iron in solution until it can be produced from the
well. A sequestered Fe acid, such as HCl + .75% Acetic acid + .55% citric
acid may provide over 15 days of sequestering time.
v.
Normally 15% sequestered HCl is used but 20% may be necessary because
of slow reaction with iron compounds.
vi.
A 10% solution of Acetic acid may be used to remove iron scales without an
additional sequestering agent. However Acetic acid is much slower than
HCl.
-----------------------------------------------------------------------------------------------Type of acid soluble scale
Gallons of 15% HCl/Cu ft of scale
----------------------------------------------------------------------------------------------CaCO3
95
Fe2O3
318
FeS
180
----------------------------------------------------------------------------------------------ACID INSOLUBLE SCALES:
i.
The only acid insoluble scale which is chemically reactive is Calcium
Sulphate or gypsum. Calcium sulphate though not reactive in acid, can be
treated with chemical solutions which can convert calcium sulphate to an
acid soluble cmpounds like Calcium carbonate or calcium Hydroxide CaCO3
or Ca(OH)2 which can be removed with acid.
-------------------------------------------------------------------------------------------Type of solution
% of gypsum dissolved
24 hours
72 hours
---------------------------------------------------------------------------------------------NH4HCO3
87.8
91.0
Na2CO3
83.8
85.5
Na2CO3 NaOH
71.2
85.5
KOH
67.6
71.5
---------------------------------------------------------------------------------------------ii.
iii.
iv.
v.
Remove converted CaCO3 scale with HCl or Acetic acid. Dissolve Ca(OH)2
with water or weak acid.
Compounds such as EDTA (Ethylene di-amine Tetra-acetic acid) and DTPA
(Di-ethylene Tri-amine Penta-acetic acid) can dissolve gypsum without the
necessity of conversion to CaCO3 or Ca(OH)2. But EDTA or DTPA are not
used because of high cost.
Scale prevention
Inhibition of Scale Precipitation by Inorganic Polyphosphates
The polyorganic acid is placed on the basis of 10 gals of chemical per 1,000
gals of water or alcohol. The polyorganic acid can also be injected in a water
solution down the annulus to reduce scale deposition in the casing, tubing,
pump, and surface equipment.
It can also be used in the power oil of hydraulic lift type of downhole pumps
Exxon Chemical's COREXIT 7605 has replaced their COREXIT 7640 to inhibit
against calcium and barium sulfate scale deposition.
Exxon Chemical 's SURFLO H-372 replaces COREXIT 7641 to inhibit against
most scales including CaC03, CaS04, and BaS04 SURFLO H-372
wasformerly sold by NL Chemicals.
Return to production.
VISCO 950 inhibits against deposition of BaSO4, CaS04, and CaC03. VISCO
950 may be added to surface water systems or may be used for continuous
feed into down the casing-tubing annulus. As an effective formation squeeze
treatment scale inhibitor, Visco 950 is best used with a 1 :9 ratio of produced
water, with 200-500 barrels of overflush into the formation.
II.
Visco 953 controls CaC03, CaS04, and BaS04 scales at very low dosages in
oil and gas wells, water injection systems, and salt water disposal systems.
For water injection systems, continuous treatment is best; for downhole usage
, batch treatment or semicontinuous treatment is most effective. Visco 953
also is used as a formation squeeze treatment scale inhibitor, mixed at a 1 :9
ratio with overflush into the formation. However, the most effective treatment
is to mix a 1-3% solution of Visco 953 with produced water, displacing the
solution into the formation.
III.
VISCO 959 is designed for formation squeeze jobs to inhibit CaC03 and
sulphate deposits in oil and gas wells and producing equipment. Typical
treatment is to preflush with 5 to 1 0 bbl of produced water, pump in VISCO
959 mixed with formation water at a ratio of one to ten, overflush with 50 to
250 bbl of formation water, depending on daily water production. Usual
treatment is about 1 65 gal of VISCO 959.
Pump in 100-150 gal. HCl spearhead to ensure CaCO3 scale clean up. Pump
in the slug consisting of 45 bbl of produced water, 100 gal of 15% HCl and
100 gal AACROHIB polymer.
Follow up with enough CaCl2 to raise the CaCl2 content in the 45 bbl slug of
water to 10,000 ppm. This raises the pH from 1.2 to about 4.5 and causes the
polymer to crosslink and precipitate as a gel in the formation.
The crosslink polymer is then pushed into the formation and dispersed with
100-200 bbl of produced water.
Case study
Details: semoga field is an oil field in the rimau block, which is located south
Sumatra Indonesia. There is also a nearby oil field in this block
These fields have experienced reservoir souring when H2S is being generated from
the reservoir and entering the system. To reduce the H2S concentration in the
facilities H2S scavenger to injected in the system.
Problem: there was a separation system problem at Free Water Knock Out (FWKO)
semoga station. FWKO outlet was dismantled for the injection purposes. It was
found that oil outlet down at the downstream valve LCV ---- 0.5 only
Reason:
X-ray diffraction and x-ray fluroscence analysis confirm that the deposit is
CaCO3 scale.
The scale dosage was 9-10 ppm only. Lab test shows H2S scavenger brand
X injection reduced scale inhibition % from 97.2 to 35.3% with a 9 ppm of
scale inhibitor.
No deposits found in oil outlet line at downstream of LCV at kaji station which
has same H2S scavenger point and dosage. Dosage was 17.3<22ppm. Lab
test shows 20 ppm dosage given 58% scale.
Solution: H2S scavenger injection will affect scale inhibitor performance it will
degrade the scale inhibition % compared with the system without H2S scavenger
injector. In maintaining the scale inhibitor performance to prevent scale growth,
increasing scale inhibitor dosage is not always the answer. It is important to
understand that scale inhibitor performance behaviour on a certain H2S scavenger
brand before taking preventive measures.
By applying the appropriate scale inhibitor concentration on an H2S scavenger
influenced system the production loss of 8,190 barrels of oil in semoga station could
have been prevented.