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OILFIELD CHEMICAL

WAX TREATMENT REV.01


BONY BUDIMAN
2021

https://www.linkedin.com/in/bony-budiman-39886031/
COMMON QUESTION

• What is wax, and what is the effect in


the oilfield ?
• What is PPD or Wax Inhibitor?
• How to select PPD ?
• How to apply PPD in the filed ?
• Field cases !

Courtesy Picture : https://dragonflytraining.files.wordpress.com/2013/10/man-with-question-01.png?w=640


OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• PPD APPLICATION
• FIELD CASES
• SUMMARY
OBJECTIVE

• Refresh simple definition of paraffin and


wax
• Sharing implication of wax in the oilfield
• Sharing PPD mechanism, how to select
and how to apply in the field.
• Sharing some field cases
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• PPD APPLICATION
• FIELD CASES
• SUMMARY
PARAFFIN

paraffin waxes 1. Paraffin are defined as a class of i-


alkanes and n-alkanes that
comprises a long hydrocarbon
chain usually attached via single
bonds.
2. High molecular weight paraffins
5 10 15 20 25 30 35 40 are commonly found in solid wax
n-alkane carbon number
deposits, where the carbon
numbers are in the range of 18 to
75 and where the melting point
ranges from 40 ◦C to 70 ◦C
PARAFFIN AND WAX

• In this presentation, we refer paraffin as a class of


hydrocarbon and wax as precipitated paraffin.You may
find another definition in others technical references.
• The precipitation of paraffin to wax occurs in two
stages :
• nucleation
• crystal growth

Courtesy picture : https://madridge.org/international-journal-of-petrochemistry/ijpr-1000122.php


WHERE WAX FORMED ?

• Wax formed anywhere where the production temperature is


below the Wax Appearance Temperature (WAT)
• Wax may found at
• Down hole
• Riser
• Flow lines
• Separator
• Storage facilities
• Transport lines

• The precipitation affected by :


• Temperature decrease (main factor)
• Pressure decrease
• Light ends hydrocarbon removed
• Asphalt content increase

Courtesy picture : HTS Consultant, Oilfield Production Chemicals and Microbiology


WAX PRECIPITATION DIAGRAM(6)

• Position A is the reservoir pressure with the oil


undersaturated. As the fluids are produced, the pressure falls
and the light ends expand in greater proportion to the
dissolved waxes, increasing their solubility and yielding a
lower WAT.
• At the bubble point (B), the volume ratio of light ends to
heavy ends is at its greatest so the WAT is at its lowest.
• Reducing the pressure still further (C) results in liberation of
dissolved gases and light ends to the gas phase. This reduces
the solubility of the wax, and so, the WAT increases
WAX DEPOSITION MECHANISM(6)

Wax deposition is considered to occur by


two primary mechanisms:
1. If the pipe wall is colder than the WAT,
wax can form and deposit at the wall.
This can occur even if the bulk fluid is
above the WAT. This is called the
“molecular diffusion mechanism.”
2. Already precipitated wax close to the
pipe wall will move to a region of lower
velocity at the pipe wall and deposit.
This is known as shear dispersion.
WAX PROBLEM
- Reduce cross section diameter
- Reduce flowrate

- Fluid viscosity-gelling increase


- Create tighter emulsion water in oil
- Increase of surface roughness
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• PPD APPLICATION
• FIELD CASES
• SUMMARY
METHOD OF MONITORING

• Crude Oil Composition • WAT / Cloud Point Monitoring


• By Gas Chromatography • Optical light scattering technique
• Fourier transform infrared spectroscopy • Cross-polarization microscopy

• Deposit Monitoring • Laser and collimator solids detection


system
• Cold Finger Test
• Near-infrared scattering
• Pour Point Test
• High-pressure, cold-stage microscope
• Tube Blocking Test
technique
• Sonic testing device
• Nuclear magnetic resonance
CLOUD POINT
cps
1000 1. Cloud point or Wax
(non) pour point Appearance Temperature
100
wax appearance temp. (w.a.t.) (WAT) is temperature when
10
(cloud point) paraffin start form crystal
no wax 2. Cloud point could be
1
observed when the viscosity
10 20 30 40 50 60 70 Temp C increase as temperature
Cooling of crude oil cooled
3. By microscope it observed as
white image
POUR POINT

• The pour point is the temperature at which


thermometer

the crude oil shows no more movement


glass pour point tube

copper outer tube

• The method refer to ASTM D-97 : Standard


crude sample Test Method for Pour Point of Petroleum
ice-bath
Products
• The principle is to observe when the crude
oil no more movement when cooled
FACTOR AFFECTING POUR POINT(10)

Wax • Table beside shows the characterization of


Pour Point API Gravity Asphaltene
Crude Oil o
( C)
0
at 15.56 C
Content (wt
Content (wt %) properties of different crudes
%)
Mexican (PC) -30.0 36.0 11.3 2.3
• It was quite surprise that there are no
Mexican (IRI) 2 -26.0 8.4 10.9 1.5
Umbarak 21.0 32.8 18.9 1.3 consistent correlation between API Gravity,
Langhnaj (India) 22.0 44.2 22.4 0.2
Karama 24.0 41.1 16.0 3.0
wax content or asphaltene content to pour
Iranian 26.0 34.9 13.1 0.3 point.
Egyptian 27.0 31.6 11.9 0.7
Farodus 30.0 31.1 8.4 3.0 • From this table, we temporary concluded that
Changqing (China) 30.0 34.0 20.8 0.1
Shengli (China) 43.0 24.2 18.3 2.6 there may be a complex interaction in the
crude between components that affect the
pour point.
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• PPD APPLICATION
• FIELD CASES
• SUMMARY
PRINCIPLE OF WAX MANAGEMENT

1. Inhibit wax are better, easier and cheaper


than remove deposited wax
2. To inhibit wax by chemical, use Pour Point
Depressant / Wax Inhibitor / Crystal Modifier
3. To remove or dissolve deposited wax by
chemical, use paraffin solvent / wax dissolver
WAX TREATMENT

MECHANICAL THERMAL CHEMICAL

PIGGING SCRAPPING INSULATION HOT LIQUID INHIBITOR DISSOLVER


WAX INHIBITOR / PPD(6)

• Wax/Paraafin Inhibitor also known as Pour Point


Depressant (PPC). Some references may stated that
Wax Inhibitor has different function compare to PPD
• PPD is chemical that decrease the pour point of crude
oil
• Most of available ready to use PPD consist of single
component active content PPD diluted in hydrocarbon
solvent. In range 20-50% active content
• Some types of PPD :
• Ethylene polymers-copolymers,
• Comb polymers
• Miscellaneous branched polymers with long alkyl group

Courtesy picture : Pour Point Depressants A Fluid Flow Improver, a Technical Data Sheet of Prosympac PCFLO-1540
ETHYLENE POLYMERS AND COPOLYMERS(6)

• The larger monomers act as branches disrupting


the normal alkanes for crystallizing as wax.
Examples are
• Ethylene/small alkene copolymers
• EVA copolymers
• Ethylene/acrylonitrile copolymers
• In one study, EVA copolymers dosed at 200 ppm
gave a reduction in yield stress of three orders of
Ethylene/vinyl acetate (EVA) magnitude for the C36 wax
COMB POLYMERS

• Comb polymers are generally regarded as the most effective


class of wax inhibitors. With dosage start from 100 ppm
• However, in severe wax cases with high WAT, even these
inhibitors may not solve the deposition problem over
extended periods.
• This is because the bulk of the wax alkanes are considerably
longer than the alkyl chains in the comb polymer. Hence,
periodic pigging or some other wax removal technique may
be needed.
• Comb polymers are usually made from one of two classes of
monomers, (meth)acrylic acid, or maleic anhydride, or both
MISCELLANEOUS POLYMERS(6)

• Some types of these polymer are :


• Alkylphenol–formaldehyde resins
• N-vinylpyrrolidone/α-olefin copolymers
• Polyethyleneimine

• Alkylphenol–formaldehyde resins have been


claimed as PPDs and flow improvers. By
themselves, they are not as effective as comb
Alkylphenol–formaldehyde
resins. polymers described earlier but they make useful
synergists
MECHANISM OF PPD

• PPD will attach the paraffin crystal


• The paraffin crystal that already
attached by PPD will still soluble in
the solution
• But if the temperature continue
cooled, at a point the crystal will
start join each others, growth and
will be deposited as wax.

Courtesy picture : https://media.noria.com/sites/Uploads/2019/7/14/f2c73ac0-2e22-43c1-b423-68949fb229ab_pour-point-oil_extra_large.jpeg


ILLUSTRATION OF PPD MECHANISM

• Without PPD, the crystal will interlock each


other create higher molecule then deposited
• PPD will interfere the interlock process by
modified the wax crystal growth.
• Wax crystal may still formed, but since the
shape of crystal destroyed by PPD, it cannot
easily join each other to form bigger crystal
at specified temperature and pressure.

Courtesy picture : Pour Point Depressants A Fluid Flow Improver, a Technical Data Sheet of Prosympac PCFLO-1540
PPD EFFECT (UNDER MICROSCOPE OBSERVATION)

1. At left-up picture, the paraffin crytal in crude


oil noted with white image. They form a
homogeny net and trap the liquid phase and
cause all crude oil no more movement
2. At right picture, the crude oil heated up to
80oC, at high temperature the paraffin
crystal net broke and the crude oil re-
flowing
3. Addition PPD create similar image to the
heating condition.
MICROSCOPY OBSERVATION

• Pictures beside compare crude oil that


untreated and treated with PPD under
microscope observation
Untreated:
Numerous Connected crystals
Treated: 1000 ppm
Few isolated crystals
• Without PPD treatment, the wax crystal
will spread evenly in the liquid then
join each others like a net so that the
oil forms a gel
• By addition of PPD wax crytal will be
isolated and will not join each others.

Untreated: Treated: 1000 ppm


Completely gelled Larger Crystals, still separate
RESUME OF PPD PRINCIPLE(9)

• PPDs do not change the temperature at which wax crystallizes or the amount of wax
that builds up.
• Their application, in fact, relies on the PPD co-crystallizing with the targeted paraffin
species present in the oil, thus modifying the wax crystal structures to one more
favorable to allow flow.
• Furthermore, the wax crystals are kept isolated by the PPD backbone and, because of
this steric hindrance, the wax crystals are no longer able to form 3-D structures that are
responsible for gelation, therefore inhibiting flow.
PARAFFIN SOLVENT

• Also known as was dissolver


• Paraffin solvent is chemical used to dissolve the wax
• Usually combination of hydrocarbon solvent, surfactant and small
component of wax inhibitor. Xylene and toluene is common
hydrocarbon solvent used as paraffin solvent.
• Injected by soaking or very high dosage up to 1 : 1
• The effectiveness will be depend of dosage, contact time and
temperature.
PPD SELECTION

A pour point depressant simply cannot be selected based on any single test. Therefore, it is
crucial to consider all of the parameters in the field that affected by the waxy crude. Some
test are as below :
• Pour Point Test - ASTM D-97
• Viscosity Test
• WAT Test
• Cold Finger Test
• Cold Filter Plugging Test
• Dynamic Test Loop
POUR POINT TEST - ASTM D97

• This is the most common selection test


• General procedure :
• Pour sample into glass jar test
• Put glass jar in ice bath with temperature
• Every temperature decrease 3oC or 5oF
tilt the jar test up to 90o for 5 second.
• Note at temperature when the liquid no
more moveas XoC
• Pour point = (X + 3) oC
ASTM D-97 RESULT AND INTERPRETATION

• Blank, crude oil without PPD, and crude oil with PPD
Chemical Dosage
o
Observed Test Temperature ( C) 50 ppm not flow at 42oC, means the Pour Point = 42+3
Type ppm 45 42 39 36 33 = 45oC.
Blank 0 Ok No Flow
PPD 1234 50 Ok No Flow • By addition PPD 1234 at dosage 100 and 250 PPM, the
PPD 1234 100 Ok Ok No Flow Pour Point decrease to 39+3 = 42oC.
PPD 1234 250 Ok Ok No Flow
PPD 1234 500 Ok Ok Ok No Flow • At dosage 500 ppm, the PP = 36+3 = 39oC
PPD 1234 750 Ok Ok Ok Ok No Flow
PPD 1234 1000 Ok Ok Ok Ok No Flow
• At dosage 750 and 1,000 ppm the PP = 33+3 = 36oC
COMMON POUR POINT LAB TEST RESULT

 In general more dosage addition more decrease of


pour point
 At one point, the dosage gives maximum
ΔT decrease, further dosage addition give flat or
inverse performance
 We shall find optimum instead of maximum
dosage. Optimum dosage is dosage where the
pour point meet target performance. Please bear
in mind that more dosage means more spent of
money since we cannot recovery the PPD back.
VISCOSITY

viscosity, cps
500 inhibitor a (500 ppm)  Pour crude oil in beaker glass
400
inhibitor b (500 ppm)  Put beaker glass in ice bath
uninhibited crude
300
a
 Check the viscosity and observe the temperature
untreated crude
200
b
 Pour point achieved when the viscosity increase extremely
100
(not linear)
5 10 15 20 25 30 35 40  At picture beside, the blue line is viscosity of blank
temperature, C (untreated cure)
 The dash line is pipeline temperature, around 13-14 oC.
 The pour point of PPD “A” is near the pipeline
temperature so we will prefer the PPD B at dosage 500
ppm.
COLD FINGER TEST

• Pour sample to beaker glass


• Dip a metal rod (that already known the initial
weight) to the crude oil.
• Pull out the metal rod. Observe by visual. If need
more information, re-weight the metal rod with the
wax
• Less wax attached in the metal rod indicate better
treatment (dosage and or type of PPD).
• This method also could apply for the wax dissolver
performance.

Courtesy picture : http://www.techboxsystems.com/wp-content/uploads/2019/08/Techbox-Systems-Multi-Place-Cold-Finger-CF6.pdf


COLD FILTER PLUGGING TEST

• The idea of this test is when wax formed,


they can become impediments to the
free flow of oil through restricted
opening.
• The sample is cooled and a vacuum is
applied across the filter.
• The time and temperatures are
measured., and when the filter stops the
oil flow, this represent the plugging
temperature point.
DYNAMIC TEST LOOP

• These devices generally use pumps to


circulate the crude oil samples through a
conduit of specific dimensions, and measure
such variables as temperature, fluid velocity,
pressure, viscosity, or even pH and
conductivity.
• The general concept of their operation is that
by varying the condition to which the sample
is exposed (pumping rate, temperature,
pressure, etc) reliable data about the transfer
of fluid can be obtained.
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• PPD APPLICATION
• FIELD CASES
• SUMMARY
APPLICATION OF PPD/ WAX INHIBITOR

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• Good mixing is critical to ensure the
PPD could attach to the paraffin
crystal.
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ot • The dosage of PPD quite high
compare to others specialty
chemicals, it could be in range 100 –
5,000 mg/liter.
OTHERS CONSIDERATION OF APPLICATION(6)

• Beside injection at wellhead, if wax is a problem downhole and a capillary string is


available, these chemicals can also be injected downhole.
• A technique used in China is to add a cylindrical solid wax inhibitor placed in a tubular
vessel or attached to the bottom of an oil pump into the well. The inhibitor gradually
dissolves over time as a slow-release system
• Due to its nature as long chain polymer, PPD can be very viscous, making them difficult to
handle, particularly for application in deepwater, subsea, or cold climates. Therefore,
deployed compositions are often low-concentration mixtures or solutions of the active
ingredient in a aromatic HC solvent
FACTOR AFFECTED PPD PERFORMANCE

• Paraffin content
• Higher and more complex the paraffin content, the pour point will be higher
• Expected Decrease of Temperature (∆T)
• Higher ∆T require higher dosage
• Injection point
• More upstream usually gives better performance. Well head is one of the best injection point
• Mixing(1)
• More homogeneous PPD in crude oil will give better performance
MIXING EFFECT(1)

Effect of Mixing • The purple bar is untreated crude, pour point is 13oC
Pour Point (oC)

15 • The yellow bar is crude + PPD without mix, the pour


10 point only decrease around 1oC.
5 • The red bar is crude + PPD with mixing 5 seconds, the
0 pour point decrease 5oC
-5
Mixing time
• The blue bar is crude + PPD with longer mixing time
up to 200 seconds and the pour point decrease
Blanko around 12oC
+ PPD & No Mix
+ PPD & Mix 5 Sec
+ PPD & mix 200sec
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• PPD APPLICATION

• FIELD CASES
• SUMMARY
1. ANDROMEDA #02

• Well Andromeda #02 send the crude oil by truck to Central Processing Plant (CPP) only
during 9 Am until 6 PM since the viscosity will increase significant after 7 PM
• The user expect to utilize the existing pipeline and produce 24 hours by using PPD with
economic cost compare to trucking cost.
1. ANDROMEDA #02 - BOTTLE TEST RESULT

 Prior to field trial. Bottle test refer to


ASTM D-97 conducted with expecting
pour point is at night lowest
temperature : 22oC.
 From bottle test result, the optimum
dosage is 2,000 mg/L
 The field trial conducted at initial
dosage 2x dosage from bottle test then
will be optimize later on
1. ANDROMEDA #02 - FIELD LAYOUT

injection
sampling
point 1
sampling The KPI is pour
Point point 2
point 22oC =
1,6 km 0,8 km

CPP 71.6oF
Andromeda
#02 o
Field result show
Pour Point ( F)
Dosage
Laboratory consistent lower
(ppm) Field Trial
Andromeda 4000
Test
71 64.2
pour point
# 11 2500 72.5 65.5 compare to
2000 72 68.8
1000 81 74 laboratory test
500 89 82.7
2, LIMA SUBSEA LINE

• Lima Subsea Line (LSL) is a crude oil


pumping line from onshore through
LIMA seabed.
# 04
• The lowest temperature at seabed is 21oC
Lima
Subsea (70oF).
LIMA Line = 2.7 LIMA Deck
# 05 kmm Separator
• The fluid from Wells Lima#04,05 and 06
gathered at Lima platform and send to
Lima Deck Separator through the 2.7 km
LIMA LSL
# 06
2, LIMA SUBSEA LINE - WELLS CHARACTERISTIC

Well Head Pour • During normal production the mix fluid


WAT
Well T Point BOPD BWPD temperature at LSL is above 70oC
P (psi) (oF)
(oF) (oF)
• The concern is the well LIMA #06 as the
LIMA # 04 360 262 103 117 61 2,984
hottest and highest production will be
temporary shutoff for workover job.
LIMA # 05 360 200 92 98 134 222 • During the shutoff of LIMA#06, the
simulation shows that mix fluid temperature
LIMA # 06 365 270 98 124 85 8,449 will be 68 – 72 oC which is in the seabed
zone temperature (70 oC)
2, LIMA SUBSEA LINE - LABORATORY TEST

Pour Point (oF)


Well 1000 2000 3000 • From the laboratory test PPD could decrease
Blank pour point below 70oF at dosage 3000 ppm
ppm ppm ppm
LIMA # 04 : 05 (5% : 95%) 85 80 75 63 with composition LIMA #04:#05 = 5 : 95
• During Well LIMA#06 shutoff, the composition
LIMA #04 : 05 (31% : 69%) 98 85 80 77
of LIMA #04 and #06 is fluctuate.
• Field trial conducted with initial dosage 5000
ppm and decrease to 1000 ppm with KPI no
decrease of production rate and no increase of
∆P
3. PIPELINE TRANSPORTATION(2)

• The pour point is 32oC and paraffin


content 35%.
• The crude transported via 40 km pipeline
to port storage with ground
temperatures of 11-18oC
• Some wax mitigation are :as per table
beside. PPD was chosen as the mitigation
plan considering cost and technical
feasibility
3. PIPELINE TRANSPORTATION - FIELD TRIAL RESULT

• On November 5, 1984, crude began


flowlng with PPD dosage 2000 ppm
with excellent performance of Pour
Point = –5oC (23oF)
• By closely monitoring pipeline
pressures, crude rheology and pour
polnts, the dose rate reduce to 960
ppm by December 25, 1984
4. DUAL CHEMICALS : PPD&CI(8)

• An operator producing from the Delaware basin in the Permian was experiencing paraffin
and corrosion issues in many of their wells.
• Paraffin problems were mainly observed in gas lift wells with buildup in the casing that
required tubing to be pulled.
• Occasionally, paraffin would deposit in the annulus also.
• These wells were at risk for corrosion due to the amount of CO2 (0.1-3 mole%), high O2
shear (25-50 pascal), and downhole pressures of 1000-1700 psi.
4. DUAL CHEMICALS : PPD&CI - CHALLANGE

• There is challenge to provide one blending chemicals that could treat both
paraffin and corrosion issue. This will provide extra benefits including reduced
number of injection points, reduced chemical injection tanks, and reduced
logistics with streamline of supply.
• The combination product would need to be gas lift qualified as no cap-string
delivery was available to the majority of wells in the area.
• Field testing consisted of compatibility and emulsion tendency to understand
the impact of the product on water quality and emulsion formation when
dosed up-to 10,000 ppm
4. DUAL CHEMICALS : PPD&CI – LABORATORY TEST
AS PPD
• PARA01975A is dual chemicals : PPD & CI
• Graph beside compare % fouling reduction
from some chemicals. Higher bar means
higher performance to reduce the
hydrocarbon fouling.
• PARA01975A performed exceptionally
well across all dosages tested when
compared to others PPD
4. DUAL CHEMICALS : PPD&CI – LABORATORY TEST
AS CI
• Corrosion RCE testing was
performed to assess the corrosion
protection performance
• Less corrosion rate in mpy and
higher % corrosion protection
indicate better performance.
• PARA01975A provided more than
98% protection at both 25 and 50
ppm,
4. DUAL CHEMICALS : PPD&CI – FIELD TRIAL

BEFORE TREATMENT • Field trial of PARA01975A was initiated with 5 wells comprised
of gas lift and rod pump applications.
• Treatment began at 250 ppm (tubing flow) and 500 ppm (annular
flow) based on oil production and was optimized during the trial.
• Result
AFTER TREATMENT • Mn : 1.1 mg/l, KPI <1.3 mg/l;
• Iron : average <40, KPI <65mg/l).
• Corrosion rate ; < 1 mpy.
• Hydrocarbon Fouling : the coupons were visibly cleaner, with much
less observed deposit forming (see picture beside)
OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• PPD APPLICATION
• FIELD CASES
• SUMMARY
SUMMARY

• Wax can cause problem in flow assurance and phase separation


• PPD in one of the effectiveness treatment of wax inhibition
• PPD has long lasting effect to the pour point decrease
• The best place of injection point is as far as possible such as at well
head
• Field result may deviate from the laboratory test, know the
minimum dosage and over treat effect will be good to determine
starting field trial dosage
REFERENCES

1. Manka, John S; Ziegler, Kim L, Factors Affecting the Performance of Crude Oil Wax-Control Additives, SPE 67326, 2001
2. Grant Slater and Ann Davls, Plpellne Transportatlon of Hlgh Pour Point New Zealand crude Using Pour Point
Depressants, SPE 15656, 1986
3. Technical Brochure Pour Point Depressants A Fluid Flow Improver, PT Prosympac Oil and Gas
4. ASTM D-97 Standard Test Method for Pour Point of Petroleum Products
5. HTS Consultant, Oilfield Production Chemicals and Microbiology
6. Production Chemicals for the 2nd edition Oil and Gas industry, Malcolm A. Kelland, CRC Press, 2014
7. Wax Formation Mechanisms, Wax Chemical Inhibitors and Factors Affecting Chemical Inhibition, Thevaruban Ragunathan
1, Hazlina Husin 1and Colin D. Wood, Department of Petroleum Engineering, Universiti Teknologi Petronas, Seri Iskandar
32610, Malaysia, 2020
8. https://www.championx.com/assets/files/CH_0577_PARA01975A_ChemTech.pdf
9. https://www.clariant.com/en/Business-Units/Oil-and-Mining-Services/Oil-Services/Oil-Innovation
10. https://www.researchgate.net/publication/322376536

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