Demulsifiers-Specialty oilfield

chemicals
Chandran Udumbasseri, Technical Consultant

Introduction

1
 Definitions
• Demulsifiers are a class of specialty oilfield chemicals used to
separate water in oil/oil in water emulsions.
• They are used in the processing of crude oil which contains
significant amount of saline water (produce water).
• This saline water should be removed from crude oil before
refining, as this saline water causes corrosion in equipments
used for crude oil refining process.

2
 Global Market..Oilfield chemicals
• As more petroleum crude oil wells are brought to
production state around the world the demand for
oilfield chemicals are expected to grow vertically.
• The global oilfield chemicals market is projected to
increase at a compound annual growth rate (CAGR) of
5.7% between 2010 and 2015 as the drilling activities
return and production rates are stimulated and new
wells brought online. The market is expected to reach a
value of $8.2 billion at the manufacturing level by 2015,
from a value of $6.2 billion in 2010.

3
 Global Market..Drilling fluids
• Drilling-related chemicals accounted for 52%
of the total 2009 market. It is projected that
by 2015, drilling-related chemicals will
increase to 55% to 56% of the oilfield
chemicals market. This sector is worth an
estimated $2.3 billion in 2010 and is expected
to be worth $3 billion in 2015, a 5.7%
compound annual growth rate (CAGR).

4
Global Market…Enhanced oil Recovery
• The largest growth rate by process application
is expected in chemical-related enhanced oil
recovery (EOR) applications. This sector is
valued at $192 million in 2010 and is
projected to reach $283 million by 2015, an
8.1% compound annual growth rate (CAGR).

5
 Global Market…Demulsifiers
• Demulsifier chemicals including desalters and
deoilers account for approximately 40% of the
world oilfield production chemicals market.
They are deployed at every crude oil
processing station worldwide.

6
 Oil & Gas Market..India
• Oil and gas production in India grew at a CAGR
of 4.2% over the 2000-09 periods. This is
expected to grow at a CAGR of 1% over the
2010-30 periods.

7
VALUE OF OILFIELD PROCESS CHEMICALS BY APPLICATION, 2010 AND 2015
($ MILLIONS)

8
 Suppliers of Demulsifiers -Around the world

• AKZO-NOBEL • Hydrates chemical Co

• Baker Petrolite • Instral BV
• BASF • Multichem - Halliburton
• Brentag • MI SWACO- Schlumberger
• Buckman • Nalco Champion
• CECA • NCPI
• Cochran • REDAOilfield
• Clariant • Scharer & Schlaofer AG
• Croda • UNIVAR
• Dorf Ketal • PCC EXOL
• Dow (Courtesy Wikipedia)
• Eonchemicals Putra

9
 Demulsifier –Main Suppliers
• Baker Petrolite
• Schlumberger
• Halliburton
• Champion (Now part of Ecolab +Nalco)
• Clariant
• Nalco (Now part of Ecolab)

10
 Growth potentials for oilfield
chemicals
• Horizontal drilling and hydraulic fracturing in shale oil
development mainly in US &Canada
• Off-shore drilling of oilfields around the world
• Increasing oil demand in Brazil, India, Africa, China, Russia,
Saudi Arabia, and a number of other Asian countries
• Well stimulation techniques - attractive option for Mexico,
Argentina & Australia
• India and China looking for hydraulic fracturing of shale

11
 Why crude oil Demulsification is
important..?
• The stability of emulsion is very specific to each drilling wells and
will vary in character as the field matures
• In addition to this emulsion there will be some free, uncombined
water, the proportion of which will increase as the water content
increases
• If water /oil separation is not carried then the following problems
are possible:
 Overloading of surface separation equipment
 Increased cost of pumping crude which contains significant water
 High viscosity of emulsion causes pressure development at pumping
 Increase vessel heating costs
 Risk of corrosion
 Storage tank bottoms form thick sludge, difficult to remove
 High levels of basic sediments, water and salt are delivered to the refinery
 Risk of catalyst poisoning

12
 Emulsion & Stability
• An emulsion is a combination of two immiscible liquids that do not mix
together under normal conditions.
• The dispersed phase is present in the mixture in small amount while the
continuous phase is present in large proportion in the mixture.
• In water in oil emulsion the dispersed phase is water and the continuous
phase is oil.
• The water may contain from trace to 70% and perhaps more but such
emulsions are unstable.
• The emulsion may be tight (difficult to break) or loose (easy to break).
• Industrial and domestic effluents contain oil in water emulsion.
• To establish whether the emulsion is oil in-water or water in-oil, add water
or kerosene to the emulsion.
• If dilution occurs on adding kerosene then the emulsion is water in-oil
emulsion and if dilution occurs on adding water then it is oil in-water
emulsion.

13
w/o and o/w emulsions-Photo
Water in oil emulsion

Oil in water emulsion

14
 Class Duration (under
Emulsion Lab condition)
Classification
The emulsion is classified
into four, namely, stable,
meso-stable, unstable and Stable-Actual >4 weeks
entrained water.
Emulsion
Their spontaneous
demulsification time is
tabulated as given: Meso Stable <3 days

Unstable Short time

Entrained water 1 day

15
Crude oil Classification based Classification Density,
on density kg/cu m
Density range of each class
of crude oil is given. Light crude <825
Use the following formula
to convert this to API
(American Petroleum
Institute) gravity Medium crude 825-875
API gravity =
[141.5/Sp.gravity] – 131.5
Heavy crude 875-1000

Extra Heavy >1000

crude

16
 Parameters West North Saudi crude
Africa sea
SARA Distribution crude crude Problematic Non-
wells problematic
The classification of wells

crude oil fraction is based Saturates, 47.9 48 37.5 30.3

on solubility, namely,
saturates (heptane %
soluble), aromatics, resins
and asphaltenes (SARA in Aromatics, 36.5 37.5 44.4 44.5
abbreviation) present in %
the crude oil.
Resin, % 15.2 14.2 13.8 20.7

Asphaltene, 0.4 0.3 4.3 4.5

%

17
 Agitation Effect
• Crude emulsions are formed by vigorous agitation of oil/water
mix
• As crude passes through chokes, wellhead valves, etc extreme
mixing conditions are experienced at the pressure gradient
and new w/o interfaces are formed
• Intensity of agitation is the main factor to determine the
stability of the emulsion
• More shearing action (turbulent flow) to oil-water mixture
causes more water droplet division to smaller ones and thus
the emulsion becomes more stable

18
 Viscosity Effect
• For high viscosity crude more agitation energy is required to
create the emulsion
• High viscosity oil maintain larger dispersed water droplets in
suspension and smaller droplets will have more resistance to
settling
• Viscous crude retards the movement of added demulsifier
• High viscosity crude forms more stable emulsion
• As the water content increases the viscosity of a stable also
increases

19
Viscosity-water cut

20
Crude oil viscosity

21
 Specific gravity Effect
• If there is much difference in the specific
gravity of oil and water phase, then faster
settling of the two phases takes place
• Heavy crude oil tends to keep water droplets
in suspension longer
• Fresh water settles more slowly than salt
water (salt water has higher specific gravity)

22
 Stabilizing Components of Crude
emulsion
• Natural surfactants: organic acids, heterocyclic nitrogen compounds
reduce surface tension slightly
• Resins are absorbed at the interface
• Asphaltenes accumulate at interface
• Paraffin wax crystals precipitate and accumulate at the interface
• Inorganic fines (silt, clays, scale) which are insolubles in the crude
oil accumulates at the interface
• More stable emulsions are formed by oil wettable solids like iron
sulfides and oxides (corrosion products)
• Added corrosion inhibitors, biocides, scale or wax inhibitors are
emulsifiers which add stability to emulsion

23
 Other crude stabilizing factors
• If crude from wellheads are flowing to separator at a lower
temperature emulsion will be less to break
• Long subsea pipe lines result in cooler crude
• Long chain surfactants at the interface can cause steric
repulsion and retard coalescence of water droplets
• Oil wetted solids prevent destabilization of emulsion
• Presence of adsorbed surfactants create mechanical barrier to
coalescence
• Ionic inorganic species generate electrostatic repulsion frces
especially in oil in water emulsion

24
 pH
• The pH of the produce water also plays an important role in
emulsion breaking.
• pH: oil-in-water prefer a low pH (4-6) and water-in-oil prefer
high pH (8-10). When pH is increased from 4 to 6 the more
stable o/w emulsion is formed. But further increase to 6-8
caused less stable o/w emulsion. When the pH is increased to
8, water-in oil emulsion is formed. The water-in oil emulsion is
stable at very high and at very low pH
• Most of the produce water is having pH in the range 6-7 which
is not favorable for stable emulsion

25
 Salt concentration
• 1.Oil-in water droplet size increase with increase of salt
concentration in water while water-in oil droplet size decrease
with salt concentration increase. Sea water gives emulsion of
small size as it is having high concentration of salt. Such
emulsion with high salt concentration water is not stable and
can be broken easily. .
• 2. The inorganic salt in water of the emulsion has adverse
effect on the emulsion stability. Adding salt to emulsion cause
depletion force.

26
 Solid Particles
• Solid particles in the emulsion stabilize the emulsion and
prevent coalescence of water droplets.
• Solid particles/wax, etc, stabilize the emulsion. They get
wetted by the water and oil in the emulsion. They serve as
mechanical barrier to prevent coalescence of the droplets.
• When a small amount of calcium sulfate (plaster of Paris)
powder is added to coconut oil-water mixture and shaken well
it can be seen that the calcium sulfate powder distribute in
the interface of water coconut oil emulsion formed.

27
• The emulsion formed with calcium sulfate powder, water and
coconut oil is more stable as compared to emulsion without
calcium sulfate powder.
• So the stability of the emulsion increases due to solid
particles.
• Asphaltenes add stability to emulsion .Large sized molecules
of asphaltenes are solid in nature at room temperature.
• Wax also adds stability to emulsion.
• At low temperatures wax and asphaltene start crystallizing.
The stability of the emulsion increases as the solid appears at
the interface.
• But as the temperature is increased to 50oC, the wax and
asphaltenes dissolve and disappear from the interface. This
will reduce the stability of the emulsion.

28
 Ageing Effect
• A sample of crude oil emulsion collected and preserved for
sometime suffer ageing
• An aged crude oil sample undergo air oxidation, photolysis,
light fraction evaporation, microbial activity
• Crude emulsion containing oxygenated compounds are very
difficult to break compared to fresh crude emulsion

29
 Crude Oil Emulsion Destabilization
• Flocculation stage: association of large and small water droplets into
clusters but without coalescence
• Creaming or dropping of water: droplet clusters separate in to phases
under the influence gravity. Density difference help dropping
• Coalescence or breaking of free water: as continuous phase separates
then interface film ruptures with free energy reduction
• Destabilization is enhanced by:
 Increased temperature
 Centrifugation
 Electrical methods
 Increased resonance time
 Chemical treatment

30
 Destabilization: heating
• Heating encourage Brownian motion and thus
collision between droplets
• Viscosity of the continuous phase reduces and
help better motion of water droplets
• Heating helps dissolution of emulsifying agent
• Heating is costly, increased asphaltene
precipitation, and increased corrosion risk

31
 Destabilization: centrifugation
• Centrifugation artificially increase G-force
(gravitational force)
• Centrifugation increase concentration of dispersed
phase in the creamed emulsion layer
• Centrifugation breaks the interfacial film of the
emulsion
• Centrifuge and hydrocyclones are used for oil in-
water emulsion

32
 Destabilization: electrical methods
• Electricity was used as early as 1906 to destabilize water in oil
emulsion
• High voltage electrostatic separator are used. Water permittivity is
higher than oil (permittivity is, which is a measure of how easily a
dielectric polarizes in response to an electric field. Permittivity
relates to a material's ability to transmit (or "permit") an electric
field).
• Electric grids are located at the top of the separator in the oil rich
phase
• Applied field causes a dipole on water drops which are attracted to
each other and destabilized by elongation (too much free water
across the electric grid causes short-circuiting)

33
Destabilization: electrical methods

34
Destabilization: electrical methods
GRID PLATES

35
Destabilization: electrical methods

36
Destabilization: electrical methods
• Interaction between droplets creates forces of
attraction resulting aggregation and coalescence
• AC electric fields are used to produce water droplet
dipoles. Droplets are not electrically charged
• Oil in water emulsions respond to dc current leading
to flocculation of droplets through electrophoresis

37
Destabilization: longer residence time
• Crude emulsions are thermodynamically unstable
• If sufficient time is given the emulsion breaks
• The residence time from well head to separator are
usually long and enable significant water separation
making the emulsion breaking more easy
• More residence time in iron pipe lines cause
corrosion risk and slug flow.
• Shorter residence time needs additional options such
as using chemical demulsifiers

38
 Terms explanation: well stimulation
• Well stimulation can be used to improve the flow of natural
gas or crude oil into a well bore.
• Intervention techniques like increasing permeability outside
the bore are used for well stimulation - clean the formation or
increase perforation and fractures in the reservoir
• To clean the formation, chemicals like formic acid (acidization)
is pumped in to the bore to dissolve the blockage
• Creating additional cracks and fractures in the reservoir
increases the permeability

39
 Well completion
• When a well is drilled the decision is whether this well can be
a producer well or be plugged and abandoned as a dry hole
• If the decision is to develop the well to produce oil, then well
completion steps should be undertaken
• well completion steps transform the drilled well to a
producing one
• The steps are, casing, cementing, perforating, gravel packing,
and installing a production tree

40
 Well completion: casing

Casing: Source: Schlumberger

41
Well completion: cementing

Cementing: Source: MPG Petroleum

42
Well completion: perforation

Perforation: Source: Halliburton

43
Well completion: gravel packing

Gravel Pack: Source: Schlumberger

44
Well completion: production tree installing

Production Tree: Source: Cameron

45
 Term Explanation: horizontal drilling
• Horizontal drilling is used to gain access to pockets of oil and
gas that may be missed or unreachable by traditional vertical
drilling.
• A vertical hole is drilled first, and then the horizontal drilling
is spurred off from there.
• The vertical part of the drill can be used for several horizontal
drills in different directions and extended for over a thousand
feet from the vertical hole.
• While horizontal drilling is about twice as costly to set up as
traditional vertical drilling, the greater quantities of oil and
gas that are returned pay for the increased investment

46
Horizontal drilling

47
Term Explanation: hydraulic fracturing
• Hydraulic fracturing is process where millions of gallons of
water, sand, and chemicals are pumped underground to break
apart the rock and release the gas.
• Fracking or hydraulic fracturing, is the process of extracting
natural gas from shale rock layers deep within the earth
• Fracking makes it possible to produce natural gas extraction in
shale rock that were once unreachable with conventional
technologies
• Horizontal drilling (along with traditional vertical drilling)
allows for the injection of highly pressurized fracking fluids
into the shale area

48
Hydraulic fracturing

49
 Terms Explanation: Shale
• Shale is a fine-grained sedimentary rock that forms from the
compaction of silt and clay-size mineral particles that we
commonly call "mud“
• Some shales have special properties that make them
important resources. Black shales contain organic material
that sometimes breaks down to form natural gas or oil
• Black organic shales are the source rock for many of the
world's most important oil and natural gas deposits

50
 Shale rock

Organic-rich black shale. Natural gas and oil are sometimes trapped in the tiny pore spaces of
this type of shale.

51
Extraction of gas/oil from Shale
Unconventional –horizontal
Conventional method drilling and hydraulic fracturing

52
 Enhanced Oil Recovery (EOR)
• Oil production is separated into three phases:
primary, secondary and tertiary (which is also known
as Enhanced Oil Recovery -EOR).
• Primary oil recovery is limited to hydrocarbons that
naturally rise to the surface, or those that use
artificial lift devices, such as pump jacks.
• Secondary recovery employs water and gas injection,
displacing the oil and driving it to the surface

53
 EOR………………
• Primary and secondary methods leave 75% of the oil
in the well. By EOR methods 75% of the this oil can
be recovered
• Secondary recovery uses water or gas injection, EOR
uses steam/gas to change the make up of the
reservoir
• Types of EOR: chemical flooding, gas injection and
thermal recovery

54
Gas/chemical injection

55
 Thermal recovery
• Heat is used to reduce viscosity of oil. Steam is applied for
thinning oil and enhance flow

56
 Chemical injection
• Chemical injection EOR helps to free trapped
oil within the reservoir.
• This method introduces long-chained
molecules called polymers into the reservoir
to increase the efficiency of water flooding or
to boost the effectiveness of surfactants,
• Surfactants help to lower surface tension that
inhibits the flow of oil through the reservoir.

57
 Gas injection-EOR
• Gas injection used as a tertiary method of
recovery involves injecting natural gas,
nitrogen or carbon dioxide into the reservoir.
• The gases can either expand and push gases
through the reservoir, or mix with or dissolve
within the oil, decreasing viscosity and
increasing flow.

58
Gas injection

59
Chemical demulsifiers for crude oil

60
• Chemical demulsifiers are used through out
the world to improve emulsion breaking
processes
• First demulsifier – Sulphonated castor oil
• Today demulsifiers are prepared from
surfactants of various hydrophilic/lipophilic
balance values:
Non-ionic
Cationic
Anionic

61
 Demulsification process
• To break crude oil emulsion the ordered structure of
natural surfactant/emulsion system must be
disrupted
• On adding demulsifier the following properties are
modified:
 Surfactant behavior at water /oil interface
 Ability to flocculate dispersed phase drops
 Ability to cause coalescence of dispersed phase
 Wettability of solids

62
 HLB values
• Surfactants are classified by HLB values
• Surface active molecules with similar structures show stability
maxima corresponding to w/o emulsifiers and o/w emulsifiers
• There is stability minimum where neither hydrophilic nor
hydrophobic groups dominate the interfacial region
• Most demulsifiers are having HLB values in the region of this
stability minimum
• Useful demulsifiers are those that adsorb or partially displace
the natural surfactant, then desorb again after film rupture
• Performance characteristic of these products can be varied by
molecular weight, solubility, charge reduction potential,
flocculation behavior, etc.

63
 Types of demulsifers
• Acid catalyzed phenol-formaldehyde resins
• Base catalyzed phenol-formaldehyde resins
• Epoxy resins
• Polyethylene amines
• Polyamines
• Di-epoxides
• Polyols
• EO/PO Block polymers
• The above are usually ethoxylated (and/or propoxylated) to provide
the desired degree of water/oil solubility. The addition of Ethylene
oxide increases water solubility, Propylene oxide decreases it.

64
 EO/PO Block polymers
• Non-ionic EO/PO Block polymers are good for
flocculating small sized water droplets
• They are called treaters
• They flocculate tiny individual water droplets
in w/o emulsion
• Molecular weight range is 1000-10000

65
 Ethoxylated alkylphenol resins
• Ethoxylated resins are good for water dropping and coalescence
• Performance of these resins can be modified by:
o Varying the alkyl group
o Degree of ethoxylation/propoxylation
o Cyclic formations
• Acid catalyzed resins are effective for water dropping and
coalescence, but good residence time is required for good water
quality
• Higher Mol Weight products show wetting capability
• Mol weight range 500-2000 shows good dropping ability

66
 Di-epoxides
• Di-epoxides are excellent emulsion breakers, they
separate water if used singly, but show good
performance in blends with resins and/or polyamines
• They are oil cleaners giving low BS&W and salt
content
• Polyethylene glycols of different mol weight are
reacted with bisphenol A to give products with
varying HLB values

67
 Polyamines
• Polyamine are similar to di-epoxides and give
low BS&W and very good desalting
• They blend with resins and give faster water
separation
• Disadvantage is that they need considerable
initial mixing and long contact time

68
 Polymerized Polyols
• Polymerized polyols show rapid penetration through oil phase
reaching emulsified water.
• This penetration is vividly demonstrated by the rapid blackening of
cream-colored emulsions and the quick brightening of water-hazed
emulsions.
• They are extremely oil soluble in nature and exhibit great tenacity
for finishing the dehydration of crudes where more water-soluble
compounds can “wash out” with the water phase of a partially
resolved emulsion.
• Polymerized polyols typically require blending with other emulsion
breaker intermediates to achieve complete treatment of water-in-
oil emulsion.

69
 Polyol Esters
• Polyol esters are a reaction product of a polyalkylene oxide
block polymer and a polyfunctional organic acid. Polyol esters
are particularly effective on fresh-water emulsions and tend
not to cause emulsion inversion or oil-in-water emulsions.
• Polyol esters act, as do most emulsion breakers, by
counteracting the effect of naturally occurring emulsifiers.
• Polyol esters are an effective emulsion breaker when used
separately or in blends with oxyalkylated phenolic resins. This
high molecular weight chemical is non-ionic in character.

70
 Resin Esters
• Resin ester intermediates are reaction products of an
oxyalkylated phenolic resin and an organic carboxylic
acid.
• Resin esters are unusually effective when used as a
detergent or as a wetting agent in emulsion breaker
formulations.
• Despite resin ester’s high detergency, they do not
cause inversion to oil-in-water emulsion. Resin esters
have also been used in limited applications as a
desalting chemical and in treating slop oils.
71
 Polyalkylene glycols
• Polyalkylene glycols are non-ionic in character. They work by
counteracting naturally occurring emulsifiers.
• These Polyols have been found to be particularly effective
when used in low salt water brine or in fresh water emulsions.
• In these cases, polyols are often formulated with sulfonates or
used as is.
• Polyols exhibit exceptional ability to lower interfacial tension
and, as a result, have a high degree of wetting activity. For this
reason, polyols can effectively disperse or deflocculate solids.
• Polyalkylene glycols can be used with effectiveness in
synergistic blends with oxyalkylated phenolic resins

72
 Sulfonates
• Sulfonates have outstanding characteristics that include low
cost and a resistance to “burning” or “overtreating” when
used in formulations to treat crude oil emulsions of the water-
in oil type.
• Sulfonates aid in emulsion breaking by counteracting naturally
occurring emulsifiers and are extremely effective in resolving
loose water emulsions stabilized by solids. Sulfonates are
often used in treating refinery “slop” emulsions as well as
tank bottoms
• Sulfonate intermediates are generally used in conjunction
with oxyalkylated phenolic resins and with polyglycols.

73
Compounds with demulsifying activity
• Polyethylene imine alkoxylate & Mono or oligo-amine
alkoxylate.
• Alkoxylated alkylphenol formaldehyde resin.
• Alkoxylated amine modified alkyl phenol formaldehyde resin.
• Co or ter polymers of alkoxylated acrylates or methacrylates
with vinyl compounds.
• Condensates of mono- or oligo- amine alkoxylates,
dicarboxylic acids and alkylene oxide block polymers (may be
quaternized at nitrogen).
• Cross linked products of all above

74
 Compounds acting as demulsifying
assistant
• Poly alkylene glycol ethers
General Formula, [R’(OA1)a ..OH]n , R’ = C7 to C20
alkyl group, phenyl group, alkyl phenyl group:
A1,A2,A3 = 1,2 alkylene group with 2 to 4 carbon
atoms, phenyl ethyl group ( there should be one 1,2
alkylene group with 4 carbon atoms); a = 1 to 50; n =
1 to 10.
• General Formula H-(OA1)b-(OA2) c-(OA3) d-OH
(where b, c and d each has value from 0 to 50 and
b+c+d is >3).
75
 Classification –water droppers
• Water droppers coalesce water droplets in the
crude oil and release free water.
• Predominant type is based on alkyl phenol
formaldehyde resins with low levels of
addition of ethylene oxide or propylene oxide.
• These demulsifiers also show excellent
desalting properties.

76
 Treaters
• The primary function of these compounds is to flocculate the
large number of submicron water droplets dispersed in the
crude oil. Water droplets are thus concentrated at the base of
the oil column prior to coalescence and the crude is
dehydrated above the settling level of the flocs.
• This can be noticed by the brightening of the top oil in
contrast to its dull appearance when the water dispersion
existed.
• The predominant type is based on high molecular poly
propylene glycol molecules with hydrophilic ‘tips’ which
solvate into the water droplets and facilitate gathering.

77
 Hybrids
• These compounds incorporate a balance of
molecular design features such that both
‘dropping’ and ‘treating’ characteristics are
exhibited.
• Hybrids are more cost effective than blends of
droppers and treaters.

78
 Desalters
• The emulsions coming along the crude to the desalting stage
have low amounts of water and are less stable. Some of the
naturally occurring emulsion stabilizers have been removed at
the 1st stage demulsification process. The droplet size is not
very small. High potential electric field applied coalesce these
polar salt water droplets.
• A good desalter demulsifier would achieve rapid water
separation at low level addition rates.

79
 Wetting agents
• Some ethoxylates, sulfonates, amine ethoxylates are
extremely useful for treating emulsions stabilized by
inorganic solids
• They selectively wet the surfaces of inorganic solids
like, clay, sulfides, iron hydroxides
• Organic solids such as paraffins can be effectively re-
solublised to the organic phase by using wetting
agents
• Sulfonated oils exhibit good wetting ability.

80
 Gas Oil Separating Plant (GOSP)
Sample Point D1 HPPT

D2 LPPT

Production
Header
D201 HPPT

D212 Desalter D211 Dehydrator

Shipment line

81
 GOSP-Saudi Aramco
• The flow chart given above is a typical gas oil separating plant
in Saudi Aramco. Almost all GOSPs have the same flow chart
except a few
• The crude is collected at Production header through pipes
from different production wells
• Production header is pipes of 36” diameter size. Demulsifier,
corrosion inhibitor, scale inhibitor and biocide are injected in
this order to this header
• Crude oil samples for “bottle testing” are collected from the
header before the injection point of demulsifier

82
 Crude processing in GOSP
• The crude oil gets mixed with demulsifier and other
additives through turbulent flow inside the pipe
• Wet Crude enter the first separator, which is called
High Pressure Production Trap (HPPT – D1 & D201 in
the flow chart). Here the separation of gas-oil-water
takes place
• Water gets collected at one side of divider baffle and
oil overflows from the top to the outlet. Water flows
out from the bottom. Gas escapes through the vent
to gas collection tanks.

83
 Crude processing …2
• The oil from outlet flows to Low Pressure Production Trap
(LPPT, D2 in the flow chart). As the pressure is reduced all gas
gets removed from crude
• Almost 70% water in crude oil is separated in HPPT while no
water is separated at LPPT separator.
• Gas freed oil flows to Dehydrator (D211 in the flow chart).
Dehydrator is electrostatic grid with aid water separation
electro statically (Slide 27,28,29).
• Water separated is removed through bottom of dehydrator.
Almost all the remaining water (30%) is separated from this
vessel.

84
 Crude processing…..3
• The oil from the outlet of dehydrator should be dry with </=
0.2% water content
• Oil from the outlet of dehydrator is mixed on-line with wash
water (vary from 10-15% by volume of crude). This water is
added to remove any crystallized salt in the dried crude from
dehydrator
• Wash water mixed crude is fed to desalter (D212, in the flow
chart). Here also the water is removed electro statically.
• The dried and desalted crude oil from desalter should meet
the specification of Saudi Aramco
• Oil specification, Salt content = < 8PTB; BS&W = < 0.2%

85
 Vendor Registration-Saudi Aramco
• Vendors are registered to Saudi Aramco after approval for
prequalification. Supplier Relations Management Unit
(SRMU) of Saudi Aramco is managing the vendor approval.
• http://www.saudiaramco.com/content/mobile/en/home/doin
g-business-with-us/materials-suppliers/registering-as-a-
materials-supplier.html
• Vendor portal is used by the supplier for submitting their
products
• For overseas vendors like India the following agency is looking
into such matters

86
 Aramco Overseas Agency
Manufacturers & India and Malaysia, Aramco Overseas Company B.V. India
Suppliers Singapore, Branch Office
Registration Indonesia, Unit 610, Level-6, Time Tower Building
Thailand, Vietnam, MG Road, Gurgaon,-122002, Haryana., India
Cambodia, & The Tel: +91 (0) 1244983900
Philippines Fax: +91 (0)124 498 3909
Email: AOC-India_registration@aramco.nl
Website: http://www.aramcooverseas.com/

The above nations can use Aramco Overseas

Agency for submitting their registrations

87
 Oil producers in Middle east area
• Saudi Arabia – Saudi Aramco
• Kuwait – KOC
• Abu Dhabi – ADNOC
• Bahrain – Bapco
• Qatar – QP
• Oman – Petroleum Development Oman (PDO)
• Syria-Syrian Petroleum (Al Furat, de Ezour, Sino)
• Iran-NIOC
• Algeria –Sonatrach
• Libya - LNOC

88
GOSP-Demulsifier consumption

89
 GPD

120
140
160
180
200

100

0
20
40
60
80
3/2/2009

120
7/2/2009

112
24/2/2009
28/2/2009 180
7/3/2009 165
180

15/3/2009
140

95
24/3/2009
29/3/2009
160

6/7/2009

70 70
16/7/2009
1/8/2009
9/8/2009 65 65
29/8/2009 57 60

7/9/2009
65

29/9/2009
10/10/2009
55 55

17/10/2009

Date/Time/Period
90

31/10/2009
GPD (S 4 Demulsifier dosage)

70

14/11/2009
90

21/11/2009
2/12/2009
150

6/12/2009
14/12/2009
125125

21/12/2009
160

28/12/2009
140

4/1/2010
113

11/1/2010
100

75

18/1/2010
Demulsifier dosage-histogram

70

1/2/2010
92

16/2/2010
90
 Dosage pattern
• Above data were from actual results
• The patterns of dosage show high value from months
November to April while it is minimum from months
May to October
• There are two dosage rates winter and summer
rates. Winter rates high and summer rates low
• The pipe lines, through which oil is delivered from
wells, are effected by temperature variation of winter
(-5C to 15C) and summer (40C to 60C)

91
Yearly consumption of demulsifiers
Yearly anticipated consumption in all 28 GOSPs, US Gallons per year

GOSP Consumption /year, GPY GOSP Consumption /year, GPY

ABQaiq-2 4460 Uthmaniyah 4 121730
ABQaiq-3 10820 Uthmaniyah 7 59500
ABQaiq-5 4450 Uthmaniyah 8 45900
ABQaiq-6 4420 Uthmaniyah 9 29750
Aindar 1 70300 Uthmaniyah 10 35160
Aindar-2 51400 Uthmaniyah 11 70330
Aindar 3 51400 Uthmainyah 12 62220
Aindar 4 48690 Uthmaniyah 13 29700
Aindar 6 43280 Hawaiyah 2 100090
SHadgm 1 59500 Hawaiyah 3 175800
SHadgm 3 108210 Hawaiyah 4 119030
SHadgm 4 86560 Harad 1 175800
SHadgm 5 119030 Harad 2 75740
SHadgm 6 43280 Harad 3 54100
Total,gallons 705800 1154850
Grand total, gallons 1,860,650
GOSPs which go bottle test bidding separately (not included here)
Shaibah, Kurais, Khursaniyah, Safaniyah, Zuluf, Tanajib, Qatif, Khafji, Hout, Manifa

92
Demulsifier formulations

93
 More bases in formulation
• Demulsifiers are not always single component, but formulated
with more than one and sometimes with 4 or more bases.
• Demulsifier reduces interfacial tension between water and
crude oil
• For better demulsification natural gas should be removed
from crude
• Demulsifier is injected at the wellhead giving adequate time
before crude reaches the separator.
• Demulsifier should reach the targeted interface to function
effectively. It should have right solubility. It is attracted to the
target through difference in polarity.

94
• The stability of emulsion vary from well to
well. So it is necessary to develop demulsifier
blends to specific targeted crude oil.
• They are selected based on their performance
in bottle tests and centrifuge tests.
• These tests help to identify products that
produce maximum water dropping with
cleanest oil phase
• The sample should be tested for fastest water
drop, sludge, quality of interface, quality of
water
95
Bottle Test Report

96
 Relative Solubility Number (RSN)
• The RSN value assigned to each demulsifier components
indicates its relative solubility in water (RSN is an empirical
value)
• As the numerical value increases the solubility of the polymer
in water increases
• Practically the product having RSN<13 are insoluble in water
• RSN 13-17 are dispersible in water at low concentration and
form gel at high concentration
• RSN>17 are completely water soluble

97
 Guidelines for RSN
• For a crude oil emulsion, a demulsifier formulation should
have RSN between 6 and 15. The RSN value can be added
algebraically.
• A 50-50 blend of two bases with RSN of 10 and 20 will yield
blend RSN as 15 (10+20 = 30/2=15)
• Synergism between intermediates make demulsifier blend
better than single component system
• Demulsifiers with very low and very high RSN are not used
individually
• Due to synergism, blends of intermediates from different
chemical groups make better demulsifiers, than blends using
intermediates from same family of compounds

98
• Some demulsifiers have special properties that give them very
good blending characteristics
This is the case with highly oil soluble (low RSN)
polyglycols. When blended with oxyalkylated resin give
excellent demulsifier formulation. Other blends are
resin with polyols, diepoxides, polyacrylates based
molecules
• To get dried oil, water droppers and oil driers are used. Water
droppers work very quickly due to flocculation of large
droplets, the base sediment will be greater than 1%
• Drying demulsifiers reduce water content fully via coalescence
but takes longer time.

99
Synergism in formulation

100
 Synergism
• In the above graph conductivity is plotted against
temperature
• As emulsion breaks the water droplets coalesce and
the conductivity increases due to salinity of water.
• As the temperature increases more emulsion breaks.
• Thus conductivity proportional to amount of
emulsion broken.
• The rate of emulsion breaking with temperature is
different for components 1,2,&3 and amount of
breaking also less in the temperature range 30C-50C

101
• The plot of DF Formulation ( ) is of formulated
demulsifier from components 1, 2 & 3.
• Compared to individual plots, the plot of
blend suddenly shoots up to the maximum
showing large amount of emulsion breaking.
• This is the synergic effect of blends

102
 Effectiveness of demulsifier
• Capable of treating a wide range of emulsions under the most
demanding field conditions - including short residence times,
high turbulence, high solids loading and water content.
• Should possess different types of property:
1.Flocculant or treater
2.Coalescer or dropper
3.Wetting Agent (wetter/dispersant)
4.Booster for special crudes (asphaltene / wax additives)
5.Solvent system (usually hydrocarbon based)
• The emulsion from a group of wells change with time.
Composition of a crude oil will change within time as well
usually the amount of water will increase during production

103
• If the demulsifier formulation is poor then:
– Poor water separation
– Emulsion build up at the oil/water interface
– High water cut in the treated oil
– Oily water
– “Sludging”, usually at the interface but can occur
throughout the oil layer. The “sludge” is a new
emulsion.
– “Bad oil” production then contaminates clean oil
in storage

104
• Good demulsifier formulation depends on the
following:
– evaluate the system,
– plan the test,
– obtain a representative sample,
– carry out a ratio test,
– screen the individual actives,
– develop and screen potential formulations,
– then follow with a final evaluation and selection

105
• For good formulation, the sample should be:
– Representative of the production system
– Composite
– Consistent with current production
– Chemical free (absence of normally injected field
chemicals)
– Contaminant free
– Fresh
– Consistently available

106
• Parameters noted in bottle tests are:
– Speed and amount of water drop
– Top oil treatment
– BS - sludge formation
– Interface quality
– Clarity of water
– Colour of oil
– Nature of centrifuge cut

107
 HLB values
• The Hydrophilic-lipophilic balance of a non-ionic surfactant is
a measure of the degree to which it is hydrophilic or lipophilic
• HLB may be theoretically calculated using the formula:
– HLB = Weight % Hydrophile/5
– Example: lauryl ethoxylate (1:4)
– Mol Weight of ethoxylate part = 176
– Mol Weight of lauryl alcohol = 186
– Weight% = [176/(176+186)]*100 = 48.6%
– HLB= 48.6/5 = 9.7
• HLB value below 9 is taken as lipophilic and HLB above 11 is
taken as hydrophilic. HLB between 9-11 is intermediate
• HLB values are used for emulsifiers
108
 HLB of blends
• When two or more emulsifiers are blended
the resulting HLB can be calculated:
– Example: Blend of 70%Tween 80 (HLB, 15) and
30% Span 80 (HLB, 4.3)
– Tween 80=0.7x15 = 10.5
– Span 80 = 0.3x4.3 =1.3
– Sum value = 11.8 is the calculated HLB for the
blend

109
HLB Value &Classification of chemicals

 Chemicals can be classified using HLB values.

Table shows the classification into groups:

110
Required HLB calculation
• Table below shows how the required HLBs
can be calculated. Here Tween 60 (HLB=4.7)
& Span 60 (HLB=14.9) are used

111
 HLB vs RSN
• Relative solubility number (RSN) provides a practical
alternative to the HLB method of assessing hydrophilic-
lipophilic balance of surfactants.
• It is a different possibility to characterize demulsifiers in the
Oilfield area.
• Raw materials for demulsifiers are mainly non-ionic
surfactants and can be characterized by the RSN number
• It was found that, within the same surfactant family, RSN
values determined at certain molar concentration showed a
good linear relationship with classic HLB values.

112
 HLB vs RSN
• The surfactant concentration in RSN titration,
solvent affected the RSN values;
• The effect of salt concentration in the titration
water was negligible.
• A generalized regression model was used to
correlate RSN values with the structure
parameters of surfactants such as carbon
number in hydrophobic groups, C-O number
and free OH number.

113
 RSN & Mol Weight relation
• Research shows that there is no overall correlation between
demulsification performance and RSN value.
• But within a given surfactant family, such as polymerized
polyols, oxyalkylated alkylphenol formadehyde resins, and
oxyalkylated alkyl resins, the degree of demulsification was
found to correlate with the RSN value.
• A maximum of dewatering performance was observed in a
specific RSN range for two surfactant families. Molecular
weight also showed a significant effect on demulsification
performance.

114
 RSN & Mol Weight correlation
• Surfactants with low molecular weight (<4000) did not break
the emulsion in dosages of 300-400 ppm regardless of RSN
value.
• For the water-in-bitumen emulsion studied in this research
work, the most effective demulsifiers are those with RSN
values between 7.5 and 12.5 and molecular weights between
7500 and 15000

115
 RSN, Water dropping, desalting
• Bottle test results of Saudi Aramco crude
showed the following correlation:
– Higher RSN causes higher water dropping up to
RSN 21.5 then decreases as RSN increases
– Low RSN (<10) showed very low salt content in dry
crude layer
– Better results were observed if the demulsifier
bases were from the same chemical family of the
same manufacturer

116
 End
• ?

117