Road Map Penelitian Surfaktan Peptida

Page 1

Surfactant Peptida LEMIGAS (SUPEL)

2011-2012
Belajar dari Pepfactant (AM-

1 & AFD-4)
Perancangan Surfaktan

Peptida LEMIGAS
Salinitas: 11.400 mg/l
APIo: 43,8
Viscositas: 0,63 cp

Phase Behavior: Fase Tengah

IFT: 0,03 dyne/cm (@ 25oC, pH 11); 0,06
dyne/cm (@ 25oC, pH 11, 1 bln)
Perubahan sudut kontak (wettability): 0,025
63o 15o

Adsorpsi: 0,19 mg/g

Achievements
1. Usulan Paten
Sekuen Molekul Asam Amino Peptida Bersifat Surfaktan Anionik
2. Karya Tulis Ilmiah
a. Pengaruh Jenis Struktur Molekul Peptida terhadap Tegangan Antar
Muka: Sebuah Upaya Pengembangan Surfaktan EOR dengan
Nanobioteknologi
b. Perancangan Surfaktan Protein untuk Pengurasan Minyak
3. 104 Inovasi Indonesia Prospektif - 2012

Page 3

CHEMICAL FLOODING: CONCEPTS AND MECHANISMS

Objektif eksplorasi-eksploitasi migas

Initial

OOIP =
366 MMstb

Primary
Recovery

Secondary
Recovery

RF = 42%

RF = 25%

Cadangan =
155 MMstb

Cadangan =
90 MMstb

Field oil rate

3
Field Life Time

Time
Page 5

Tertiary
Recovery
RF = 64%

Cadangan =
235 MMstb

Reservoar Model

aliran masuk

Hukum kekekalan massa:

aliran masuk - aliran keluar sink/source akumulasi

np

u i
1

n p
q i S i
t 1
1

A
x

np

more familiar
form
Page 6

aliran keluar

1
1

uo qo
So
x Bo
t Bo

x+x

Oil recovery phases and EOR technology

25%
primary

OOIP
+25%
secondary

+15%
tertiary

???

Field Life Time

Field oil rate

Recovery factor

Time

N p qodt
0

RF

Np
N

LEMIGAS

Page 7

Who is the hero in the reservoir engineering

Page 8

Physics

Newton and Einstein

Biology

Darwin

Reservoir
Engineering

Henry Darcy (1856)

Illustration of a typical chemical flood

Injection
Fluids
Production Well

Injection
Pump

Oil

Injection
Well

Driving
Fluid
( Water )

Page 9

Tapered
Polymer
Slug for
Transition
to Drive
Water

Polymer
Solution
for
Mobility
Control

Surfactant
Slug for
Releasing
Oil

Additional
Oil
Recovery
( Oil Bank )

LEMIGAS

Recovery factor for displacement processes

Oil recovery pada setiap proses displacement fungsi dari:
- Volume reservoar yang disapu (swept) oleh fluida injeksi, dinyatakan dengan
volumetric displacement efficiency (EV) macroscopic.
- Recovery factor pada area yang disapu oleh fluida injeksi, dinyatakan dengan
displacement efficiency (ED) microscopic.

Material balance untuk oil displaced (Np) dinyatakan sebagai:

S
S
N p o1 o 2 V p EV
Bo1 Bo 2

Recovery factor:
RF

Page 10

Np
N1

So1 = saturasi minyak pada awal displacement

So2 = saturasi minyak pada akhir displacement
Bo1 = FVF minyak pada awal displacement
Bo2 = FVF minyak pada akhir displacement
Vp = reservoir pore volume

So 2 Bo1
So1Bo 2

ED EV

ED 1

ED E A EI

EA = areal displacement efficiency

EI = vertical displacement efficiency

Stability of displacement

EV

ED
So1

So2
So2< So1

Page 11

So1

Stability of displacement
M>1

Stability of displacement is controlled by mobility ratio,

M defined as:
D= mobility of displacing fluid
D
M
phase behind the front
d
d= mobility of displaced fluid
phase ahead of the front

Page 12

M<1

Stability of displacement in dipping reservoirs

interface

oil

Unconditionally stable
Mo < 1
>

oil

Unconditionally stable
Mo = 1
=

oil

Stable if Ng > Mo - 1
Mo > 1
<

oil

Unstable if Ng < Mo - 1
Mo > 1
<

water

water

water

water

Page 13

Ng

k wg sin
u w

1 Darcy = 10-12 m2
1 bbl = 0.1589873 m3
1 cp = 0.001 kg/m.s

Example:
Recovery factor for a waterflood and EOR displacements
Initial

Primary Rec.

OOIP =
366 MMstb
Cadangan =
90 MMstb

WF

Cadangan =
155 MMstb

Page 14

SPF

Cadangan =
235 MMstb

Factors affecting displacement efficiency

Areal displacement
efficiency affected by:

Vertical displacement
efficiency affected by:

Displacement efficiency
affected by:

Mobility ratio

Mobility ratio

Lateral heterogeneity

Gravity segregation

characteristics

Injection volume

Layer heterogeneity

Fluid viscosity

Injection/production

Injection volume

Rock wettability

well pattern

Relative permeability

Injection volume
Gravity forces
Capillary forces

Page 15

Flooding patterns

Injector
Page 16

Producer

Areal displacement efficiency

Five-spot pattern:

EA

1
1 0.2062 ln M 0.0712 0.511 f w 0.3048 ln M 0.123 0.4394

Direct line drive:

EA

Page 17

1
1 0.3014 ln M 0.1568 0.9402 f w 0.3714 ln M 0.0865 0.8805

Vertical displacement efficiency

Any change in a parameter in R v/g that reduces its numerical value contribute to gravity effects, which leads
to early breakthrough of the displacing fluid.
Page 18

Vertical displacement efficiency

Dykstra-Parsons Method

0
0
Mo krw
o kro
w

Y WOR 0.4 18.948 2.499VDP

0.8094VDP 1.137 10X

2
X 1.6453VDP
0.935VDP 0.6891

EI 0.199 0.182 ln Y 0.016 ln Y 2 4.62 103 ln Y 3 4.3 104 ln Y 1 2.77 104 Y

Page 19

Microscopic displacement efficiency

The residual oil saturation is a function of the trapping mechanisms.

Trapping mechanisms are a function capillary.

Page 20

Microscopic displacement efficiency

ED 1

So 2 Bo1
So1Bo 2

Capillary desaturation curve relates the amount of trapped nonwetting or wetting

phase as a function of capillary number.
Other forms of capillary number
Laboratory
N vc

u
0
0
[(krw
/ w ) ( kro
/ o )]

u
N vc w

N vc

u w

0
krw

Field
N vc

Page 21

0.565 q w
h Ap

N vc

0.565 q w
h Ap

Microscopic displacement efficiency

Immiscible and miscible processes based on mixing between displacing fluid and oil.
Imbibition and drainage processes based on wettability of the porous medium.

Effect of wettability changes, mixing fluids, and interfacial tension on oil-water relative
permeability curves

Page 22

Chemical flooding

Chemical floods are methods where one or more of specially selected

chemical substance are added to the injection water with the main
objective of increasing oil recovery factor beyond waterflood levels.
The following mechanisms can be achieved with chemical floods:
Increasing the macroscopic volumetric displacement efficiency due to
reduction of mobility ratio.

Achieved by using polymers.

Increasing the microscopic displacement efficiency due to reduction of

residual oil saturation.

Achieved by using surfactants and alkaline.

Increasing the imbibition efficiency due to alteration of reservoir rock

wettability.

Page 23

Achieved by using surfactants and alkaline.

Chemical flooding

Most filed applications are designed that utilize at least two chemical
substances.
These combination floods include:
Surfactant polymer (SP), also known as micellar-polymer (MP),
Alkaline surfactant polymer (ASP),
Alkaline polymer (AP).
Thin film spreading agent surfactant polymer (TFSA-P)

Page 24

The role of chemical substances

The role of polymer:
Decreasing mobility ratio by increasing polymer solution viscosity
The role of surfactant:
Lowering oil-water interfacial tension
Altering rock wettability
Lowering bulk-phase viscosity
Promoting emulsification
The role of alkaline:
In alkaline flooding, high-pH chemical system is injected. Alkaline and acid
hydrocarbon species in crude oil react to generate the surfactant.
The role of TFSA:
Altering rock wettability towards a more water-wet
Lowering oil-water interfacial tension.
Page 25

Polymer

Page 26

Polymer substance
Polymers are made up of very large molecules and act as thickeners when
dissolved in water that result in high solution viscosity
Polymer types:
Parameter

Page 27

Bio-polymers

Synthetic polymers

Such as

Xanthan

Polyacrylamides

Made by

Fermentation

Hydrolysis

Charge

Neutral

Negatively charged

Effect of salinity

Less sensitive

More sensitive

Viscosity

High

Medium

Price

Expensive

Less expensive

Effect of bacteria

Attacked

Not attacked

Effect of shear

Thinning

Thickening

Polymer solution viscosity

Solution viscosity affected by:
Polymer type and Concentration
Salinity
Shear rate
Visco-elastic effects
Inaccessible pore volume (IPV)

Page 28

Permeability reduction and visco-elastic effects

All polymers exhibit shear thinning, non-Newtonian behavior in laboratory viscometers.
In porous media at very high shear rates, bio-polymers maintain this behavior while HPAM
shows behaves different than laboratory viscometers.
Viscosity of bio-polymers decrease with shear rate till
but retain original viscosity if shear rate is
decreased back to low values.
This behavior (shear thinning) is related to high
molecule elasticity short relaxation time (period
required for molecules to retain original shape after
distortion).

Bio-polymers exhibit low apparent viscosity near

injection wells and, consequently; improved injectivity.
HPAM polymers exhibit long relaxation time and some permanent distortion if subjected to
very high shear rate and their apparent viscosity may increase (shear thickening).
Some permeability reduction results from injecting HPAM polymers into reservoir rocks.
Page 29

Permeability reduction and visco-elastic effects

Resistance factor, permeability reduction factor, and residual resistance factor are
the technique index of describing the retention amount of polymer and polymer
gel in the porous media. They are denoted by RF, Rk, and RRF.
P3
kw
kw w
P2 k w p
R

Rk

RF
RF
RF

P1 k wafter
k

P k
p
p
1

p w

Experimental procedure:
1. Saturating the core by formation water, injected water flooding, recorded the
pressure P1.
2. Injected chemical flooding 4PV 5PV, recorded the pressure P2.
3. Injected subsequent water 4PV 5PV, recorded the pressure P3.

The injection rate is 0.3 mL/min, the time interval of pressure record is 30
min.

Page 30

Inaccessible PV
Polymer molecules are larger than water
molecules and are large relative to some
pores in a porous rock.
Because of this, polymers do not flow
through all the pore space contacted by
brine.
The fraction of the pore space not
contacted by the polymer solution is called
the inaccessible pore volume (IPV).
The magnitude of IPV can range from 1%
to 30%, depending on the polymer and
porous medium.

Page 31

Polymer retention
Polymer adsorption is the main form of retention.
Measured in laboratory using representative core and fluid samples.
Polymer adsorption (p) is a function of polymer concentration (Cpl) in the injected
slug. Mathematical expression is:

p a pC pl 1 b pC pl

p
= polymer adsorption, mg/g or g/kg
ap, bp = constants depend on polymer type

Converted to represent volume of polymer solution per unit pore volume,

D pl p p 1 C pl

Page 32

s = rock solid density, kg/m3

= porosity, fraction
Cpl = polymer concentration in solution, g/m3
Dpl = polymer adsorption, fraction of floodable PV,
usually referred to as polymer frontal advance loss

Polymer degradation
Temperature
Temperatures in the range 120-130C, could cause most polymer solutions to crack
and lose their viscosity

Hydrolysis
Can reduce viscosity of all polymers specially at high temperature. This effect more
pronounced in low pH environment.

Oxidation
Presence of oxygen, even in very low concentrations can prompt chemical reactions
that lead to polymer loss.

Microbial
Some types of bacteria in the system can attack and break polymer molecules.

Share rate
High shear rates (in surface pipes, valves, well perforations and near injection
wellbore) can break polymer molecules into smaller segments.
Page 33

Suitable polymer
A suitable polymer should exhibit:
Good viscosity characteristics
High water solubility and easy mixing
Low retention in reservoir rock
Shear, temperature, chemical and biological stability
Ability to flow in the reservoir rock
Reasonable injectivity

Acceptable resistance and residual resistance:

Relatively low values are desirable for mobility control.
High values are desirable for plugging and profile control.

Page 34

Suitable polymer
A suitable polymer should exhibit:
Good viscosity characteristics
High water solubility and easy mixing
Low retention in reservoir rock
Shear, temperature, chemical and biological stability
Ability to flow in the reservoir rock
Reasonable injectivity

Acceptable resistance and residual resistance:

Relatively low values are desirable for mobility control
High values are desirable for plugging and profile control

Page 35

Selecting polymer

Polymer concentration required to achieve a maximum

mobility ratio.
M

PF

krp

kro

p krw w

behind

o krw w minimum

Polymer solution slug size required

V ps D pl IPV VF 1 Sor 1 H K1 0.78 0.22 p w

log H K VDP 1 VDP 0.2

Total mass of polymer required for a flood

Polimer mass, kg 10-3Vb nEvV ps C pl

Page 36

0.25 4

Surfactants

Courtesy from Gary A. Pope

Page 37

Surfactant substances

Surfactants or surface active agents are chemical substances that concentrate at

a surface or fluid/fluid interface when present at low concentration in a system.
Most common surfactants monomer consist of a hydrocarbon portion (nonpolar lypophile) called tail and an ionic portion (polar - hydrophile) as the head.
Classified according to the ionic nature of the head:
Anionic: sodium dodecyl sulfate (C12H25SO4Na+). Exhibit negative charge and yield anions
when dissolved in water.

Cationic: dodecyltrimethyl ammonium bromide (C12H25Na+Me3Br-). Exhibit positive charge

and yield cations when dissolved in water.

Nonionic: dodecyl hexaoxyethylene glycol monoether (C12H25[OCH2CH2]6OH). Neutral and

do not ionize in water but provide characteristics similar to surfactants.

Page 38

Surfactant substances

Anionic surfactants ionize in water into inorganic cations and hydrocarbonsulfonate anions.
As the surfactant concentration increases, several of the sulfonate anions combine
together in the form of micelles. For this reason, surfactant floods are usually
referred to as Micellar Floods.
Micelles

Critical Micelle Concentration

(CMC)

IFT

Individual
monomers

Surfactant Concentration

Page 39

Surfactant-water-oil phase behavior

Salinity increases
Surfaktan

Surfaktan

Type II-

Daerah
1 Fasa

Daerah
1 Fasa

Minyak
Mikroemulsi

Brine

Page 40

Daerah
2 Fasa

Minyak

minyak

Brine

Plait
Point

Brine
Minyak

Type II+

Daerah Mikroemulsi
1 Fasa

Mikroemulsi

2 Fasa
2 Fasa
Daerah
3 Fasa

Plait
Point

Surfaktan

Type III

Brine

Daerah
2 Fasa

Brine
Minyak

Optimal salinity
1.0E+00
IFT mo
IFT mw

IFT (dyne/cm)

1.0E-01

1.0E-02

1.0E-03
l

1.0E-04

Interfacial tensions are equal and

minimum

Vo/Vs atau Vw/Vs)

20.0
16.0
Vo/Vs

12.0

Vw/Vs

8.0
4.0
0.0
0.2

0.6

1.0

1.4

1.8

2.2

2.6

3.0

Kadar Garam (% Berat NaCl)

Page 41

At optimal salinity:

Solubilization parameters are equal

and maximum

Optimal salinity

Displacement efficiency is maximum at optimal salinity

Page 42

Surfactant retention

Surfactant anions get retained in reservoir rocks due to:

Adsorption on positively-charged surfaces

Reaction with divalent cations

Trapping of oil-continuous micro-emulsions

Use of co-surfactants can

reduce surfactant
retention
Langmuir Isotherm
s

Page 43

as Csl
1 bs Csl

Surfactant retention
Many studies relate surfactant retention in reservoir rocks to clay content and
water salinity
Laboratory and field tests can provide reliable retention values

Page 44

Selecting suitable surfactant

Possible candidate reservoirs for surfactant flood applications:

Medium to high oil gravity

Reasonably low salinity and hardness of formation water

Temperatures less than 100 C

Relatively high residual oil saturation

Relatively low clay content with low cation exchange capacity

Select several surfactants based on preliminary screening
Conduct preliminary lab tests for further screening
Select 2 3 surfactants for detail lab tests
Find the right formulation and additives
Conduct core floods
Make final selection and design field pilot test
Page 45

Selecting suitable surfactant

Determination of surfactant retention

Determination of residual oil saturation
Surfactant slug volume required
Mass of surfactant required
Estimating RF from SP floods

Page 46

References
Don W. Green and G. Paul Willhite, 2003, Enhanced Oil Recovery, SPE Textbook Series Vol. 6, the
Society of Petroleum Engineers Inc., USA.
Ezzat E. Gomaa, 2011, Enhanced Oil Recovery - Methods, Concepts, and Mechanisms, KOPUM IATMI.
L.P. Dake, 2002, Fundamentals of Reservoir Engineering, Elsevier Science B.V. Amsterdam, the
Netherlands.
Larry W. Lake, 2005, Petroleum Engineering Handbook Chemical Flooding, Society of Petroleum
Engineers, Richardson, Texas, USA.
Hestuti, E., Usman, Sugihardjo, 2009, Optimasi Rancangan Injeksi Kimia ASP untuk Implementasi
Metode EOR, Simposium Nasional IATMI 2009, Bandung, IATMI 09 00X.
Zhijan, Q., Zhang, Y., Zhang, X., Dai, J., 1998, A successful ASP Flooding Pilot in Gudong Oil Field,
The 1998 SPE/DOE Improved Oil Recovery Symposium, Oklahoma, USA, SPE 39613.
Harry L. Chang, Xingguang, S., Long, Xiao., Zhidong, G., Yuming, Y., Yuguo, X., Gang, C., Kooping,
S., and James, C. Mack, 2006, Successful Field Pilot of In-Depth Colloidal Dispersion Gel (CDG)
Technology in Daqing Oil Field, SPE Reservoir Evaluation & Engineering (Desember 2006), pp. 664
673.

Page 47

?
?

Page 48

Do You Have
Any Questions?