Copyright: Shell Brands International AG 2008 2/10/2011

Application of Application of Internal Olefin Internal Olefin SulfonatesSulfonates and Other and Other Surfactants to EOR Surfactants to EOR

Part 1: Part 1: Industrial Production, Industrial Production, Structure Performance Relationships, Structure Performance Relationships,

Shell Global Solutions

Structure Performance Relationships, Structure Performance Relationships, HandleabilityHandleability

Julian BarnesJulian Barnes

ContentsContents

•• Commercial scale production of IOS surfactants (ENORDETCommercial scale production of IOS surfactants (ENORDETTMTM))

•• Chemical reactionsChemical reactions

•• Molecular structureMolecular structure

•• Structure Structure –– Performance (Phase Performance (Phase BehaviourBehaviour) Relationships) Relationships

•• Octane (model crude)Octane (model crude)•• Octane (model crude)Octane (model crude)

•• Results and molecular modelingResults and molecular modeling

•• Crude oilsCrude oils

•• Surfactant Surfactant –– field matchingfield matching

•• HandleabilityHandleability optimisationoptimisation for field applicationsfor field applications

•• ConclusionsConclusions

Production of IOS Production of IOS –– Chemical reactions (I)Chemical reactions (I)

•• Internal olefin + SO3 => Internal olefin + SO3 => ββ, , γγ and and δδ sultonessultones

•• NeutralisationNeutralisation by by NaOHNaOH => =>

HydroxyAlkaneSulfonateHydroxyAlkaneSulfonate (HAS) and (HAS) and AlkeneSulfonateAlkeneSulfonate (AS)(AS)

R R

S OO

O

n

•• Low concentration of Low concentration of didi--sulfonatessulfonates strongly influence strongly influence hydrophilicityhydrophilicity

•• Final composition depends on feed (linearity, branching) and Final composition depends on feed (linearity, branching) and

sulfonationsulfonation conditionsconditions

R

S

R

O O

O

OH

Na+

R

SO O

O

R

Na+

Production of IOS Production of IOS –– Chemical reactions (II)Chemical reactions (II)

• Our pilot scale production work has shown:

• Representative full scale commercial production in falling film “mono-tube” reactor (*)

• Process parameter control => consistent product composition and performance

• Specific process aids at low level improve production efficiency• Specific process aids at low level improve production efficiency

(*) Ballestra & Chemithon sulfonation technology

Production of IOS Production of IOS –– Molecular structure Molecular structure LCLC--MS analysisMS analysis

40

50

60

70

80

90

% A

bu

nd

an

ce

Hydroxy Alkane Sulfonate

Alkene Sulfonate

•• HAS / AS ratio decreases from IOS 15HAS / AS ratio decreases from IOS 15--18 to 2418 to 24--2828

•• DiDi--sulfonatesulfonate increases for High (vs. Low) SOincreases for High (vs. Low) SO33

0

10

20

30

IOS 15-18 IOS 20-24

(Low

SO3)

IOS 20-24

(High

SO3)

IOS 19-23

(Low

SO3)

IOS 19-23

(High

SO3)

IOS 24-28

% A

bu

nd

an

ce

Alkene Sulfonate

Di-Sulfonate

Structure Performance Relationships: Structure Performance Relationships: Phase Phase BehaviourBehaviour –– octane octane -- 9090°°C (I)C (I)

8

10

12

14

Op

tim

al

sali

nit

y, %

Na

Cl

IOS 15-18

IOS 19-23 Low SO3

IOS 19-23 High SO3

IOS 20-24 Low SO3

95% confidence limits based on samples with slightly different process conditions

Phase behaviour principle

0

2

4

6

Op

tim

al

sali

nit

y, %

Na

Cl

IOS 20-24 Low SO3

IOS 20-24 High SO3

IOS 24-28

•• Optimal salinity decreases with increased carbon chainOptimal salinity decreases with increased carbon chain

•• High SOHigh SO33 (high (high didi--sulfonatesulfonate) increases optimal salinity ) increases optimal salinity

salinity

Structure Performance Relationships: Structure Performance Relationships: Phase Phase BehaviourBehaviour –– octane octane -- 9090°°C (II)C (II)

20

25

30

35

40

45

50

So

lub

ilis

ati

on

Pa

ram

ete

r, m

l/m

l

IOS 15-18

IOS 20-24 Low SO3

IOS 20-24 High SO3

IOS 19-23 Low SO3

Moderate

Optimal Salinity

with High Sol

Ratio

•• Trend: Decreasing optimal salinity Trend: Decreasing optimal salinity �� increasing increasing ssolubilisationolubilisation ratioratio

•• IOS 19IOS 19--23: high 23: high solubilisationsolubilisation at moderate salinityat moderate salinity

0

5

10

15

20

0 5 10 15

So

lub

ilis

ati

on

Pa

ram

ete

r, m

l/m

l

Optimal Salinity, %NaCl

IOS 19-23 Low SO3

IOS 19-23 High SO3

IOS 24-28

Typical

band

Structure Performance Relationships: Structure Performance Relationships: Molecular modelingMolecular modeling

R² = 0.85

6

8

10

12

14

Op

tim

al

sali

nit

y, %

Na

Cl

y = -58x + 81R² = 0.96

12

14

16

Op

tim

al

sali

nit

y, %

Na

Cl

Advanced model based on molecularmolecular descriptors

•• Optimal salinity: Optimal salinity: HLBHLB & molecular descriptor correlations work & molecular descriptor correlations work

•• SolubilisationSolubilisation Ratio:Ratio: Molecular descriptor correlations under developmentMolecular descriptor correlations under development

Standard HLB modelmodel

0

2

4

5 7 9 11 13

Op

tim

al

sali

nit

y, %

Na

Cl

HLB

R² = 0.96

0

2

4

6

8

10

1.15 1.2 1.25 1.3 1.35 1.4 1.45

Op

tim

al

sali

nit

y, %

Na

Cl

DPSA / MW

IOS 19-23?

Structure Performance Relationships: Structure Performance Relationships: Surfactant Surfactant -- Crude Oil interactionsCrude Oil interactions

Tail

oil

ETail-Oil

Tail

oil

ETail-Oil

Surfactant

interaction with

oil and brine

Interaction

energies ETail-Oil

and E

Internal olefin sulfonate

Alcohol ethoxy sulfate

Naphthenate Asphaltene aggregatesolvated by resins

SurfactantSurfactant tails solvated by crude oil molecules

Head

oil

brine

EHead-Brine

Head

oil

brine

EHead-Brine

and EHead-Water

must be large

for low IFT

OHSOO

O

Na+

O

O

O

OO

OO

OS

O

OO

O O

Na+

Na+-

-

-

oil phase

aqueous phase

Synthetic surfactantssurfactantsand….

Interfacially active crude components

Structure Performance Relationships: Structure Performance Relationships: Crude Oil Crude Oil -- IOS 24IOS 24--28 / IOS 1528 / IOS 15--1818

NaphthenicResins (%) Asphaltenes (%) acids (ppm)

Crude A 7.6 0.2 3230

Crude B 10.5 0.2 3010

Crude C 12.2 5.3 1500Crude D 13.6 6.6 na

Crude E 14.9 1.7 1856

High activity High activity Less compatible, viscous phases

NOTE: the crude oils are:

• Regionally different

• Low viscosity (API: 26-38)

• Low TAN (low soaps level)

salinity

% KCl: 0.5 0.75 1.0 1.25 1.50

Crude D

salinity

% NaCl 0.25 0.50 0.75 1.0 1.25 1.50

Crude E

salinity

% NaCl 0.25 0.37 0.50 0.75 1.0

Crude A

viscous

phases

Structure Performance Relationships: Structure Performance Relationships: Crude Oil Crude Oil -- IOS 24IOS 24--28 / IOS 1528 / IOS 15--1818

Crude A 7.6 0.2 3230

Crude B 10.5 0.2 3010

Crude C 12.2 5.3 1500Crude D 13.6 6.6 na

Crude E 14.9 1.7 1856

High activity High activity Less compatible, viscous phases

NOTE: the crude oils are:

• Regionally different

• Low viscosity (API: 26-38)

• Low TAN (no soaps)

Resins (%) Asphaltenes (%) acids (ppm)Naphthenic

salinity

% KCl: 0.5 0.75 1.0 1.25 1.50

Crude D

salinity

% NaCl 0.25 0.50 0.75 1.0 1.25 1.50

Crude E

salinity

% NaCl 0.25 0.37 0.50 0.75 1.0

Crude A

viscous

phasesSolubilisation benefits from long tailed IOS. Applied successfully in single well

tracer test with 90+% oil recovery (ref: Buijse et al, companion PEA meeting paper)

Matching Surfactants to Reservoir Matching Surfactants to Reservoir ConditionsConditions

IOS 20-24IOS 19-23

C16, 17 EOx sulfonate

C12, 13 EOx sulfonate

IOS 24-28

IOS 15-18

as secondary blending

component

IOS 15-18

Am

bie

nt

to 1

40

°CSalinity ranges based on optimal salinities measured with octane

•• The surfactants cover wide range of temperatures and salinitiesThe surfactants cover wide range of temperatures and salinities

C12, 13 EOx sulfonate

C16, 17 POx sulfate

C12, 13 POx sulfate C16, 17 EOx sulfate

C12, 13 EOx sulfate

Se

a w

ate

r

0 5 10 15 20 25

Salinity, %NaCl

Am

bie

nt

to

60

°C

Surfactant ManufacturingCurrent surfactant manufacturing largely 10-14 carbon number (ca. 6 mln ton pa)Good EOR surfactant properties requires 16-28 carbon number

EthyleneNatural Fats

and Oils

Paraffin

waxes

Normal

ParaffinsStarting Materials

Surfactants

Raw Materials

Alpha /

Internal

Olefins

Fatty

Acids

Detergent

range

alcohols

Ethylene

Oxide

PO

Alpha

Internal

olefin

sulfonate

Fatty

amine

oxides

Fatty

alkanol

amides

Alkyl

glyceryl

ether

sulfonate

Alcohol

sulfates

Alcohol

ethoxy-

sulfates

Sulphonat

es

carboxyla

tes

alcohol

ethoxylate

Linear

Alkyl

aromatic

sulfonate

Paraffin

sulfonate

Benzene

Toluene

Xylene

HandleabilityHandleability OptimisationOptimisation::For Logistics & Surface FacilitiesFor Logistics & Surface Facilities

IOS 15IOS 15--18, 35% AM18, 35% AM

Low viscosity liquidLow viscosity liquid

IOS 19IOS 19--23, 35% AM23, 35% AM

High viscosity liquidHigh viscosity liquid

IOS 19IOS 19--23, 66% AM23, 66% AM

PastePaste

HandleabilityHandleability optimisationoptimisation::Surfactant Physical PropertiesSurfactant Physical Properties•• OptimiseOptimise viscosity (and pour point) appropriate for manufacture, viscosity (and pour point) appropriate for manufacture,

transport, pumping, blendingtransport, pumping, blending

•• No phaseNo phase--separation; separation; pumpablepumpable

•• MinimiseMinimise water (and water (and maximisemaximise % active) for shipment% active) for shipment

•• IOS IOS rheologyrheology characteristics:characteristics:

•• SemiSemi--soluble / colloidal dispersion in watersoluble / colloidal dispersion in water•• SemiSemi--soluble / colloidal dispersion in watersoluble / colloidal dispersion in water

•• IO chain lengthIO chain length↑↑:: viscosityviscosity ↑↑

•• %active%active↓↓: : viscosity viscosity ↓↓

•• shear rateshear rate↑↑ : : viscosityviscosity ↓↓ ↓↓

•• Blends of IOS + solvent can help to lower viscosity, e.g.:Blends of IOS + solvent can help to lower viscosity, e.g.:

•• IOS 24IOS 24--28 HAM with water28 HAM with water => 19,000 => 19,000 cPcP (paste) (paste)

•• IOS 24IOS 24--28 HAM with SBA/water => 830 28 HAM with SBA/water => 830 cPcP (liquid)(liquid)

NOTENOTE: More : More viscometricviscometric data (with shear & temperature) is in the papedata (with shear & temperature) is in the paperr

HandleabilityHandleability optimisationoptimisation: : RheologyRheology Diagram for IOS 24Diagram for IOS 24--2828

5 8 14 21 ====> 33 ====> 64

60℃℃℃℃ Liquid Liquid Liquid Thick Liquid Thick Liquid Thick Liquid

50℃℃℃℃ Liquid Liquid Thick Liquid Gel/Paste Gel/Paste Gel/Paste

40℃℃℃℃ Liquid Liquid Thick Liquid Gel/Paste Gel/Paste Gel/Paste

℃℃℃℃

•• IOS 24IOS 24--28: 28: pumpablepumpable at 60at 60°°C for wide range of %activeC for wide range of %active

•• Comparable diagram for IOS 15Comparable diagram for IOS 15--18 is liquid throughout 18 is liquid throughout

℃℃℃℃

30℃℃℃℃ Liquid Thick Liquid Flowy Gel Gel/Paste Gel/Paste Gel/Paste

20℃℃℃℃ Thick Liquid Flowy Gel Gel/Paste Gel/Paste Gel/Paste Gel/Paste

10℃℃℃℃ Thick Liquid Flowy Gel Gel/Paste Gel/Paste Gel/Paste Gel/Paste

5 8 14 21 ====> 33 ====> 64

Active Matter (%w)

ConclusionsConclusions

•• Wide range of commercialWide range of commercial--scale ENORDET EOR surfactants manufactured scale ENORDET EOR surfactants manufactured

and successfully applied in field testsand successfully applied in field tests

•• IOS structure control through understanding of IOS structure control through understanding of sulfonationsulfonation process process conditions conditions

•• IOS performance correlations developed & applied for model and crude oils IOS performance correlations developed & applied for model and crude oils

•• HandleabilityHandleability options developed to options developed to optimiseoptimise surfactant logistics and surface surfactant logistics and surface

facility design facility design

•• IOSs are “candidate workhorses” in IOSs are “candidate workhorses” in cEORcEOR

•• Good activity in a wide range of crudes and salinitiesGood activity in a wide range of crudes and salinities

•• Stable at high TStable at high T

•• Require fewer production steps c.f. potential alternatives for high TRequire fewer production steps c.f. potential alternatives for high T