DEVELOPMENT OF CHEMICALS AND EVALUATION METHODS FOR ENHANCEMENT OF CO 2 EOR CONFORMANCE

DEVELOPMENT OF CHEMICALS AND EVALUATION METHODS FOR ENHANCEMENT OF CO2 EOR CONFORMANCE Vörös Cs.1, Dudás J.2, Jónap K.1, Kalocsai P.3*, Törő M.3, Székely E.4, Simándi B.4, Vágó Á.3 1

Univ. of Miskolc Research Inst. of Applied Earth Sciences, Miskolc 2 Univ. of Pannonia, Research Inst. of Chem. and Proc. Eng., Veszprém 3 MOL Plc., E&P, IFA, Budapest 4 BME Dept. Chem. Env. Proc. Eng., Budapest * corresponding author: [email protected]

Project strucure MOL Nyrt. •Projecet Management

Pannon Egyetem •Organition chemichals

ME AFKI

BME •Solubility tests •Determination of distribution coefficients •Estimation of viscosity enhancement

Kihívások és jövőbeni technológiák az EOR megvalósításában

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•Estimation of viscosity enhancement with core-holder viscometer

2013. április 23-24. Szolnok, Garden Hotel

Background Economic potential of EOR methods are increasing worldwide. Meanwhile, application of carbon dioxide of industrial origin for enhanced oil recovery offers CO2 sequestration possibilities as well. One of the key issues of CO2 flooding is the conformance determined by oil to CO2 mobility ratio. Maximized efficiency might be obtained by increasing CO2 viscosity ending up at one or less mobility ratio. The most promising option of viscosity enhancement is thickening carbon dioxide by added chemicals before injection. Successful application of thickened CO2 EOR might be an alternative of WAG method (Water-alternatinggas injection) Kihívások és jövőbeni technológiák az EOR megvalósításában

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Viscous miscible fingering

In case of 1≤M

In case of 10~M


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Displacement fronts


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Mobility ratio

•The viscosity ratio leads to the mobility ratio. •Unfavorable mobility ratio contributes to miscible fingering and reducing the areal sweep efficiency. •Low viscosity of CO2 contributes to the low vertical efficiency, especially in stratified reservoir. Viscosity of CO2

That isMobiliti what the project is allthe about. areal sweep efficiency ratio


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Why should apply CO2 flooding? Advantage of CO2 flooding Available in large amount from natural reservoir Has not effect to the net global warming. Inexpensive Non-flammable, non-toxic Reduced oil viscosity Oil swelling Pressure maintenance


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Why should not apply CO2 flooding? Disadvantage of CO2 flooding Corrosion Recirculation (environment protection) CO2 low viscosity CO2 viscosity 0,04-0,06 cP Oil viscosity 0,6-1,0 cP High mobility ratio Low sweep efficiency Kihívások és jövőbeni technológiák az EOR megvalósításában

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Increase the sweep efficiency CO2 mobility reduction WAG decrease the relative permeability of CO2 by increasing the water saturation Advantage: water prolongs the duration of the CO2 flood. Disadvantage: water shield the residual oil from CO2 and reduces the displacement.

Generation of CO2 foam, Advantage: foam blocks preferential flow channels. Disadvantage: the surfactant adsorbs and the foam breaks down.

Increasing viscosity of CO2 via addition of a “thickening agent” Kihívások és jövőbeni technológiák az EOR megvalósításában

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The ideal candidate is soluble in supercritical carbon dioxide (scCO2), increases the viscosity of the solution by an order of magnitude compared to pure scCO2. is stable, available, cheap and applicable, remains in scCO2 phase when contacted with water, preferably remains in scCO2 phase when contacted with oil (test oil: dodecane).


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Is original research necessary? Literature survey identified promising compounds: high molecular wieght poilmers (PDMS) with entrainer (to increase solublility) fluorinated polimers What kind of compounds we examine? two commercial oligomers (poli-1-decene and poli-vinylethyl-ether) increase the viscosity of CO2 12-14-foldsin a concentration less than 1 m/m% Zhang, S., She, Y., Gu, Y.: Evaluation of polymers as direct thickeners for CO2 enhanced oil recovery, J. Chem. Eng. Data, 56, 1069-1079 (2011). Kihívások és jövőbeni technológiák az EOR megvalósításában

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Poli-1-decene 185 bar, 56 °C, 0,73 m/m%

But, Is it true that all the literature included?

The scientific literature states: Applied in low concentration an order of magnitude increase the viscosity of CO2 solution.

0 min

15 min

60 min

30 min

45 min


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Necessary measurements Determination of solubility (pressure – temperature dependance). Determination of distribution coefficients What tests should be performed to ScCO2 – water determine a compound is suitable or not ScCO2 – oil (dodecane) suitable to increase the viscosity of CO2? Estimation of viscosity enhancement by falling body viscosimetry – determination of density is required on true (Berea) core sample Kihívások és jövőbeni technológiák az EOR megvalósításában

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Solubility determination by static analytical method 7: tempreature control

14

9: HPLC pump; 6: stirrer 4

15

3 13: pressure transducer;

10: solvent

5 2 1: high pressure view cell 11

12: CO2 cyclinder

Fill the cell. Increasing the pressure. Observe the changes. If we can prepare a homogeneous phase it is means the compound is soluble in CO2. Changing the concentration determines the max. conc. depends from T and P.

8 CO2 inlet


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Necessary measurements Determination of solubility (pressure – temperature dependance). Determination of distribution coefficients ScCO2 – water ScCO2 – oil (dodecane)

Estimation of viscosity enhancement by falling body viscosimetry – determination of density is required on true (Berea) core sample Kihívások és jövőbeni technológiák az EOR megvalósításában

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Determination of distribution coefficients computer converter

stirrer

thermocouple T

P sampling valve

T P Visual Cell

T controller

pressure transducer

sampling valve

CO2 cylinder Kihívások és jövőbeni technológiák az EOR megvalósításában

CO2 supply ‹16›


Quantitative analysis by chromatography with inner standards quantities


distribution factors

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Test method by falling body viscosimetry CONTORLLER

P

AIR THERMOST.

COIL pump

CO2 cylinder

view cell

MOVEMENT MECHANICS

After properly mixing the solution filled through into a test-tube.

MULTIMETER <19>

0

MOVING MAGNET

10

20

30

40

MAGNETIC CORE

COILS

ALUMINIUM BODY

½” stainless steel pipe, lenght: 25 cm We measure the time between the two coil-signal.

<20>

Calculations (s  f ) (s  f ) K K t  K t (s  f )t  K t (s  f )n vt s Viszkozitásmérés 153 bar/3

Viszkozitásmérés 102 bar/1

t~23

8,00E+05

8,00E+05

6,00E+05

6,00E+05

4,00E+05

4,00E+05

2,00E+05

2,00E+05

0,00E+00 -2,00E+05

0

5

10

15

20

25

30

35

U (nV)

U (nV)

t~15

0,00E+00 -2,00E+05

-4,00E+05

-4,00E+05

-6,00E+05

-6,00E+05

-8,00E+05

-8,00E+05

-1,00E+06

-1,00E+06 t (egység)

Viscosity

0

10

20

30

t (egység)

Speed


Delay time ‹21›


40

Calibration by scCO2

P (bar) 102 153 205 200 153 102

T (°C) 65 65 65 65 65 65

Literature value Measured Number of (mPa*s) (mPa*s) Deviation repetitions 0.0235 0.0235 10 0.0427 0.0435 1.7% 10 0.0572 0.0572 10 0.0561 0.0558 -0.5% 5 0.0427 0.0421 -1.5% 5 0.0235 0.0235 0.0% 5

T= 65 °C, K1=3.72E-6 m/s, s=3183.5 kg/m3


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Isooctanol (65 °C) The examinations was conducted on a given temperature.

viscosity (mPas)

1,00 0,00

0,05

0,10

0,15

0,20

0,25

0,10

R² = 0,9981 153 bar 200 bar 0,01

isooctanol molar fraction

The present diagram shows the test method is suitable to determine the effect of viscosity enhance. Kihívások és jövőbeni technológiák az EOR megvalósításában

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MOLCO-30 dependence on temperature at constant density MOLCO30: derivative of isooctanol

Concentration Kihívások és jövőbeni technológiák az EOR megvalósításában

Viscosity ‹24›




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Test method by core-holder viscosimetry Transmitter units

Dosing pump

Gas booster

record the differential pressure change

Thermostat

Core holder Injected into the core

Gas tank

given speed

Back-pressure regulator Visual cell

Mantle pump

solution prepared in the visual cell

Viscosity

Flow resistance


Pressure drop ‹26›

Data acquisition and control


Core-holder viscometer Thermostate Visual cell and core-holder Differential pressure transmitter Dosing pump Gas booster ….

Mantle pump Data acquisition and control Kihívások és jövőbeni technológiák az EOR megvalósításában

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Structure of visual cell and core-holder hydraulic fluid came from the dosing pump

4. piston

solution

1. 2. 3. 1. 2. 3. 4.


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Berea core Rubber mantle Mantle area Cell body


Measuring results dP [bar]

P [bar]

Inline pressure Differencial Pressure

t [sec] dP [mbar]

This nine point describes the behavior of given compound.

Pure scCO2

Compound and scCO2


Pure scCO2 ‹29›


Different compounds effect From the normalized data can easy The question is: identification the effective Can be seen something fromand this ineffective examinations? compounds. Effective compounds


Ineffective compounds

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Tested compounds Prepared six series from MOLCO compounds (more than 70 different chemicals), Determined their solubility in scCO2 and And How is the project now? distribution coefficients, Suitable compounds were examined in falling-body viscometer Suitable compounds were examined in core-holder viscometer Kihívások és jövőbeni technológiák az EOR megvalósításában

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Results After the examination 6 series MOLCO family find some chemichals which increase the viscosity of scCO2. MOLCO30 10 MOLCO37 MOLCO29


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Thank you for your attention!


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DEVELOPMENT OF CHEMICALS AND EVALUATION METHODS FOR ENHANCEMENT OF CO 2 EOR CONFORMANCE

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