Evaluation of Cellulose Nanocrystals as a Green "Smart Water" Additive in Enhanced Oil Recovery from Sandstone Reservoirs

DVD*UHHQ³6PDUW:DWHU´$GGLWLYHLQ (QKDQFHG2LO5HFRYHU\IURP

6DQGVWRQH5HVHUYRLUV

'RFWRUDO7KHVLVE\

6LOMH1HGODQG0ROQHV

7KHVLVVXEPLWWHGLQSDUWLDOIXOILOPHQWRI WKHUHTXLUHPHQWVIRUGHJUHHRI

3+,/2623+,$('2&725 3K'

)$&8/7<2)6&,(1&($1'7(&+12/2*<

'(3$570(172)3(752/(80(1*,1((5,1*

LL 8QLYHUVLW\RI6WDYDQJHU

16WDYDQJHU 125:$<

ZZZXLVQR

‹6LOMH1HGODQG0ROQHV ,6%1 ,661

3K'7KHVLV8L6QR

LLL

7KLVWKHVLVLVVXEPLWWHGLQSDUWLDOIXOILOPHQWRIWKHUHTXLUHPHQWVIRUWKHGHJUHH RI 3KLORVRSKLDH 'RFWRU 3K' DW WKH 8QLYHUVLW\ RI 6WDYDQJHU 8L6 DQG FRQVLVWV RI WKUHH SDSHUV 7KH ZRUN SUHVHQWHG LQ WKLV WKHVLV ZDV PDLQO\

SHUIRUPHG DW WKH 8JHOVWDG /DERUDWRU\ DW WKH 'HSDUWPHQW RI &KHPLFDO (QJLQHHULQJ1718DWWKH6PDUW:DWHU/DERUDWRU\IDFLOLW\DWWKH'HSDUWPHQW RI3HWUROHXP(QJLQHHULQJ8L6DQGDWWKH17181DQR/DE1RU)DEIDFLOLW\

7KH SURMHFW KDV EHHQ IXOO\ IXQGHG WKURXJK WKH 125&(/ 3URMHFW 7KH 125ZHJLDQ1DQR&(/OXORVH7HFKQRORJ\3ODWIRUPLQLWLDWHGDQGOHGE\7KH 3DSHU DQG )LEUH 5HVHDUFK ,QVWLWXWH 3), LQ 7URQGKHLP DQG IXQGHG E\ WKH 5HVHDUFK&RXQFLORI1RUZD\WKURXJKWKH1$123URJUDPJUDQWQXPEHU 7KH ZRUN KDV EHHQ VXSHUYLVHG E\ $VVRFLDWH 3URIHVVRU 'U 6NXOH 6WUDQG8L6DQGFRVXSHUYLVHGE\$VVRFLDWH3URIHVVRU'U.ULVWRIHU*3DVR 1718 DQG 3URIHVVRU ,,6HQLRU 5HVHDUFK 6FLHQWLVW 'U .ULVWLQ 6\YHUXG 17183),

,FRPSOHWHGP\0DVWHURI6FLHQFHLQ%LRWHFKQRORJ\ZLWKDVSHFLDOLVDWLRQLQ ELRFKHPLVWU\DQGELRSRO\PHUFKHPLVWU\DWWKH'HSDUWPHQWRI%LRWHFKQRORJ\

DW1718LQ-XQH,ZDVDFFHSWHGDVD3K'FDQGLGDWHDWWKH'HSDUWPHQW RI3HWUROHXP(QJLQHHULQJ8L6LQ$SULO

LY

Y

:ULWLQJ D 3K ' LV D GDXQWLQJ WDVN DQG , FRXOG QRW KDYH SXOOHG WKURXJK ZLWKRXW WKH JXLGDQFH KHOS DQG VXSSRUW IURP D ODUJH DQG GLYHUVH JURXS RI SHRSOHRYHUWKHODVWWKUHH\HDUV

)LUVWDQGIRUHPRVW,ZRXOGOLNHWRH[SUHVVP\WKDQNVDQGJUDWLWXGHWR P\ VXSHUYLVRUV HVSHFLDOO\ $VVRFLDWH 3URIHVVRU 6NXOH 6WUDQG 3K' DQG 6HQLRU 5HVHDUFK 6FLHQWLVW .ULVWLQ 6\YHUXG 'U,QJ IRU WKHLU WKRURXJK JXLGDQFH DQG DVVLVWDQFH WKURXJKRXW WKLV SURMHFW 7KDQNV VKRXOG DOVR EH H[WHQGHG WR $VVRFLDWH 3URIHVVRU .ULVWRIHU * 3DVR 3K' IRU DOZD\V EHLQJ DYDLODEOHIRUFRXQVHOOLQJ

6HFRQG , ZRXOGOLNH WR WKDQN FROOHDJXHVVWDIIDQGIULHQGVIURP WKH 6PDUW:DWHUJURXSDW8L67KH8JHOVWDG/DERUDWRU\DW1718DQG3),IRU JHQHUDO JXLGDQFH DQG KHOS LQ WKH ODE DQG IRU LQWHUHVWLQJ GLVFXVVLRQV RYHU FRIIHHV DQG EHHUV RYHU WKH \HDUV 3DUWLFXODUO\ , ZRXOG OLNH WR PHQWLRQ WKH DVVLVWDQFH , JRW IURP ,YDQ ' 3 7RUULMRV DQG $OHNVDQGU 0DPRQRY ZKHQ SHUIRUPLQJ WKH FRUH IORRGLQJ H[SHULPHQWV DW 8L6 , FRXOG QRW KDYH GRQH LW ZLWKRXW\RXUKHOSDQGSDWLHQFH

7KH5HVHDUFK&RXQFLORI1RUZD\VKRXOGDOVREHWKDQNHGIRUWKHIXOO ILQDQFLDOVXSSRUWRIWKH125&(/LQLWLDWLYHWKURXJKWKH1$12SURMHFW ,DOVRRZHP\WKDQNVWR3),DQG.ULVWLQ6\YHUXGIRULQLWLDWLQJ125&(/DQG WDNLQJPHLQRQWKHSURMHFWDVRQHRIWKUHH3K'VWXGHQWV

, ZRXOG OLNH WR WKDQN P\ IULHQGV DQG IDPLO\ LQ 7URQGKHLP 0RVV cOHVXQGDQG6WDYDQJHUIRUDOZD\VEHOLHYLQJLQPHDOWKRXJKLWKDVQRWDOZD\V EHHQ FOHDUWR \RX ZKDW , DFWXDOO\ GR 6SHFLILFDOO\ , ZRXOG OLNH WR WKDQN P\

SDUHQWV 7RQMH 1 0ROQHV DQG 7RUH / 0ROQHV IRU OHWWLQJ PH KDYH P\ ROG URRPEDFNDQGDOORZLQJPHWROLYHDWKRPHLQ6WDYDQJHUIRUH[WHQGHGSHULRGV RI WLPH DV ZHOO DV WKHLU XQOLPLWHG VXSSRUW DQG ORYH , ZDQW WR WKDQN P\

EURWKHUV 7RUMH DQG 6LQGUH - 0ROQHV IRU WKHLU FKHHUIXO VXSSRUW DQG P\

JUDQGIDWKHU &KULVWLDQ 1HGODQG IRU DOZD\V EHLQJ JHQXLQHO\ LQWHUHVWHG LQ KHDULQJDERXWP\ZRUNDQGIRULQVSLULQJFRQYHUVDWLRQVRYHUWKH\HDUV

/DVW EXW QRW DW DOO OHDVW , ZDQW WR WKDQN P\ ILDQFpH 6LJXUG 5ROODQG 3HWWHUVHQIRUKLVXQFRQGLWLRQDOORYHSDWLHQFHDQGVXSSRUW<RXNHHSP\IHHW RQWKHJURXQGDQGP\KHDGRXWRIWKHVNLHVDQGLWPHDQVWKHZRUOGWRPH, ORYH\RX

YL

YLL

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

,QWKLVWKHVLVZRUNFHOOXORVHQDQRFU\VWDOV&1&KDYHEHHQLQYHVWLJDWHGDVD SRWHQWLDO JUHHQ DGGLWLYH DOWHUQDWLYH IRU HQKDQFHG RLO UHFRYHU\ (25 LQ FRPELQDWLRQZLWKWKH6PDUW:DWHUORZVDOLQHEULQHWHFKQRORJ\3UHVHQWHGLQ WKLV WKHVLV DUH VWXGLHV LQYHVWLJDWLQJ WKH HIIHFWV RI GLIIHUHQW SK\VLFDO DQG FKHPLFDO HQYLURQPHQWV WKDW ORZ FRQFHQWUDWLRQ &1& GLVSHUVLRQV PD\ EH VXEMHFWHGWRDWRLOUHVHUYRLUFRQGLWLRQV)LUVWYDULRXVFRQFHQWUDWLRQVRI&1&

GLVSHUVHGLQGHLRQL]HGZDWHUDQGLQDSSP1D&OEULQHZHUHVXEMHFWHGWR YDULDWLRQVLQVDOLQLW\S+DQGWHPSHUDWXUHDQGWKHUHVXOWVFRQILUPHGWKDWWKH GLVSHUVLRQV UHPDLQHG VWDEOH ZLWKLQ WKH VDOLQLWLHV NQRZQ WR DIIHFW WKH ZHWWDELOLW\ RI VDQGVWRQH DV ZHOO DV WKH S+ UDQJH H[SHFWHG LQ VDQGVWRQH RLO UHVHUYRLUV6WDEOHGLVSHUVLRQVZHUHDOVRREVHUYHGZKHQKHDWHGWRWHPSHUDWXUHV UDQJLQJ IURP WR ƒ& $W H[WHQGHGKHDW DJLQJ DW ƒ& DQG ƒ& IRU VHYHQ GD\V EHJLQQLQJ GHJUDGDWLRQ ZDV REVHUYHG IRU ERWK W\SHV RI &1&

GLVSHUVLRQV ZLWK YLVFRVLW\ LQFUHDVH DQG S+ GHFUHDVH DV WKH PRVW LPSRUWDQW LQGLFDWRUV&1&GLVSHUVHGLQSSP1D&OEULQHZDVJHQHUDOO\PRUHKHDW WROHUDQWWKDQWKH&1&GLVSHUVHGLQGHLRQL]HGZDWHU$IOXLGWKDWLQFUHDVHVLWV YLVFRVLW\ ZLWK KHDW DQG WLPH ZLOO EH HDVLHU WR LQMHFW GXH WR D ORZ LQLWLDO YLVFRVLW\DQGZKHQWKHYLVFRVLW\LQFUHDVHVLQWKHSRURXVUHVHUYRLUWKLVHIIHFW FRXOGOHDGWRLQFUHDVHGVZHHSHIILFLHQF\DQGEHWWHURLOUHFRYHU\

7KH LQMHFWLYLW\ RI &1& LQWR D KLJKSHUPHDEOH VDQGVWRQH FRUH KDV EHHQ LQYHVWLJDWHG E\ SHUIRUPLQJ IORRGLQJ H[SHULPHQWV RQ ZDWHU VDWXUDWHG FRUHV XVLQJ LQFUHDVLQJ FRQFHQWUDWLRQV RI &1& DQG LQFUHDVLQJ WHPSHUDWXUH

YLLL

7KHVH LQYHVWLJDWLRQV FRQILUPHG WKDW PRVW RI WKH YLVFRVLW\ JHQHUDWLQJ &1&

SDUWLFOHV WUDYHOOHG WKURXJK WKH FRUHV DW DOO WKH WHVWHG WHPSHUDWXUHV DQG &1&

FRQFHQWUDWLRQV 2LO UHFRYHU\ H[SHULPHQWV VKRZHG WKDW ZKHQ &1&/6 EULQH ZDV XVHG LQ WHUWLDU\ PRGH DQ LQFUHDVH LQ XOWLPDWH UHFRYHU\ ZDV REVHUYHG 'XULQJWHUWLDU\&1&/6LQMHFWLRQWKH&1&SDUWLFOHVLQFUHDVHGIOXFWXDWLRQVLQ GLIIHUHQWLDO SUHVVXUH ZKLFK FRXOG EH OLQNHG WR ORJ MDPPLQJ LQ SRUH WKURDWV DQGUHPRELOLVDWLRQRIRLOLQWKHSRUHVSDFH7KHVHUHVXOWVLQGLFDWHWKDW&1&

SDUWLFOHVPD\KDYHSRWHQWLDODVDJUHHQIORRGLQJIOXLGDGGLWLYHEXWWKDWIXUWKHU

LQYHVWLJDWLRQVDUHQHHGHG

L[

I. 6LOMH 1HGODQG 0ROQHV ,YiQ ' 3LxHUH] 7RUULMRV .ULVWRIHU * 3DVR 6NXOH 6WUDQG .ULVWLQ 6\YHUXG “Sandstone injectivity and salt stability of cellulose nanocrystals (CNC) dispersions – Premises for use of CNC in enhanced oil recovery”, Industrial Crops and Products, 2016. Vol. 93, 152 –160.

II. 6LOMH 1HGODQG 0ROQHV .ULVWRIHU * 3DVR 6NXOH 6WUDQG .ULVWLQ 6\YHUXG “The effects of pH, time and temperature on the stability and viscosity of cellulose nanocrystal (CNC) dispersions – Implications for use in enhanced oil recovery” Submitted to Cellulose, 03.02.2017.

III. 6LOMH1HGODQG0ROQHV$OHNVDQGU0DPRQRY.ULVWRIHU*3DVR6NXOH 6WUDQG .ULVWLQ 6\YHUXG“Investigation of a new application for cellulose nanocrystals – A study of the enhanced oil recovery potential from sandstone by use of a green additive”Submitted to Cellulose, 21.03.2017.

[

[L

Poster at 249^th ACS National Meeting and Exposition – Chemistry of Natural Resources

7LWOH Sandstone Core-flooding using Low-Saline Water and Crystalline Nanocellulose.

$XWKRUV6LOMH1HGODQG0ROQHV,YDQ'3LxHUH]7RUULMRV.ULVWRIHU*3DVR 6NXOH6WUDQG.ULVWLQ6\YHUXG

'DWH±^WK0DUFK

/RFDWLRQ'HQYHU&286$

Talk at TAPPI Nano’s 2016 International Conference on Nanotechnology for Renewable Materials

7LWOHSandstone Injectivity of Cellulose Nanocrystals - A Premise for use in Enhanced Oil Recovery.

&RPPHQWPLQXWHWDON

$XWKRUV6LOMH1HGODQG0ROQHV,YDQ'3LxHUH]7RUULMRV.ULVWRIHU*3DVR 6NXOH6WUDQG.ULVWLQ6\YHUXG

'DWH±^WK-XQH

/RFDWLRQ*UHQREOH)UDQFH

Talk at PFI’s 6^th Research Seminar: Recent advances in cellulose nanotechnology research – Production, characterization and applications

7LWOHSandstone Injectivity of Cellulose Nanocrystals - A Premise for use in Enhanced Oil Recovery.

&RPPHQWPLQXWHWDON

$XWKRUV6LOMH1HGODQG0ROQHV,YDQ'3LxHUH]7RUULMRV.ULVWRIHU*3DVR 6NXOH6WUDQG.ULVWLQ6\YHUXG

'DWH±^WK2FWREHU /RFDWLRQ7URQGKHLP1RUZD\

[LL

[LLL

3UHIDFHLLL

$FNQRZOHGJHPHQWVY

$EVWUDFWYLL /LVWRISXEOLFDWLRQVL[

3RVWHUDQGFRQIHUHQFHFRQWULEXWLRQV[L /LVWRIILJXUHV[YLL /LVWRIWDEOHV[[LLL

$EEUHYLDWLRQVDQGQRPHQFODWXUH[[Y 0RWLYDWLRQDQG2XWOLQH ,QWURGXFWLRQWR1DQRFHOOXORVH

&HOOXORVH

&HOOXORVHQDQRFU\VWDOV&1&

%DFNJURXQG 3URGXFWLRQ &ROORLGDOEHKDYLRXURIFHOOXORVHQDQRFU\VWDOV

5KHRORJ\

&HOOXORVHSURGXFWVLQWKHRLOLQGXVWU\

%DVLF&RQFHSWVRI2LO5HFRYHU\

,QWURGXFWLRQ 0LQHUDORJLFDOGHVFULSWLRQRIVDQGVWRQHV

4XDUW]

0LFDV )HOGVSDUV

&OD\V

2LOUHFRYHU\PHFKDQLVPV

[LY

3ULPDU\UHFRYHU\

6HFRQGDU\UHFRYHU\

7HUWLDU\UHFRYHU\±(QKDQFHGRLOUHFRYHU\

*HQHUDOGHVFULSWLRQDQGFKDUDFWHULVDWLRQRI(25SURFHVVHV )XQGDPHQWDOVRI3RURXV6\VWHPV6XUIDFHDQG&ROORLG&KHPLVWU\

'LVSODFHPHQWIRUFHV 'LVSODFHPHQWHIILFLHQF\

)OXLGIORZLQSRURXVPHGLD

&DSLOODU\IRUFHV

*UDYLW\IRUFHV

9LVFRXVIRUFHV

,QWHUUHODWLRQRIIRUFHV 6XUIDFHIRUFHV

(OHFWULFDOGRXEOHOD\HU('/

'/92WKHRU\

'LVMRLQLQJSUHVVXUH

:HWWDELOLW\

'HILQLWLRQDQGFODVVLILFDWLRQ (YDOXDWLRQRIZHWWLQJLQSRURXVURFN

)DFWRUVLQIOXHQFLQJZHWWDELOLW\

(25LQ6DQGVWRQHXVLQJ6PDUW:DWHUDQG&1&

:KDWLVD³6PDUW:DWHU´"

6PDUW:DWHU(25LQVDQGVWRQH

3UHPLVHVIRU6PDUW:DWHU(25 6PDUW:DWHU(25PHFKDQLVP 3URSRVHGPHFKDQLVPIRU6PDUW:DWHUIORRGLQJZLWK&1&

0DWHULDOVDQG0HWKRGV

[Y

%ULQHV

&RUHPDWHULDO

&UXGHRLO

0HWKRGV 5KHRORJ\

=HWDSRWHQWLDO

$WRPLFIRUFHPLFURVFRS\

&RUHUHVWRUDWLRQ

&RUHIORRGLQJ

5HVXOWVDQG'LVFXVVLRQ

=HWDSRWHQWLDO

6WDELOLW\ZLWKLQFUHDVLQJVDOLQLW\

S+HIIHFWV 7HPSHUDWXUHLQIOXHQFH

5KHRORJ\

(IIHFWRI&1&FRQFHQWUDWLRQ (IIHFWRIVDOLQLW\

(IIHFWRIS+

+HDWDJLQJ

$WRPLFIRUFHPLFURVFRS\

&RUHIORRGLQJ

,QMHFWLYLW\VWXGLHVDQGHIIHFWRILQFUHDVLQJ&1&FRQFHQWUDWLRQ

(IIHFWRILQFUHDVLQJWHPSHUDWXUH 2LOUHFRYHU\H[SHULPHQWV

[YL

&RQFOXGLQJUHPDUNVDQGIXWXUHZRUN &KDUDFWHULVDWLRQDQGWHPSHUDWXUHVWDELOLW\

'LVSHUVLRQVWDELOLW\

9LVFRVLW\

(IIHFWVRIKHDWDJLQJRQ&1&GLVSHUVLRQV

&RUHIORRGLQJH[SHULPHQWV ,QMHFWLYLW\

(QKDQFHGRLOUHFRYHU\H[SHULPHQWV )XWXUHZRUN

$SSHQGL[

$&DOFXODWLRQRIGHVLUHGFRUHZHLJKWDW6_ZL

$&DOFXODWLRQRI+IRUPHGIURPS+UHGXFWLRQ

$SSHQGHGSDSHUV

3DSHU,

3DSHU,,

3DSHU,,,

[YLL

Figure 2.1:7KHFKHPLFDOVWUXFWXUHRIFHOOXORVH Figure 2.2: 6FKHPDWLF VWUXFWXUH RI FHOOXORVHIURP SODQW FHOO ZDOOVWRVLQJOH FHOOXORVH FKDLQV FRQVLVWLQJ RI UHSHDWLQJ FHOORELRVH XQLWV $GDSWHG IURP 7VXFKLNDZD Figure 2.3: &1& LQ DTXHRXV GLVSHUVLRQ SLFWXUHG ZLWK DWRPLF IRUFH PLFURVFRS\$)0 Figure 2.4:*HQHUDOSURGXFWLRQSURFHGXUHIRU&1&$GDSWHGIURP'XIUHVQH E Figure 2.5:6FKHPDWLFRIDFLGK\GURO\VLVRI&1&QRWWRVFDOH Figure 2.6:,OOXVWUDWLRQRIDELSKDVLFGLVSHUVLRQRI&1&LQZDWHUDVLWZRXOG ORRNWKURXJKFURVVHGSRODULVHUV7KHLVRWURSLFSKDVHLVVKRZQRQWKHOHIWDQG DQLVRWURSLF SKDVH LV VKRZQ RQ WKH ULJKW 3KRWRJUDSK RI ELSKDVLF &1&

GLVSHUVLRQIURP;'RQJHWDO Figure 2.7:*UDSKLFSUHVHQWDWLRQRIWKHHOHFWULFDOGRXEOHOD\HURIDQHJDWLYHO\

FKDUJHGSDUWLFOH Figure 2.8: 6KHDU UDWH GHSHQGHQF\ LOOXVWUDWHG IRU D &1& GLVSHUVLRQ 7KH GLIIHUHQW VKHDU UHJLRQV DUH LQGLFDWHG ZLWK EOXH GDVKHG OLQHV $GDSWHG IURP 6KDILHL6DEHW Figure 3.1:7\SLFDODQWLFOLQDOSHWUROHXPWUDSVLPSOLILHGQRWWRVFDOH7KHRLO PLJUDWHV IURP WKH VRXUFH URFN WKURXJK WKH SHUPHDEOH URFN LQWR WKH RLO UHVHUYRLUDERYHWKHZDWHUOLQH Figure 3.2:+\GURFDUERQDFFXPXODWLRQGXHWRDIDXOWVWUXFWXUH Figure 3.3:6RUWLQJLPSDFWRQUHVHUYRLUSRURVLW\$GDSWHGIURP-DKQHWDO F Figure 3.4 &U\VWDO ODWWLFH VWUXFWXUHV IRU WKH PRVW FRPPRQ FOD\ PLQHUDOV

$GDSWHGIURP1LFKROV Figure 3.5: 2LO UHFRYHU\ PHFKDQLVP VHTXHQFH $GDSWHG IURP $KPHG F Figure 3.6: 6FKHPDWLF FODVVLILFDWLRQ RI (25 PHWKRGV $GDSWHG IURP 7KRPDV Figure 4.1: 6LPSOLILHG DQG LGHDOLVHG PRGHO RI D SRUH FKDQQHO FRQWDLQLQJ D ZDWHU SKDVH DQG DQ RLO SKDVH ZLWK D PHQLVFDO LQWHUIDFHR LV WKH FXUYDWXUH

[YLLL

UDGLXVr_c LV WKH FDSLOODU\ UDGLXV DQGθ_c LV WKH ZHWWLQJ DQJOH $GDSWHG IURP

=RORWXNKLQ 8UVLQG Figure 4.2: *UDYLW\ VHJUHJDWLRQ LQ GLVSODFHPHQW SURFHVVHV $GDSWHG IURP

*UHHQ :LOOKLWHF Figure 4.3: ('/ WKLFNQHVV DV D IXQFWLRQ RI WKH VDOLQLW\ RI WKH GLVSHUVLQJ PHGLXP$GDSWHGIURP(DVWPDQ Figure 4.4:3RWHQWLDOLQWHUDFWLRQHQHUJ\EHWZHHQWZRSDUWLFOHVDVDIXQFWLRQRI WKHLUGLVWDQFH Figure 4.5: &RQWDFW DQJOH PHDVXUHPHQW LQ D ZDWHUZHW OHIW DQG RLOZHW ULJKWV\VWHP$GDSWHGIURP&UDLJ Figure 5.1:6FKHPDWLFRYHUYLHZRIWKH6PDUW:DWHUPHFKDQLVPZKHUHORZ VDOLQLW\ IORRGLQJ FDXVHV DFLGLF DQG EDVLF PDWHULDO DGVRUEHG RQWR QHJDWLYHO\

FKDUJHG FOD\ PLQHUDOV WR EH UHPRYHG LQ DQ DONDOLQH HQYLURQPHQW GXH WR GHVRUSWLRQ RI &D IURP WKH FOD\ VXUIDFH $GDSWHG IURP 7 $XVWDG HW DO 66WUDQGHWDO Figure 5.2: /6 EULQH FDXVHV D ZHWWDELOLW\ DOWHUDWLRQ OHDGLQJ WR SRVLWLYH FDSLOODU\IRUFHVDQGLQFUHDVHLQVZHHSHIILFLHQF\$GDSWHGIURP66WUDQGHW DO Figure 5.3:$VLPSOLILHGLOOXVWUDWLRQRIKRZLQMHFWLRQRI&1&WRJHWKHUZLWK /6 EULQH PLJKW LQFUHDVH WKH RLO UHFRYHU\ E\ ORJMDPPLQJ IROORZHG E\

PLFURVFRSLFIORZGLYHUVLRQ,QDWKHLQMHFWHGIOXLGIROORZVWKHSDWKRIOHDVW UHVLVWDQFH7KH RLO KDV KLJKHU YLVFRVLW\ WKDQWKH LQMHFWHG &1&/6 EULQHDQG DYRLGV VZHHSLQJ ,Q E WKH &1& SDUWLFOHV KDV FDXVHG D ORJMDP LQ WKH IORZ SDWK7KLVLVSODXVLEOHLIWKHSRUHWKURDWQDUURZVVXIILFLHQWO\VRWKHSDUWLFOHV DUHVTXHH]HGWKURXJK7KLVPD\DIIHFWWKHIORZSDWKRIWKHLQMHFWHGEULQHDQG LQFUHDVHLQSUHVVXUHGXHWRGHFUHDVHLQSHUPHDELOLW\FDQOHDGWRPRELOLVDWLRQ RIWKHRLOGURSOHW$GDSWHGIURP$XUDQGHWDO Figure 6.1: 6FKHPDWLF RYHU WKH SURGXFWLRQ SURFHGXUH DW )3/ )RU WKLV SURFHVVWKHHQGSURGXFWKDGDFRQFHQWUDWLRQRIZWEXWWKLVFDQEHWXQHG YLDXOWUDILOWUDWLRQ$GDSWHGIURP5HLQHU 5XGLH Figure 6.2:2XWFURSVDQGVWRQHFRUHVDPSOH60 Figure 6.3:$)0ZLWKWLSKROGHUODVHUDQGPLUURUV Figure 6.4:+DVVOHUFRUHKROGHUXVHGLQWKHH[SHULPHQWV Figure 6.5: 6FKHPDWLF RI WKH FRUH IORRGLQJ VHWXS XVHG LQ ZDWHU IORRG DQG (25H[SHULPHQWV/LQHYDOYHVDUHVKRZQLQJUH\DQGZHUHXVHGWRUHJXODWH OLQHIORZ

[L[

Figure 7.2: =HWD SRWHQWLDO RI D ZW &1& GLVSHUVLRQ DV DQ HIIHFW RI GLVSHUVLRQS+PHDVXUHGDWƒ&

Figure 7.3:=HWDSRWHQWLDODVDIXQFWLRQRILQFUHDVLQJWKHWHVWLQJWHPSHUDWXUH IURP±ƒ&

Figure 7.4:9LVFRVLW\RI&1&/6GLVSHUVLRQVDWLQFUHDVLQJVKHDUUDWHVIURP

±V0HDVXUHPHQWVZHUHSHUIRUPHGDWƒ&

Figure 7.5: 9LVFRVLW\ PHDVXUHPHQWV SHUIRUPHG RQ &1&/6 GLVSHUVLRQV DW VKHDUUDWHVIURP±V$OOGLVSHUVLRQVKDGD&1&FRQFHQWUDWLRQRI ZWZLWKDQLQFUHDVLQJDPRXQWRI1D&O0HDVXUHPHQWVZHUHSHUIRUPHG DWƒ&

Figure 7.6:9LVFRVLW\RI&1&',GLVSHUVLRQVYVVKHDUUDWHPHDVXUHGDW

ƒ&

Figure 7.7:9LVFRVLW\RI&1&/6GLVSHUVLRQVYVVKHDUUDWHPHDVXUHGDW

ƒ&

Figure 7.8: 9LVXDO HYDOXDWLRQ RI &1& VDPSOHV DIWHU DJLQJ DW ƒ& D 6KRZV&1&',DQG&1&/6GLVSHUVLRQVULJKWDIWHUVDPSOHSUHSDUDWLRQW E 6DPSOHV DIWHU KRXUV &1&', LV VOLJKWO\ GDUNHU WKDQ &1&/6 F 6DPSOHVDIWHUKRXUV7KH&1&',VDPSOHLVVWLOOPRUHPLVFRORXUHGWKDQWKH

&1&/6VDPSOHG6DPSOHVDIWHUKRXUV,WZDVQRWSRVVLEOHWRGLVWLQJXLVK EHWZHHQWKHVDPSOHVGXHWRKHDY\GLVFRORXUDWLRQLQERWKVDPSOHV Figure 7.9:9LVFRVLW\PHDVXUHPHQWVRI&1&',SHUIRUPHGDWq&RQ ZWVDPSOHVDIWHUKHDWDJLQJDWGLIIHUHQWWHPSHUDWXUHV Figure 7.10:9LVFRVLW\PHDVXUHPHQWVRI&1&/6SHUIRUPHGDWq&RQ ZWVDPSOHVDIWHUKHDWDJLQJDWGLIIHUHQWWHPSHUDWXUHV Figure 7.11: 9LVFRVLW\ GHYHORSPHQW IRU D ZW &1&', GLVSHUVLRQ WHVWHGDWƒ&(DFKSRLQWLVRQHYLVFRVLW\PHDVXUHPHQWDQGZDVSHUIRUPHG IRUPLQXWHVDWVDQGEHWZHHQHDFKVXFKPHDVXUHPHQWWKHVDPSOHZDV UHVWHGIRUPLQXWHV Figure 7.12: 9LVFRVLW\ GHYHORSPHQW IRU D ZW &1&/6 GLVSHUVLRQ WHVWHGDWq&(DFKSRLQWLVRQHYLVFRVLW\PHDVXUHPHQWDQGZDVSHUIRUPHG IRUPLQXWHVDWVDQGEHWZHHQHDFKVXFKPHDVXUHPHQWWKHVDPSOHZDV UHVWHGIRUPLQXWHV Figure 7.13:/RQJWLPHKHDWDJLQJH[SHULPHQWDWƒ&IRUDQGZW

&1&/6

[[

Figure 7.14: &1& FU\VWDOOLWHV GLVSHUVHG LQ ', ZDWHU DQG GHSRVLWHG RQWR D PLFDGLVFEHIRUHULQVLQJZLWK',ZDWHUWRGLOXWHWKHVDPSOH7KHEDUVKRZQRQ WKHULJKWLQGLFDWHVWKHKHLJKWRIWKHSDUWLFOHV Figure 7.15:&1&GLVSHUVLRQLQ/6EULQHSULRUWRKHDWDJLQJ Figure 7.16: &1& SDUWLFOH DJJORPHUDWHV LQ /6 EULQH SULRU WR KHDW DJLQJ GLOXWHGRQWRPLFDGLVF Figure 7.17:&1&GLVSHUVLRQLQ/6EULQHDIWHURQHZHHNRIKHDWDJLQJDW

ƒ&

Figure 7.18:'LOXWHG&1&DJJORPHUDWHVLQ/6EULQHDIWHURQHZHHNRIKHDW DJLQJDWƒ&

Figure 7.19:&1&GLVSHUVLRQLQ/6EULQHKHDWDJHGDWƒ&IRURQHZHHN 5LEERQOLNHVWUXFWXUHVFDQEHREVHUYHG Figure 7.20:'LOXWHG&1&DJJORPHUDWHVLQ/6EULQHDIWHURQHZHHNRIKHDW DJLQJDWƒ&

Figure 7.21: 'LIIHUHQWLDO SUHVVXUH GHYHORSPHQW DV D IXQFWLRQ RI LQMHFWHG

&1&/6 EULQHV DW DPELHQW WHPSHUDWXUH ,QMHFWLRQ UDWH ZDV 39GD\

P/PLQ 7KH JDS LQ WKH ZW &1&/6 PHDVXUHPHQW ZDV FDXVHG E\

FRPSXWHUIDLOXUHOHDGLQJWRKRXUVRIGLIIHUHQWLDOSUHVVXUHPHDVXUHPHQWV EHLQJORVW Figure 7.22: 6KHDU YLVFRVLW\ RI EXON VDPSOHV FRPSDUHG WR WKH UHVSHFWLYH HIIOXHQWVDPSOHVRIWKHLQMHFWHG&1&/6EULQHV$Q/6EULQHUHIHUHQFHLVDOVR VKRZQ Figure 7.23:S+FKDQJHLQ&1&/6PHDVXUHGIRUHDFKLQMHFWHGSRUHYROXPH 7KHEXON&1&/6S+ZDVDQGIRUDQGZW&1&

UHVSHFWLYHO\

Figure 7.24:9LVXDOLQVSHFWLRQRIWKHHIIOXHQWRIZW&1&/6EULQH Figure 7.25'LIIHUHQWLDOSUHVVXUHDVDIXQFWLRQRILQMHFWHGSRUHYROXPHV39 GXULQJ LQMHFWLRQ RI ZW &1& LQ /6 EULQH LQWR D /6 VDWXUDWHG VDQGVWRQHFRUH,QMHFWLRQUDWHZDVP/PLQ39GD\

Figure 7.26:9LVFRVLW\DWƒ&RIZW&1&LQ/6EULQHVDPSOHVEHIRUH LQMHFWLRQDQGLQHIIOXHQWVDPSOHVDIWHULQMHFWLRQLQWRFRUH60DWDQG

ƒ&

Figure 7.28:2LOUHFRYHU\LQ22,3RI/6EULQHDQG&1&/6EULQHLQMHFWHG ILUVWZLWKDUDWHRI39GD\DQGDWODVWDW39GD\DOODWƒ&7KHUHVXOWV DUH VKRZQ DV D IXQFWLRQ RI LQMHFWHG SRUH YROXPHV WLPH 7KH GLIIHUHQWLDO SUHVVXUHIRUWKHZKROHPHDVXUHPHQWLVDOVRLQFOXGHG

[[L

WLPH 7KH GLIIHUHQWLDO SUHVVXUH LV VKRZQ DV D IXQFWLRQ RI LQMHFWHG SRUH YROXPHV

[[LL

[[LLL

Table 2.1: &ROORLGDO VWDELOLW\ RI GLVSHUVLRQV ZLWK LQFUHDVLQJ ]HWD SRWHQWLDO

$GDSWHGIURP6DORSHNHWDO Table 3.1: (OHPHQWDO FRPSRVLWLRQ RI FUXGH RLO *DU\ HW DO 6SHLJKW Table 3.2:3URSHUWLHVRIWKHPRVWFRPPRQFOD\PLQHUDOVTechnical Manual for Drilling, Completion and Workover Fluids Table 4.1:&RQWDFWDQJOHVIRUDZDWHURLOV\VWHP$GDSWHGIURP=RORWXNKLQ 8UVLQG Table 6.1: &1& FKDUDFWHULVWLFV DGDSWHG IURP +HJJVHW HW DO DQG 6DFXLHWDO Table 6.2:%ULQHFRPSRVLWLRQV7'6 WRWDOGLVVROYHGVROLGV— YLVFRVLW\

Table 6.3:0LQHUDORJLFDOSURSHUWLHVRIWKHRXWFURSVDQGVWRQHFRUHVXVHGLQWKH H[SHULPHQWVJLYHQLQZW$GDSWHGIURP3LxHUH]7RUULMRVHWDO Table 6.4:3K\VLFDOFRUHSURSHUWLHV Table 6.5:&UXGHRLOSURSHUWLHV Table 7.1:S+YDOXHVRISUHSDUHG&1&GLVSHUVLRQV Table 7.2:S+YDOXHVLQZW&1&VDPSOHVGLVSHUVHGLQ',ZDWHUDQG/6 EULQHEHIRUHDQGDIWHUWLWUDWLRQZLWKHLWKHUP01D2+RUP0+&O Table 7.3:S+FKDQJHRYHUWLPHIRUZW&1&GLVSHUVLRQVVDPSOHVDJHG DWƒ&.

Table 7.4:S+FKDQJHIRUZW&1&GLVSHUVLRQVDJHGKRXUVDW

ƒ&.

Table 7.5: 7KH LQ S+ LQ ZW &1&', DQG &1&/6 EHIRUH DQG DIWHU

G\QDPLFKHDWDJLQJDWq&

Table 7.6:7KHS+ LQ DQG ZW &1& VDPSOHV EHIRUHDQGDIWHU WKH ORQJWHUPVKHDUUHVWPHDVXUHPHQWV Table 7.7:2YHUYLHZRIFRUHSHUPHDELOLWLHVDIWHUIRUZDUGDQGUHYHUVHIORRGLQJ RI /6 EULQH ZLWK HOHYDWHG LQMHFWLRQ UDWH P/PLQ DQG VWDEOHU GLIIHUHQWLDO SUHVVXUH Table 7.8: &RUH SHUPHDELOLW\ 60 DIWHU FRUH FOHDQLQJFRUH UHJHQHUDWLRQ DQGSULRUWRLQMHFWLYLW\WHVWVDWDQGƒ&3HUPHDELOLW\LQGLFDWHV WKHFDOFXODWHGYDOXHVEHWZHHQPHDVXUHPHQWVDIWHUUHJHQHUDWLRQ

[[LY

Table 7.9S+GHYHORSPHQWLQZW&1&LQEXON/6EULQHEHIRUHDQG HIIOXHQWVDPSOHVDIWHUFRUHIORRGLQJDWDQGƒ&

Table 7.10:0HDVXUHGS+LQEXONDQGHIIOXHQWZKHQLQMHFWHGDWƒ&

[[Y

1/κ 'HE\HOHQJWK

$)0 $WRPLFIRUFHPLFURVFRS\

$*8 $QK\GURJOXFRVHXQLW

$1 $FLGQXPEHU

%1 %DVHQXPEHU

&%5 &UXGHRLOEULQHURFNV\VWHP

&(& &DWLRQH[FKDQJHFDSDFLW\

&0& FDUER[\PHWK\OFHOOXORVH

&1& &HOOXORVHQDQRFU\VWDOV

&1&', &1&GLVSHUVHGLQ',ZDWHU

&1&/6 &1&GLVSHUVHGLQ/6EULQH

&1) &HOOXORVHQDQRILEULOV

G): )RUPDWLRQZDWHUGLOXWHGWLPHV ', 'HLRQLVHGZDWHU

'3 'HJUHHRISRO\PHULVDWLRQ E *OREDOGLVSODFHPHQWHIILFLHQF\

E 6WUHQJWKRIWKHHOHFWULFILHOG

E_D 0LFURVFRSLFGLVSODFHPHQWHIILFLHQF\

('/ (OHFWULFDOGRXEOHOD\HU (25 (QKDQFHGRLOUHFRYHU\

ε 'LHOHFWULFFRQVWDQW ε0 3HUPLWWLYLW\RIIUHHVSDFH

εr 'LHOHFWULFFRQVWDQWRIGLVSHUVLQJPHGLXP

η 9LVFRVLW\

E_V 0DFURVFRSLFYROXPHWULFGLVSODFHPHQWHIILFLHQF\

φ 3RURVLW\

φ_c 0LQLPXPRYHUODSFRQFHQWUDWLRQ )3/ )RUHVW3URGXFWV/DERUDWRU\

): )RUPDWLRQZDWHU

g *UDYLWDWLRQDODFFHOHUDWLRQFRQVWDQW g_c &RQYHUVLRQIDFWRU

H +HLJKWRIFROXPQ +&O +\GURFKORULFDFLG +(& +\GUR[\HWK\OFHOOXORVH +3$0 +\GURO\VHGSRO\DFU\ODPLGH +3ȕ&' K\GUR[\SURS\OȕF\FORGH[WULQ +62 6XOSKXULFDFLG

I_AH $PRWW+DUYH\LQGH[

[[YL

,)7 ,QWHUIDFLDOWHQVLRQ I_o 2LOZHWWLQJLQGLFH I_w :DWHUZHWWLQJLQGLFH ,25 ,PSURYHGRLOUHFRYHU\

J 6XUIDFHFXUYDWXUH k 3HUPHDELOLW\

k_rw 5HODWLYHSHUPHDELOLW\RIZDWHU L /HQJWKRIFDSLOODU\WXEH /'9 /DVHU'RSSOHUYHORFLPHWU\

λ_D 0RELOLW\RIGLVSODFLQJIOXLG λ_d 0RELOLW\RIGLVSODFHGIOXLG /3* /LTXLGSHWUROHXPJDV

/6 /RZVDOLQLW\EULQHSSP1D&O /6( /RZVDOLQLW\HIIHFW

M 0RELOLW\UDWLR

P0 0LOOLPRODU

Pȍ 0LOOL2KP

0,( 0XOWLFRPSRQHQWLRQH[FKDQJH PHT 0LOOLHTXLYDOHQWV

μ 9LVFRVLW\

μ_E (OHFWURSKRUHWLFPRELOLW\

μM 0LFURPRODU

μS 0LFUR6LHYHUW P6 0LOOL6LHYHUW

1D&0& 6RGLXPFDUER[\PHWK\OFHOOXORVH 1D2+ 6RGLXPK\GUR[LGH

N_c &DSLOODU\QXPEHU 12. 1RUZHJLDQNURQHU

13' 1RUZHJLDQ3HWUROHXP'LUHFWRUDWH 2(' 2OMHRJ(QHUJLGHSDUWHPHQWHW 22,3 2ULJLQDORLOLQSODFH

25' 2[LGDWLYHUHGXFWLYHGHSRO\PHULVDWLRQ 263$5 2VOR3DULV&RPPLVVLRQ

ΔP 3UHVVXUHGLIIHUHQFH

3D 3DVFDO

3$& 3RO\DQLRQLFFHOOXORVH 3$1, 3RO\DQLOLQH

P_b %XEEOHSRLQWSUHVVXUH P_c &DSLOODU\SUHVVXUH P_res 5HVHUYRLUSUHVVXUH Π 'LVMRLQLQJSUHVVXUH

[[YLL

SSP 3DUWVSHUPLOOLRQ

39 3RUHYROXPH

r 3RUHUDGLXV

52 5HYHUVHRVPRVLV

U 'HQVLW\

σ ,QWHUIDFLDOWHQVLRQ

ΔS_ws &KDQJHLQZDWHUVDWXUDWLRQVSRQWDQHRXVLPELELWLRQ ΔS_wf &KDQJHLQZDWHUVDWXUDWLRQIRUFHGLPELELWLRQ ΔS_os &KDQJHLQRLOVDWXUDWLRQVSRQWDQHRXVLPELELWLRQ ΔS_of &KDQJHLQRLOVDWXUDWLRQIRUFHGLPELELWLRQ 6'6 6RGLXPGRGHF\OVXOSKDWH

S_oi ,QLWLDORLOVDWXUDWLRQ S_or 5HVLGXDORLOVDWXUDWLRQ S_wi ,QLWLDOZDWHUVDWXUDWLRQ S_wr ,UUHGXFLEOHZDWHUVDWXUDWLRQ 7'6 7RWDOGLVVROYHGVROLGV 7*$ 7KHUPRJUDYLPHWULFDQDO\VLV 72& 7RWDORUJDQLFFRQWHQW θ &RQWDFWDQJOH

v 9HORFLW\

9': YDQGHU:DDOVIRUFHV ZW :HLJKWSHUFHQW ζ =HWDSRWHQWLDO

c $QJVWURP

[[YLLL

1 Motivation and Outline

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cP FRPPLWWHH ZDV DSSRLQWHG E\ WKH 1RUZHJLDQ 0LQLVWU\ RI 3HWUROHXP DQG (QHUJ\ 2(' DQG LQ WKH\

FRQFOXGHGWKDW DQLQFUHDVHLQRLOUHFRYHU\RIRQO\ IURPWKH1RUZHJLDQ 6KHOI ZDV ZRUWK ELOOLRQ 12.cP HW DO 6HYHQ \HDUV ODWHUWKLV VXPLVSUREDEO\VPDOOHUGXHWRWKHGHFOLQHLQRLOSULFHVEXWVWLOODFRQVLGHUDEOH DPRXQWRIPRQH\

'HYHORSLQJ DQG DSSO\LQJ HFRQRPLFDOO\ YLDEOH DQG HQYLURQPHQWDOO\ IULHQGO\

HQKDQFHGRLOUHFRYHU\(25PHWKRGVLVWKHUHIRUHRIFUXFLDOLPSRUWDQFH7KH HIIHFWRILPSOHPHQWLQJORZVDOLQLW\IORRGLQJEULQHVLQRLOUHFRYHU\KDVEHHQ NQRZQIRUDOPRVW\HDUVDQGLQWKLVWKHVLVZRUNWKHDLPZDVWRFRPELQH ORZVDOLQLW\IORRGLQJZLWKDQHZSRWHQWLDOELRSRO\PHUQDQRSDUWLFOHDGGLWLYH QDPHO\ FHOOXORVH QDQRFU\VWDOV &1& 'XH WR LWV UHQHZDEOH VRXUFH PDWHULDO DQG WKH DEVHQFH RI GDQJHURXV EUHDNGRZQ SURGXFWV PDNHV &1& D VDIH DQG JUHHQDOWHUQDWLYHWRH[LVWLQJWHFKQRORJLHV

7KHWKHVLVZRUNKDVEHHQGLYLGHGLQWRWZRVHSDUDWHSDUWVFKDUDFWHUL]DWLRQRI WKH FHOOXORVLF PDWHULDO XQGHU SK\VLFDO FRQGLWLRQV WKDW LV HQFRXQWHUHG LQ RLO UHVHUYRLUV DQG FRUH IORRGLQJ VWXGLHV ZKHUH ILUVW WKH LQMHFWLYLW\ RI EULQHV FRQWDLQLQJ &1& ZDV VWXGLHG WR GHWHUPLQH VXLWDEOH SRO\PHU FRQFHQWUDWLRQV DQG WHPSHUDWXUH SHUIRUPDQFH DQG DW ODVW HQKDQFHG RLO UHFRYHU\ WHVWV DOO DW ODERUDWRU\VFDOH

Motivation and Outline

2 Introduction to Nanocellulose

2.1 Cellulose

&HOOXORVH LV D SRO\PHULF ELRPDWHULDO DQG LW LV WKH PRVW DEXQGDQW PDWHULDO SURGXFHG E\ WKH ELRVSKHUH ZLWK [ WRQV RI HVWLPDWHG DQQXDO SURGXFWLRQ.OHPPHWDO&HOOXORVHEDVHGPDWHULDOVKDYHEHHQLQXVH DV HQJLQHHULQJ PDWHULDOV IRU WKRXVDQGV RI \HDUV DQG VWLOO DUH WRGD\ ZLWK D KXJH PDUNHW DQG LQGXVWULHV IRU IRUHVW SURGXFWV DQG WKHLU GHULYDWLYHV 7RGD\

WKH ODUJHVW FRQVXPHU RI FHOOXORVH LV WKH SDSHU DQG FDUGERDUG LQGXVWU\

'XIUHVQHD,Q$QVHOPH3D\HQILUVWXVHGWKHWHUP³FHOOXORVH´

DQGKHHVWDEOLVKHGWKURXJKSXULILFDWLRQRISODQWWLVVXHWKDWWKHILEURXVFRQWHQW RI SODQW FHOOV KDV D XQLTXH FKHPLFDO VWUXFWXUH 3D\HQ ,Q :LOOVWlWWHU DQG =HFKPHLVWHU HVWDEOLVKHG WKH EDVLF FHOOXORVH IRUPXOD :LOOVWlWWHU =HFKPHLVWHU

&HOOXORVH LV IRXQG LQ WKH SURWHFWLYH FHOO ZDOOV RI SODQWV EDFWHULD IXQJL DQG FHUWDLQDQLPDOVWXQLFDWHVDQGLVDQLPSRUWDQWHOHPHQWIRUPDLQWDLQLQJWKHLU VWUXFWXUDOLQWHJULW\ ,WLVFRPSRVHGRI'JOXFRS\UDQRVHULQJVOLQNHGWRJHWKHU WKURXJKȕJO\FRVLGLFERQGV$GMDFHQWULQJVDUHDUUDQJHGLQVXFKDZD\VR WKHJOXFRVLGLFR[\JHQVSRLQWVLQRSSRVLWHGLUHFWLRQVDQGWKHUHSHDWLQJXQLWRI FHOOXORVHLVQDPHGFHOORELRVHDVLQGLFDWHGLQ)LJXUH

Figure 2.1:7KHFKHPLFDOVWUXFWXUHRIFHOOXORVH

7KHFHOORELRVHXQLWVFRYDOHQWO\OLQNWRIRUPDOLQHDUKRPRSRO\PHUFRQVLVWLQJ RIEHWZHHQDQGUHVLGXHVDQGWKHGHJUHHRISRO\PHUL]DWLRQ'3 GHSHQGV RQ WKH FHOOXORVH VRXUFH ZLWK ZRRG FHOOXORVH KDYLQJ D '3 RI DSSUR[LPDWHO\JOXFRS\UDQRVHXQLWV6M|VWU|P$VJOXFRVHXQLWV

Introduction to Nanocellulose

DUHQPcORQJVWUHWFKHGJOXFRVHFKDLQVPD\EHEHWZHHQDQG —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

Figure 2.2:6FKHPDWLFVWUXFWXUHRIFHOOXORVHIURPSODQW FHOOZDOOVWRVLQJOHFHOOXORVHFKDLQV FRQVLVWLQJRIUHSHDWLQJFHOORELRVHXQLWV$GDSWHGIURP7VXFKLNDZD

2.2 Cellulose nanocrystals (CNC)

&HOOXORVH QDQRFU\VWDOV &1& LV D VXEHQWLW\ RI FHOOXORVH ILEUHV DQG DUH SURGXFHG ³WRSGRZQ´ WKURXJK DFLG K\GURO\VLV RI WKH FHOOXORVH ZKHUH WKH DPRUSKRXVUHJLRQVRIWKHILEUHVDUHGLVVROYHG

2.2.1 Background

$V PHQWLRQHG SUHSDUDWLRQ RI &1& LV QRW D V\QWKHVLV EXW D ³WRSGRZQ´

SURFHVV ZKHUH ILEURXV FHOOXORVH PDWHULDO LV VSOLW XS LQWR FU\VWDOOLQH HQWLWLHV 7KLVSKHQRPHQRQZDVILUVWREVHUYHGE\1LFNHUVRQDQG+DEUOHZKHQERLOLQJ RIFHOOXORVHILEUHVLQDFLGLFVROXWLRQOHGWRDGHJUDGDWLRQOLPLWDIWHUDFHUWDLQ WLPHRIK\GURO\VLVWUHDWPHQW1LFNHUVRQ +DEUOH7KLVZRUNLQVSLUHG 5nQE\ DQG KLV FRZRUNHUV DW WKH 8QLYHUVLW\ RI 8SSVDOD WR LQYHVWLJDWH WKH SUHSDUDWLRQRIVWDEOHFROORLGDOVXVSHQVLRQVRIDPRQJRWKHUVZRRGFHOOXORVH WKURXJKFRQWUROOHGK\GURO\VLVZLWKVXOSKXULFDFLG$QH[DPSOHRIDQDTXHRXV

&1&GLVSHUVLRQLVVKRZQLQ)LJXUH

Figure 2.3:&1&LQDTXHRXVGLVSHUVLRQSLFWXUHGZLWKDWRPLFIRUFHPLFURVFRS\$)0

Introduction to Nanocellulose

5nQE\VXJJHVWHGWKDW³PLFHOODUVWULQJV´FU\VWDOOLQHUHJLRQVZHUHWKHEXLOGLQJ EORFNVRIZRRGDQGFRWWRQFHOOXORVHDQGWKDWWKHVHFRXOGH[LVWLQDIUHHIRUP RULQDJJUHJDWHVDQGKDYHDFRQVWDQWZLGWKRIaQP7KHVHEXLOGLQJEORFNV FRXOGEHVHWIUHHE\XOWUDVRQLFPHFKDQLFDOWUHDWPHQWDQGK\GURO\VLVZRXOG FXW WKHVH VWULQJV LQWR ³PLFHOOHV´ RU VKRUW IUDJPHQWV 5nQE\

2.2.2 Production

6LQFH WKH V WKH SURGXFWLRQ RI ZRRG &1& KDV EHFRPH UHODWLYHO\

VWDQGDUGLVHG 7KH ILEUHV DUH XVXDOO\ K\GURO\VHG XVLQJ HLWKHU VXOSKXULF DFLG +62RUK\GURFKORULFDFLG+&OZKLFKSURGXFHVFU\VWDOOLWHVZLWKVOLJKWO\

GLIIHUHQW SURSHUWLHV 6LQFH WKH FHOOXORVH PXVW EH GLUHFWO\ K\GURO\VHG D IHZ SUHWUHDWPHQW VWHSV DUH QHFHVVDU\ 7KH JHQHUDO SURFHGXUH LV JLYHQ LQ )LJXUH

Figure 2.4:*HQHUDOSURGXFWLRQSURFHGXUHIRU&1&$GDSWHGIURP'XIUHVQHE

)LUVWLIWKHPDVVLVXQWUHDWHG WKHELRPDVVLVGHZD[HGE\XVLQJWROXHQHDQG HWKDQRORUEHQ]HQHDQGHWKDQRO7KHQIROORZVDQDONDOLH[WUDFWLRQDQG DIWHUWKDWDEOHDFKLQJVWHS7KHDONDOLWUHDWPHQWLVSHUIRUPHGWRVROXELOLVHWKH SHFWLQV DQG KHPLFHOOXORVHV LQ WKH PDWHULDO DQG WKH EOHDFKLQJ VWHS UHPRYHV UHVLGXDO SKHQROLF FRPSRXQGV OLNH OLJQLQ SRO\SKHQROV DQG SURWHLQV 7KLV H[WUDFWLRQ PHWKRG KDVEHHQ UHODWLYHO\ VWDQGDUGLVHG VLQFHWKH V :LVHHW DO 7KH H[WUDFWLRQ DQG EOHDFKLQJ SURFHVVHV PD\ EH UHSHDWHG VHYHUDO WLPHV DQG ILOWUDWLRQ DQG ZDVKLQJ ZLWK GLVWLOOHG ZDWHU LV SHUIRUPHG EHWZHHQ HDFKVWHS,IWKHVWDUWLQJELRPDVVLVEOHDFKHGIURPWKHSURGXFHUWKLVVWHSFDQ EHRPLWWHG

7KH QH[W VWHS LV WR K\GURO\VH WKH DPRUSKRXV GRPDLQV RI WKH ILEUHV 7KHVH UHJLRQV DUH UDQGRPO\ RUJDQLVHG DQG KDYH D ORZHU GHQVLW\ FRPSDUHG WR WKH QDQRFU\VWDOOLQHSDUWV%URZQ-U 6D[HQDGH6RX]D/LPD %RUVDOL

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

±QPZLWKZLGWKVIURP±QP.OHPPHWDO

7KHVHQHJDWLYHO\FKDUJHGVXUIDFHJURXSVFUHDWHDQHOHFWURVWDWLFGRXEOHOD\HU ('/ DURXQG WKH SDUWLFOH ZKLFK SURPRWHV LWV GLVSHUVDELOLW\ LQ ZDWHU 7KH HOHFWURVWDWLFUHSXOVLRQVEHWZHHQWKH('/VRILQGLYLGXDOSDUWLFOHVDUHWKHPDLQ FDXVHV RI WKH GLVSHUVLRQ VWDELOLW\ RI VXOSKXULF DFLG K\GURO\VHG &1&

'XIUHVQHE

Introduction to Nanocellulose

2.2.3 Colloidal behaviour of cellulose nanocrystals

:KHQ GLVSHUVHG LQ ',ZDWHU FHOOXORVH QDQRFU\VWDOV IRUP FROORLGDO GLVSHUVLRQV)RUDGLVSHUVLRQWREHWHUPHG³FROORLGDO´WKHGLVSHUVHGSDUWLFOHV PXVW KDYH D VL]H UDQJH EHWZHHQ QP DQG —P 7KH VWDELOLW\ RI VXFK GLVSHUVLRQVGHSHQGVRQDQXPEHURIGLIIHUHQWSDUDPHWHUVSDUWLFOHGLPHQVLRQ VL]H SRO\GLVSHUVLW\ DQG WKH VXUIDFH FKDUJH &HOOXORVH QDQRFU\VWDOV SURGXFHG XVLQJ VXOSKXULF DFLG ZLOO EH VWDEOH LQ DQ DTXHRXV GLVSHUVLRQ GXH WR WKH QHJDWLYHO\FKDUJHGKDOIHVWHUVXOSKDWHJURXSVFUHDWHGRQWKHVXUIDFHGXULQJWKH K\GURO\VLV VWHS )LJXUH 7KHVH FDXVHV DQ ('/ WR IRUP DURXQG WKH SDUWLFOHV DQG WKXV WKH SDUWLFOHV DUH HOHFWURVWDWLFDOO\ VWDELOLVHG $UDNL HW DO

Figure 2.5:6FKHPDWLFRIDFLGK\GURO\VLVRI&1&QRWWRVFDOH

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

SDUWLFOHV LQ WKH VDPH GLUHFWLRQ DORQJ D GLUHFWLQJ YHFWRU ZKLFK UHVXOWV LQ D QHPDWLF OLTXLG FU\VWDOOLQH DOLJQPHQW 7KH FKLUDO QHPDWLF SLWFK 3 LV WKH GLVWDQFHLWWDNHVIRUWKHFU\VWDOOLQHSDUWLFOHVWRWDNHDIXOOƒWZLVW,Q)LJXUH WKLVLVJLYHQDV3LQGLFDWLQJWKDWWKHFU\VWDOOLWHVDUHRQO\WZLVWLQJƒ

3FDQEHWXQHGE\DOWHULQJWKHWHPSHUDWXUHRIWKHGLVSHUVLRQRUE\DGGLQJRWKHU PROHFXOHVOLNHVDOWV:KHQWKHSLWFKLVLQWKHVDPHRUGHUDVWKHZDYHOHQJWKRI

YLVLEOHOLJKWLWFDQUHIOHFWSRODULVHGOLJKWGH9ULHV.RSSHWDO ,I WKH FRQFHQWUDWLRQ LV IXUWKHU LQFUHDVHG WKH GLVSHUVLRQ UHDFKHV D FULWLFDO FRQFHQWUDWLRQ ZKHUH WKH &1& PD\ IRUP D FKLUDO QHPDWLF RUGHUHG SKDVH ZKLFKZLOOGLVSOD\W\SLFDOFKROHVWHULFOLTXLGFU\VWDORSWLFDOSURSHUWLHV;0 'RQJHWDO0DUFKHVVDXOWHWDO0DUFKHVVDXOWHWDO5HYRO HWDO5HYROHWDO

Figure 2.6: ,OOXVWUDWLRQ RI D ELSKDVLF GLVSHUVLRQ RI &1& LQ ZDWHU DV LW ZRXOG ORRN WKURXJK FURVVHGSRODULVHUV7KHLVRWURSLFSKDVHLVVKRZQRQWKHOHIWDQGDQLVRWURSLFSKDVHLVVKRZQRQ WKHULJKW3KRWRJUDSKRIELSKDVLF&1&GLVSHUVLRQIURP;'RQJHWDO

7KH FROORLGDO VWDELOLW\ RI FKDUJHG QDQRSDUWLFOHV OLNH &1& LQ GLVSHUVLRQ LV PDLQO\JRYHUQHGE\WKH]HWDSRWHQWLDOȗ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

Introduction to Nanocellulose

SDUWLFOHZKLOHWKHIUHHFRXQWHULRQVLQWKHGLIIXVHOD\HUEXONPHGLXPGRQRW 7KHHOHFWURNLQHWLFSRWHQWLDOWKXVIRUPHGLQWKHVOLSSLQJSODQHLVNQRZQDVWKH ]HWD SRWHQWLDO QRUPDOO\ JLYHQ LQ P9 $ KLJK ]HWD SRWHQWLDO HLWKHU QHJDWLYH SRVLWLYH LQGLFDWHV D VWURQJ HOHFWURVWDWLF UHSXOVLRQ EHWZHHQ WKH SDUWLFOHV LQYROYHG6XUIDFHIRUFHVZLOOEHPRUHWKRURXJKO\GHVFULEHGLQ&KDSWHU

Figure 2.7:*UDSKLFSUHVHQWDWLRQRIWKHHOHFWULFDOGRXEOHOD\HURIDQHJDWLYHO\FKDUJHGSDUWLFOH

7KH UHSXOVLRQ LQKLELWV DJJORPHUDWLRQ DQG VHWWOLQJ RI WKH GLVSHUVHG SDUWLFOHV DQG OHDGV WR D VWDEOH GLVSHUVLRQ ,Q 7DEOH WKH FROORLGDO VWDELOLW\ RI GLVSHUVLRQV ZLWK LQFUHDVLQJ ]HWD SRWHQWLDO LV JLYHQ +DQDRU HW DO +XQWHU6DORSHNHWDO

Table 2.1: &ROORLGDO VWDELOLW\ RI GLVSHUVLRQV ZLWK LQFUHDVLQJ ]HWD SRWHQWLDO $GDSWHG IURP 6DORSHNHWDO

Zeta potential (mV) Colloidal stability

WR“ 5DSLGIORFFXODWLRQFRDJXODWLRQ

“WR“ ,QFLSLHQWVWDELOLW\

“WR“ 0RGHUDWHVWDELOLW\

“WR“ *RRGVWDELOLW\

!“ ([FHOOHQWVWDELOLW\

2.2.4 Rheology

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

$VDGD$W\SLFDOYLVFRVLW\SURILOHIRU&1&LQGLVSHUVLRQLVLOOXVWUDWHG LQ)LJXUH

Figure 2.8: 6KHDUUDWHGHSHQGHQF\LOOXVWUDWHGIRUD&1&GLVSHUVLRQ7KHGLIIHUHQWVKHDUUHJLRQV DUHLQGLFDWHGZLWKEOXHGDVKHGOLQHV$GDSWHGIURP6KDILHL6DEHW

5HJLRQ , DSSHDU DW ORZ VKHDU UDWHV UHSUHVHQWLQJ D FRQVWDQW GHFUHDVH LQ YLVFRVLW\GXHWRWKHPDWHULDOIORZLQJLQGRPDLQV,QUHJLRQ,,WKHVHGRPDLQV DUH VWDUWLQJ WR EUHDN XS DQG WKLV IRUPV D SODWHDX LQ WKH IORZ FXUYH DV

Introduction to Nanocellulose

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

7KH VKHDU G\QDPLFV RI D &1& GLVSHUVLRQ ZLOO DOVR EH GHSHQGHQW RQ WKH FRQFHQWUDWLRQ RI GLVSHUVHG &1& %HUFHD DQG 1DYDUG GLYLGHG WKLV EHKDYLRXULQWRWZRGLIIHUHQWUHJLPHVLVRWURSLFDWUHVW±ZWGLOXWH DQGVHPLGLOXWHUHJLPHVDQGDQLVRWURSLFDWUHVW±ZWFRQFHQWUDWHG UHJLPH)RUWKHLVRWURSLFUHJLPHWKHYLVFRVLW\SURILOHH[KLELWHGWZRSODWHDXV

$WORZVKHDUWKHGLVSHUVLRQVKRZHGDWUXH1HZWRQLDQYLVFRVLW\ZLWKURGVLQ UDQGRP RULHQWDWLRQ LQGHSHQGHQW RI WKH VKHDU UDWH DQG DW KLJK VKHDU WKH SODWHDX LQGLFDWHG URGV ZHOO RULHQWHG LQ D VWHDG\ VWDWH IDVKLRQ DQG WKXV QR FKDQJHLQYLVFRVLW\ZDVREVHUYHG7KHGLVSHUVLRQVLQWKHDQLVRWURSLFUHJLPHF

! ZW H[KLELWHG WKH VDPH EHKDYLRXU DV REVHUYHG LQ WKH 2UWV VWXG\

DQG/LPD %RUVDOLZLWKDSODWHDXUHJLRQVXUURXQGHGE\WZR VKHDUWKLQQLQJUHJLRQVDVVHHQLQ)LJXUH%HUFHD 1DYDUG

(OHFWURYLVFRXVHIIHFWVPXVWDOVREHWDNHQLQWRFRQVLGHUDWLRQZKHQORRNLQJDW VKHDUG\QDPLFVRIFKDUJHGSDUWLFOHV7KHVHHIIHFWVFDXVHVFKDUJHGSDUWLFOHVWR KDYH KLJKHU ORZVKHDU YLVFRVLW\ WKDQ QRQFKDUJHG SDUWLFOHV 5XVVHO :LHUHQJD 3KLOLSVH &KDUJHG %URZQLDQ SDUWLFOHV H[SHULHQFH ('/

GHIRUPDWLRQ XQGHU VKHDU SULPDU\ HOHFWURYLVFRXV HIIHFW DV ZHOO DV RYHUODSSLQJ RI WKH GRXEOH OD\HUV VHFRQGDU\ HOHFWURYLVFRXV HIIHFW ZKLFK FRQWULEXWHV WR WKH KLJKHU ORZVKHDU YLVFRVLW\ &RQZD\ 'REU\'XFODX[

+XQWHU :KHQ WKH LRQLF VWUHQJWK RI WKH GLVSHUVLQJ PHGLXP LV LQFUHDVHG WKH FRQWULEXWLRQ IURP WKH HOHFWURYLVFRXV HIIHFWV LV UHGXFHG 1D&O UHGXFHVWKHVL]HRIWKH('/DQGDVPDOOHUGRXEOHOD\HUOHDGVWROHVVGLVWRUWLRQ XQGHU VKHDU DQG UHGXFHV RYHUODSSLQJ DQG LQWHUDFWLRQV EHWZHHQ WKH SDUWLFOHV UHVXOWLQJLQDORZHUYLVFRVLW\%ROXNHWDO

2.3 Cellulose products in the oil industry

7KHXVHRIFHOOXORVHQDQRFU\VWDOVIRURLOUHODWHGSXUSRVHVLVQRWDFRPSOHWHO\

QHZLGHD$VWKH\DUHGHULYHGIURPFRPSOHWHO\UHQHZDEOHVRXUFHVSODQWVDQG WUHHV DQG GR QRW SURGXFH DQ\ KDUPIXO GHJUDGDWLRQ SURGXFWV WKH\ DUH UHJDUGHGDVDJUHHQFKHPLFDODFFRUGLQJWRWKH263$5&RPPLVVLRQ¶V2VOR 3DULV 3/2125 OLVW FKHPLFDO SRVLQJ OLWWOH RU QR ULVN WR WKH HQYLURQPHQW 263$5 &XUUHQWO\ QR UHSRUWV DUH IRXQG RQ &1& EHLQJ DSSOLHG LQ RLOILHOGV IRU UHFRYHU\ SXUSRVHV EXW LQYHVWLJDWLRQV RQ ODERUDWRU\ VFDOH DUH FXUUHQWO\EHLQJSHUIRUPHGERWKXVLQJVDQGVWRQHFRUHIORRGLQJ$DGODQGHWDO 0ROQHVHWDODQGODVHUHWFKHGJODVVPRGHOV:HLHWDO ,QWKHILHOG&1&LVEHLQJXVHGDVDFHPHQWVWUHQJWKHQHUE\DGGLQJLWWRZHOO IOXLGVDQGLWKDVDOVREHHQXVHGDVDYLVFRVLW\PRGLILHULQZDWHUEDVHGIOXLGV LQWHQGHG IRU IUDFWXULQJ DQG JUDYHO SDFNLQJ 5DH -RKQVWRQ 5LQFRQ 7RUUHV +DOO 7KH HIIHFW RI UHSODFLQJ VROLG FRQWHQW LQ EHQWRQLWH GULOOLQJIOXLGVZLWK&1&DQGRU&1)KDVDOVREHHQH[SORUHGZLWKDQDLPWR LPSURYHFRVWHIILFLHQF\HFRIULHQGOLQHVVDQGVDIHW\RIVXFKIOXLGV$GGLWLRQ RI &1)&1& WR WKH EHQWRQLWHEDVHG GULOOLQJ IOXLGV LPSURYHG ERWK WKH UKHRORJLFDODQGILOWUDWLRQSHUIRUPDQFHRIWKHIOXLGV6RQJHWDO

$VHOHFWLRQRIGLIIHUHQWFHOOXORVHGHULYDWLYHVKDYHDOVREHHQLQYHVWLJDWHGDQG XWLOLVHGIRUGLIIHUHQWSHWUROHXPLQGXVWU\UHODWHGDSSOLFDWLRQV$PRQJWKHVHDUH SRO\DQLRQLF FHOOXORVH 3$& 0DKWR 6KDUPD DQG VRGLXP FDUER[\PHWK\OFHOOXORVH1D&0&'RO]HWDOZKLFKZHUHWHVWHGDVD UKHRORJ\ PRGLILHU LQ GULOOLQJ IOXLGV &0& KDV DOVR EHHQ XVHG WR GRSH SRO\DQLOLQH 3$1, IRU XVH DV D OLTXLG SHWUROHXP JDV /3* VHQVRU ZLWK SURPLVLQJUHVXOWV5DYLNLUDQHWDO

)RU RLOUHFRYHU\ SXUSRVHV GLIIHUHQW K\GURSKRELFDOO\ DQGRU K\GURSKRELFDOO\

PRGLILHG K\GUR[\HWK\O FHOOXORVH +(& YDULHWLHV KDV EHHQ LQYHVWLJDWHG :HYHU HW DO %\ YDU\LQJ WKH PRGLILFDWLRQ RI WKH SDUHQW FHOOXORVLF VWUXFWXUHWKHUKHRORJLFDOSURSHUWLHVRIWKHSRO\PHUGLVSHUVLRQVFDQEHWXQHG IRU H[DPSOH E\ DGGLQJ VXUIDFWDQWV OLNH VRGLXP GRGHF\O VXOSKDWH 6'6 RU K\GUR[\SURS\OȕF\FORGH[WULQ+3ȕ&'.M¡QLNVHQHWDO

Introduction to Nanocellulose

3 Basic Concepts of Oil Recovery

3.1 Introduction

3HWUROHXP RU FUXGH RLO LV D PLQHUDO VXEVWDQFH WKDW LV GHULYHG IURP GHFRPSRVHG RUJDQLF PDWWHU WKDW KDV EHHQ VXEMHFWHG WR HOHYDWHG WHPSHUDWXUH DQG SUHVVXUH E\ 0RWKHU 1DWXUH IRU PLOOLRQV RI \HDUV ,W KDV D FRPSOH[

K\GURFDUERQ PL[WXUH ZLWK SURSHUWLHV YDU\LQJ ZLWK FRPSRVLWLRQ DQG LW FDQ H[LVW LQ D JDVHRXV OLTXLG RU VHPLOLTXLG VWDWH &RPSRQHQWV DQG SK\VLFDO FKDUDFWHULVWLFV RI FUXGH RLO FRPH LQ D ZLGH YDULHW\ EXW WKH HOHPHQWDO FRPSRVLWLRQLVUDWKHUXQLIRUPDQGLVJLYHQLQ7DEOH

Table 3.1:(OHPHQWDOFRPSRVLWLRQRIFUXGHRLO*DU\HWDO6SHLJKW

Element Percentage (in wt. %)

&DUERQ& ±

+\GURJHQ+ ±

6XOSKXU6 ±

1LWURJHQ1 ±

2[\JHQ2 ±

&UXGH RLOV FRQWDLQ ERWK DFLGLF DQG EDVLF FRPSRQHQWV ZKLFK DUH TXDQWLILHG WKURXJK WKHLU UHVSHFWLYH DFLG DQG EDVH QXPEHUV $1 DQG %1 UHVSHFWLYHO\

%RWKYDOXHVDUHUHSRUWHGLQPJ.2+JDQGWKH$1LQGLFDWHVWKHDPRXQWRI .2+LQPJQHHGHGWRQHXWUDOLVHWKHDFLGLFFRPSRQHQWVLQJRIFUXGHRLO )RU%1PJ.2+UHSUHVHQWVWKHHTXDODPRXQWRIEDVLFPDWHULDOWKDWLVSUHVHQW LQJRIFUXGHRLO&DUER[\OLFJURXSV&22+LVWKHPDLQDFLGLFFRPSRQHQW SUHVHQW LQ FUXGH RLO DQG DUH PRVWO\ ERXQG WR ODUJH PROHFXOHV LQ WKH KHDY\

IUDFWLRQVRIWKHK\GURFDUERQVOLNHUHVLQVDQGDVSKDOWHQHV1LWURJHQLVSDUWRI PRVW RI WKH EDVLF FRPSRQHQWV LQ WKH IRUP RI DURPDWLF PROHFXOHV 51 8VXDOO\%1!!$1GXHWRFDUER[\OLFJURXSVGHFRPSRVLQJRYHUJHRORJLFDO WLPHHVSHFLDOO\DWKLJKHUWHPSHUDWXUHV66WUDQGHWDO

+\GURFDUERQV DUH IRUPHG LQ VHGLPHQWDU\ URFNV ZKLFK DUH ULFK LQ RUJDQLF PDWWHUOLNHFRDOVVKDOHVRUFDUERQULFKOLPHVWRQHFDOOHGsource rocks7KLV URFN W\SH LV DEOH WR UHOHDVH YHU\ ODUJH DPRXQWV RI OLTXLG DQG JDVHRXV K\GURFDUERQV 7KH RULJLQ RI SHWUROHXP KDV EHHQ GHEDWHG VLQFH WKH V

Basic Concepts of Oil Recovery

6SHLJKW DQG PDQ\ K\SRWKHVHV KDYH EHHQ SUHVHQWHG RYHU WKH \HDUV 7KHRQHWKDWLVFXUUHQWO\LQIDYRXUDVVHUWVWKDWRLODQGJDVLVGHULYHGIURPWKH RUJDQLF UHVLGXHV RI PDULQH SK\WRSODQNWRQ DV ZHOO DV VRPH IRUDPLQLIHUD DQG DOJDH6NLQQHUHWDO

3K\WRSODQNWRQ DQG EDFWHULD LV WKH PDLQ RUJDQLF PDWWHU LQ PDULQH EDVLQV EXULHG LQ FOD\ DQG PXG LQ WKH VHDIORRU +HUH WKH VHGLPHQWV DUH VORZO\

FRQYHUWHG WR VKDOH GXH WR WKH EXULDO SUHVVXUH DQG WKH JHRWKHUPDO KHDW WUDQVIRUPV WKH RUJDQLF PDWWHU LQWR petroleum 7KH WHPSHUDWXUH PRVW IDYRXUDEOH IRU K\GURFDUERQ JHQHUDWLRQ LV FDOOHG WKHoil window DQG UDQJHV IURPDURXQGWRƒ&$ERYHWKLVWHPSHUDWXUHJDVIRUPDWLRQLVGRPLQDQW DQGLILWEHFRPHVZDUPHUWKDQƒ&WKHSHWUROHXPJHQHUDWLRQFDSDFLW\LV ORVW6HOOH\ 0RULOO7KHFKHPLFDOUHDFWLRQVWKDWDUHLQYROYHGLQFUXGH SHWUROHXPJHQHUDWLRQLVFDOOHGmaturation =RORWXNKLQ 8UVLQD 7KHUHDUHWZRW\SHVRIHYLGHQFHWKDWVXSSRUWVWKHK\SRWKHVLVWKDWFUXGHRLOLVD SURGXFWRIGHFRPSRVLWLRQRIRUJDQLFPDWHULDOGHULYHGIURPOLYLQJRUJDQLVPV )LUVW RLO KDV WKHVDPH RSWLFDO SURSHUWLHV DV K\GURFDUERQV WKDW DUH NQRZQ WR RULJLQDWH IURP RUJDQLF PDWWHU DQG VHFRQG LW FRQWDLQV QLWURJHQ DV ZHOO DV RWKHU FRPSRXQGV OLNH PHWDOORSRUSK\ULQ SLJPHQWV WKDW FDQ RQO\ EH GHULYHG IURPRUJDQLFPDWWHU$OLHWDO6NLQQHUHWDO

0DWXUDWHG SHWUROHXP FDQ RQO\ EH DFFXPXODWHG LI FHUWDLQ FULWHULD DUH PHW ZKLFKLVWKHXQLTXHFRPELQDWLRQRIVRXUFHURFNDQGFRQGLWLRQVXLWDEOHWRWUDS WKHSURGXFHGK\GURFDUERQV&UXGHRLOLVOHVVGHQVHWKDQZDWHUDQGLIUHOHDVHG IURP WKH VRXUFH URFN LQWR D QHLJKERXULQJ SRURXV URFN WKH RLO ZLOO PLJUDWH XSZDUGV XQWLO LW UHDFKHV PLQLPXP SUHVVXUH HLWKHU E\ HVFDSH WKURXJK WKH JURXQG VXUIDFH RU PHHW D EDUULHU DOVR FDOOHG Dtrap 7KH K\GURFDUERQV DFFXPXODWH LQ WKH WUDS IRUPDWLRQ E\ H[SHOOLQJ WKH SUHH[LVWLQJ SRUH ZDWHU IURPWKHSRUHPDWUL[7KLVK\GURFDUERQFRQWDLQLQJSDUWRIWKHWUDSLVFDOOHGD petroleum reservoir DQG WKH K\GUDXOLFDOO\ FRQQHFWHG ZDWHUEHDULQJ SDUW LV FDOOHGDQaquiferDVLQGLFDWHGLQ)LJXUH

Figure 3.1:7\SLFDODQWLFOLQDOSHWUROHXPWUDSVLPSOLILHGQRWWRVFDOH7KHRLOPLJUDWHVIURP WKHVRXUFHURFNWKURXJKWKHSHUPHDEOHURFNLQWRWKHRLOUHVHUYRLUDERYHWKHZDWHUOLQH

7KHRLOUHVHUYRLUURFNPXVWEHVXIILFLHQWO\SRURXVDQGSHUPHDEOHWRDOORZWKH K\GURFDUERQVWRDFFXPXODWHDQGWKHSRURVLW\LVXVXDOO\EHWZHHQDQG 6SHLJKW

3HWUROHXPWUDSVH[LVWLQGLIIHUHQWIRUPVEXWWKH\FDQEHURXJKO\GLYLGHGLQWR structural traps WHFWRQLF VWUXFWXUH RI WKH URFN DQG stratigraphic traps VHDOLQJHIIHFWVE\XQFRQIRUPLWLHVDQGURFNW\SH7KHWUDSW\SHLOOXVWUDWHGLQ )LJXUHLVDQanticlinal trapZKLFKLVDWHFWRQLFVWUXFWXUHWKDWLVIRUPHGE\

D ORFDOLVHG XSOLIW DQGRU IROGLQJ RI VHGLPHQWDU\ URFNFaults DV VKRZQ LQ )LJXUH DUH VWUDWLJUDSKLF WUDSV DQG DUH XVXDOO\ FUHDWHG WKURXJK WZR GLIIHUHQWJHRORJLFDOPHFKDQLVPVclay smearZKHUHFOD\LVVPHDUHGRQWRWKH IDXOWSODQHGXHWRVKHDU IRUFHVGXULQJPRYHPHQWZKLFKSURYLGHVDVHDORU juxtaposition ZKHUH WKH IDXOWLQJ KDV FDXVHG DQ LPSHUPHDEOH URFN WR EH MX[WDSRVHGDJDLQVWWKHUHVHUYRLUURFN-DKQHWDOF

Basic Concepts of Oil Recovery

Figure 3.2:+\GURFDUERQDFFXPXODWLRQGXHWRDIDXOWVWUXFWXUH

)DXOWV DQG GRPHVDQWLFOLQHV DUH WKH WZR PRVW W\SLFDO IRUPV RI WUDSV RQ WKH 1RUZHJLDQ&RQWLQHQWDO6KHOIPetroleum Resources: Norwegian Continental Shelf=RORWXNKLQ 8UVLQD

3.2 Mineralogical description of sandstones

7KH PLQHUDORJ\ RI DQ RLO UHVHUYRLU LV RI JUHDW LPSRUWDQFH ZKHQLW FRPHV WR ZHWWLQJSURSHUWLHVDQGRWKHUSDUDPHWHUVZKLFKPD\KDYHLPSOLFDWLRQVIRUWKH RLOUHFRYHU\SURFHVV7KHPDLQIRFXVRIWKLVWKHVLVZRUNLVRLOUHFRYHU\IURP VDQGVWRQHVDQGKHUHIROORZVDVKRUWUHYLHZRIWKHPRVWLPSRUWDQWDVSHFWVRI VDQGVWRQHPLQHUDORJ\

6DQGVWRQHV DUH sedimentary URFNV DQG DUH IRUPHG WKURXJK lithification

³WXUQHG LQWR URFN´ GXH WR GHSRVLWLRQ RIclastic PDWHULDO *U ³NODVWRV´

³EURNHQ´RUdetritus /DW³ZRUQGRZQ´&ODVWLFVDQGGHWULWXVLVWKHUHVXOWRI ZHDWKHULQJ IUDJPHQWDWLRQ DQG HURVLRQ RI ROGHU URFN W\SHV 6RPH RI WKH FODVWLFVPD\EHbioclasticsPHDQLQJWKH\DUHGHULYHGIURPVKHOOVRUVNHOHWDO SDUWV RI GHDG RUJDQLVPV 6HGLPHQWV DUH WUDQVSRUWHG YLD ZDWHU ULYHUV VHD FXUUHQWV ZLQG LQ GHVHUWV DQG LFH JODFLHUV 7KH W\SH RI WUDQVSRUW GHWHUPLQHV WKH HQHUJ\ DYDLODEOH IRU FRPSRQHQW PRYHPHQW DQG JRYHUQV WKH VL]HVKDSHDQGVRUWLQJRIVHGLPHQWJUDLQV6RUWLQJLVDYHU\LPSRUWDQWDVSHFW

RI UHVHUYRLU TXDOLW\ DV LW FRQWUROV SDUDPHWHUV VXFK DV porosity DQG permeabilityZKLFKLVLOOXVWUDWHGIRUSRURVLW\LQ)LJXUH-DKQHWDOF

=RORWXNKLQ 8UVLQD

Figure 3.3:6RUWLQJLPSDFWRQUHVHUYRLUSRURVLW\$GDSWHGIURP-DKQHWDOF

6HGLPHQWV GHSRVLWHG RQ ODQG VXUIDFH RU VHDEHG LV EXULHG FRPSUHVVHG DQG FHPHQWHGWKURXJKDFKHPLFDOSURFHVVFDOOHGdiagenesisRYHUJHRORJLFDOWLPH

=RORWXNKLQ 8UVLQD

$FFRUGLQJWRWKH8GGHQ:HQWZRUWKVFDOHWKHFODVWVL]HVIRUVDQGVWRQHVYDU\

IURP —P WR PP 8GGHQ :HQWZRUWK 6DQGVWRQHV DQG FRQJORPHUDWHVFRQVWLWXWH±RIVHGLPHQWDU\URFNV

$ ODUJH QXPEHU RI GLIIHUHQW PLQHUDOV FDQ RFFXU LQ VDQGVWRQHV EXW WKH PRVW FRPPRQ DUH TXDUW] IHOGVSDUV PLFDV DQG FOD\ PLQHUDOV $ FRPPRQ FKDUDFWHULVWLF RI WKHVH LV WKDW WKH\ DOO DUH VWDEOH XQGHU VXUIDFH FRQGLWLRQV 1LFKROV

3.2.1 Quartz

4XDUW]LVWKHFKHPLFDOO\VLPSOHVWRIWKHVLOLFDWHPLQHUDOVZLWKIRUPXOD6L2 DQG LV WKH PRVW FRPPRQ PLQHUDO VSHFLHV IRXQG LQ VDQGVWRQHV FRQWULEXWLQJ IURP ± 7KH FDXVH RI WKLV SUHYDOHQFH LV LWV KLJK UHVLVWDQFH WR ZHDWKHULQJ DQG RWKHU GLVLQWHJUDWLQJ PHFKDQLVPV KDYLQJ D KDUGQHVV RI RQ Mohs’ scale ,W LV FRPPRQ LQ URFN W\SHV VXFK DV JUDQLWH JQHLVV DQG VFKLVW 6DQGVWRQHLVEURDGO\GLYLGHGLQWRDUHQLWHVDQGZDFNHDFFRUGLQJWRWKH 'RWW

Basic Concepts of Oil Recovery

FODVVLILFDWLRQGLDJUDP'RWW-UZKLFKGLVSOD\VWKHUHODWLYHSURSRUWLRQV RIFODVWVDQGPDWUL[VLOWDQGFOD\PDWHULDO,IWKHDPRXQWRIPDWUL[LV WKHURFNLVFODVVLILHGDVDQareniteDQGLIWKHPDWUL[FRQWHQWLVEHWZHHQ±

LW LV FDOOHG D wacke 7KHVH URFN W\SHV DOVR KDYH VHYHUDO VXE FODVVLILFDWLRQV DFFRUGLQJ WR WKH SUHVHQFH RI RWKHU PLQHUDO JUDLQV 1LFKROV 3HWWLMRKQHWDO

3.2.2 Micas

0LFDVDUHphyllosilicatesDQGDUHUHODWLYHO\DEXQGDQWLQVDQGVWRQHDVGHWULWDO JUDLQV DQG DUH GHULYHG IURP LJQHRXV PHWDPRUSKLF DQG VHGLPHQWDU\ URFN IRUPDWLRQV7KHWZRPRVWFRPPRQIRUPVDUHZKLWHPLFDmuscoviteDQGWKH EURZQPLFDbiotite7KH\KDYHDGLVWLQFWLYHSODW\VKDSHDQGKDYHDWHQGHQF\

WR EH FRQFHQWUDWHG LQ EDQGV RQ EHGGLQJ SODQHV 1LFKROV 3HWWLMRKQ

3.2.3 Feldspars

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

IHOGVSDUK\GURJHQLRQVĺFOD\FDWLRQVVROLGVZDWHU )HOGVSDUXVXDOO\FRQVWLWXWHVEHWZHHQ±RIWKHVDQGVWRQHDQGLVWKXV OHVVSUHYDOHQWWKDQTXDUW]GXHWRWKHLUKLJKHUVXVFHSWLELOLW\WRZHDWKHULQJDQG GHJUDGDWLRQ7KHUHDUHWZRPDLQIDPLOLHVRIIHOGVSDUV ZLWKSRWDVKIHOGVSDUV PLFURFOLQH EHLQJ WKH PRVW SUHYDOHQW GXH WR D KLJKHU UHVLVWDQFH WR GHJUDGDWLRQ PHFKDQLVPV 3RWDVK IHOGVSDUV .$O6L2 FRQVLVW RI RUWKRFODVH ZKLFK LV YHU\ FRPPRQ LQ JUDLQV RI VHGLPHQWDU\ URFNV DQG WKH VOLJKWO\ OHVV

FRPPRQ PLFURFOLQH ZKLOH WKH SODJLRFODVH IHOGVSDUV DUH DOELWH 1D$O6L2 DQGDQRUWKLWH&D$O6L2&UXQGZHOO1LFKROV

3.2.4 Clays

&OD\PLQHUDOVDUHXVXDOO\DSURGXFWRIWKHEUHDNGRZQRIVLOLFDWHPLQHUDOVOLNH IHOGVSDUV DQGFDQ EHGHVFULEHG FKHPLFDOO\ DV DOXPLQLXP VLOLFDWHV7KH\ DUH VLPLODU WR PLFDV ZLWK D OD\HUHG FU\VWDOOLQH VWUXFWXUH DQG DUH HVVHQWLDOO\

FRPSRVHG RI VLOLFD DOXPLQD DQG ZDWHU 7KH\ IUHTXHQWO\ FRQWDLQ ODUJH TXDQWLWLHV RI PDJQHVLXP DQG LURQ DV ZHOO DV OHVVHU DPRXQWV RI VRGLXP DQG SRWDVVLXP 7KHUH DUH WZR SDWWHUQV RI OD\HULQJ RFFXUULQJ LQ FOD\V IRXQG LQ VDQGVWRQHUHVHUYRLUVDQGWKHVHFRQVLVWRIWZREXLOGLQJXQLWVWKHILUVWRQHLV WHWUDKHGUDOVLOLFDVKHHWVDQGWKHVHFRQGRQLVOD\HUVRIRFWDKHGUDODOXPLQLXP 7KHEXLOGLQJXQLWVDUHOLQNHGWRJHWKHULQSODQDUOD\HUVE\VKDULQJR[\JHQLRQV EHWZHHQ6LDQG$OLRQVDQGWKHILUVWW\SHRIOD\HULQJKDVWZROD\HUVDQGLV FDOOHGWKHkandite groupZKLOHWKHVHFRQGOD\HULQJW\SHKDVWKUHHOD\HUVDQG LV FDOOHG WKHsmectite group $OWKRXJK WKH 6L DQG $O LRQV DUH WKH PDLQ RFFXSDQWV RI WKH VSDFH EHWZHHQ WKH WHWUDKHGUDO DQG RFWDKHGUDO OD\HUV RWKHU FDWLRQVZLOODOVREHSUHVHQWWRHQVXUHFKDUJHEDODQFH1LFKROV:RUGHQ 0RUDG 7KH IRXU PRVW FRPPRQ FOD\ PLQHUDOV RFFXUULQJ LQ VHGLPHQWDU\URFNVDUHJLYHQLQ)LJXUH7XFNHU

Basic Concepts of Oil Recovery

Figure 3.4&U\VWDOODWWLFHVWUXFWXUHVIRUWKHPRVWFRPPRQFOD\PLQHUDOV$GDSWHGIURP 1LFKROV

Kaolinite LV WKH PRVW FRPPRQ PHPEHU RI WKH NDQGLWH JURXS DQG KDV WKH FKHPLFDO IRUPXOD $O6L22+,W LV FRPSULVHG RI RQH WHWUDKHGUDO OD\HU OLQNHG WRRQ RFWDKHGUDO OD\HU WKURXJK 2+2 ERQGV DQG WKXV WHUPHG D OD\HUVWUXFWXUH.DROLQLWH LVGHVFULEHGDVERRNOHW SDJHVUHVLVWDQWWRFKHPLFDO WUHDWPHQW DQG LV JHQHUDOO\ IRUPHG IURP JUDQLWH EHGURFN OLWKRORJLHV OHDFKHG E\DFLGLFZDWHUVMontmorillonite LVDFOD\PLQHUDOLQWKHVPHFWLWHJURXSDQG LV NQRZQ DV D VZHOOLQJ FOD\ GXH WR LWV DELOLW\ WR DEVRUE ZDWHU ZLWKLQ LWV VWUXFWXUH,WLVDFOD\ZKLFKPHDQVLWKDVRQHRFWDKHGUDOVKHHWVDQGZLFKHG

EHWZHHQ WZR WHWUDKHGUDO VKHHWVIllite LV DOVR D OD\HU VPHFWLF FOD\ ULFK LQ SRWDVVLXP$VPRQWPRULOORQLWHLWLVDVWUXFWXUHDQGWKXVFRPSULVHGRIRQH RFWDKHGUDO OD\HU EHWZHHQ WZR WHWUDKHGUDO OD\HUV ZKHUH RSSRVLQJ WHWUDKHGUDO OD\HUVDUHERXQGWRJHWKHUZLWK2.2ERQGV7KLVLVDYHU\VWURQJERQGDQG SUHYHQWVWKHFOD\PLQHUDOIURPVZHOOLQJChlorite KDVDVWUXFWXUHZKLFK FRQVLVWVRIDOD\HUWHWUDKHGUDORFWDKHGUDOWHWUDKHGUDOZKLFKLVQHJDWLYHO\

FKDUJHG DQG LQWHUOD\HUHG ZLWK D SRVLWLYHO\ FKDUJHG RFWDKHGUDO OD\HU ZLWK FDWLRQVDQGK\GUR[\OLRQV1LFKROV:RUGHQ 0RUDG

&OD\ PDWHULDOV KDYH RQH YHU\ FKDUDFWHULVWLF SURSHUW\ ZKLFK GLVWLQJXLVKHV WKHP IURP RWKHU VLOLFDWH PDWHULDOV DQG WKLV LV WKH RFFXUUHQFH RI QHJDWLYH FKDUJHVWKDWDUHORFDWHGDWWKHHGJHVHQGVRIWKHXQLWFHOOV7KHVHFKDUJHVPD\

FDXVHWKHVXEVWLWXWLRQRIFDWLRQVRULQWHUDFWLRQVZLWKWKHVXUURXQGLQJPHGLDWR VWDELOLVHWKHFKDUJHV7KLVVLWXDWLRQGHSHQGVRQWKHS+FRQGLWLRQVDQGWKHVH JURXSV DUH WKHUHIRUH QDPHG YDULDEOH FKDUJHV 3HUPDQHQW FKDUJHV GHSHQG RQ FDWLRQVXEVWLWXWLRQ ZLWKLQWKH OD\HUV EXW ERWKFKDUJHW\SHV FRQWULEXWH WR WKH FDWLRQH[FKDQJHFDSDFLW\&(&RIDFOD\PLQHUDO9HOGH 0HXQLHU

&(&LVDPHDVXUHRIDFOD\PLQHUDO¶VDELOLW\WRDWWUDFWDQGELQGFDWLRQVIURP WKHVXUURXQGLQJPHGLXPDQGLVGHQRPLQDWHGPLOOLHTXLYDOHQWVPHTSHU JRIVDPSOH,WLVGHILQHGDVWKHTXDQWLW\RIH[FKDQJHDEOHFDWLRQVWKDWWKHFOD\

FDQKROGDWDJLYHQS+XVXDOO\S+%HUJD\DHWDO&DWLRQVFDQEH RUJDQLVHG LQ VHULHV EDVHG RQ KRZ VWURQJ WKHLU UHSODFLQJ SRZHU LV EXW WKH GHILQLWHSRVLWLRQLVJRYHUQHGE\WKHW\SHRIFOD\DQGWKHVL]HRIWKHLRQWKDWLV UHSODFHG7KHGHJUHHRIDWWUDFWLRQIRUGLIIHUHQWFDWLRQVWRZDUGVFOD\PDWHULDOV LVVKRZQEHORZ<RQJHWDO

Li⁺Na⁺K⁺Mg²⁺Ca²⁺Sr²⁺Ba²⁺Cu²⁺ H⁺

7KLVVHULHVRIUHSODFLQJSRZHUWKXVLPSOLHVWKDWZKHQHTXDOFRQFHQWUDWLRQVRI 1DDQG&DH[LVWVWKH&DFDWLRQVZLOOEHEHWWHUDWGLVSODFLQJ1DIURPWKH FOD\VXUIDFHWKDQ1DZLOOEHDWGLVSODFLQJ&D,IWKHFRQFHQWUDWLRQRIDORZ UHSODFLQJ SRZHU FDWLRQ LV KLJK HQRXJK UHODWLYH WR WKH FRQFHQWUDWLRQ RI WKH KLJKHU UHSODFLQJ SRZHU FDWLRQ WKH KLJK UHSODFLQJ SRZHU FDWLRQ PD\ EH GLVSODFHG5H]DHL'RXVW

Basic Concepts of Oil Recovery

7KHNH\SURSHUWLHVRIWKHPRVWFRPPRQFOD\PLQHUDOVDUHFROOHFWHGLQ7DEOH

Table 3.2: 3URSHUWLHV RI WKH PRVW FRPPRQ FOD\ PLQHUDOV Technical Manual for Drilling, Completion and Workover Fluids

Property Kaolinite Illite Chlorite Montmorillonite

Structure

Particle size

(μm) ± /DUJHVKHHWV

XSWR ± ±

CEC (meq/100

g) ± ± ± ±

Surface area

BET (m²/g) ± ± ±

3.3 Oil recovery mechanisms

7KH OLIH RI DQ RLO UHVHUYRLU FRQVLVWV RI VHYHUDO SKDVHV )LUVW DQG IRUHPRVW DFFHVVLVJDLQHGDIWHUWKRURXJKO\HYDOXDWLRQRIWHFKQLFDOHFRQRPLFSROLWLFDO VRFLDO DQG HQYLURQPHQWDO DVSHFWV RI WKH FRQVLGHUHG UHJLRQ 7KH IROORZV WKH exploration SKDVH ZKHUH RLO DQG JDV LV VRXJKW DIWHU E\ JHRORJLVWV DQG JHRSK\VLFLVWV IRU H[DPSOH E\ WKH XVH RI VHLVPLF VXUYH\V ERWK RQ DQG RIIVKRUH7KLVSURFHVVPD\ODVWIRU\HDUV7KHQIROORZVWKHevaluationSKDVH ZKHUH WKH SRWHQWLDO RLOILHOG LV PRUH WKRURXJKO\ LQYHVWLJDWHG WKURXJK WKH GULOOLQJRIWHVWZHOOVDQGDGHFLVLRQLVWDNHQZKHWKHUWRGHYHORSWKHILHOGRU QRW ,Q WKHdevelopment SKDVH WKH FRPSOHWH SURGXFWLRQ LV SODQQHG D ILHOG GHYHORSPHQWSODQ)'3LVGUDZQXSDQGSODQWVIDFLOLWLHVDQGLQIUDVWUXFWXUH DUHEXLOW$WODVWWKHproductionFDQEHJLQDQGWKLVSKDVHFDQODVWIRU±

\HDUVVRPHWLPHVHYHQORQJHUGHSHQGLQJRQWKHRLOILHOG7KHWLPHOLQHFRQVLVWV RIDEXLOGXSSHULRGDSODWHDXSHULRGDQGDGHFOLQHSHULRGZKLFKLVXVXDOO\

WKHORQJHVWRQH7KLVLVWKHSKDVHZKHUHWKHRLOUHFRYHU\WDNHVSODFHDQGLV XVXDOO\ GLYLGHG LQWR WKUHH PDLQ VWDJHV SULPDU\ VHFRQGDU\ DQG WHUWLDU\ RLO UHFRYHU\JLYHQDFRQYHQWLRQDORLOUHVHUYRLU'HSHQGLQJRQWKHFKDUDFWHULVWLFV RI WKH RLO UHVHUYRLU WKH RUGHU RI WKHVH SURFHVVHV FDQ EH DOWHUHG DQG DOVR VNLSSHG*UHHQ :LOOKLWHD)LJXUHVKRZVDQRYHUYLHZRIW\SLFDO DSSOLFDWLRQ VHTXHQFH RI WKH GLIIHUHQW RLO UHFRYHU\ SKDVHV $Q RLO ILHOG LV

decommissioned ZKHQWKHQHWHFRQRPLFDOLQFRPHLVORZHUWKDQWKHRSHUDWLRQ FRVWV-DKQHWDOE:LQWHUVKDOO

3.3.1 Primary recovery

3ULPDU\RLOUHFRYHU\FRQFHUQVWKHSDUWRIWKHRLOSURGXFWLRQZKHUHQRH[WHUQDO IRUFHLVDGGHGWRWKHSURGXFWLRQSURFHVVOLNHIOXLGLQMHFWLRQ7KXVWKHRQO\

UHDVRQ K\GURFDUERQV DUH SURGXFHG LV D QDWXUDO UHGXFWLRQ LQ SUHVVXUH LQ WKH UHVHUYRLU 7KHUH DUH GLIIHUHQW QDWXUDO GULYLQJ PHFKDQLVPV DQG WKH JHQHUDO SHUIRUPDQFH RI DQ RLO UHVHUYRLU LV GHWHUPLQHG E\ ZKDW NLQG RI HQHUJ\ WKDW SURGXFHVWKHRLO%DVLFDOO\WKHVHGULYLQJPHFKDQLVPVFDQEHGLYLGHGLQWRVL[

GLIIHUHQWW\SHV$KPHGE$KPHG 0F.LQQH\

Rock and liquid expansion drive: 7KLVVLWXDWLRQRFFXUVZKHQWKHSUHVVXUHLQ WKHUHVHUYRLUH[FHHGVWKHEXEEOHSRLQWDQGWKHRLOUHVHUYRLULVundersaturated :KHQ WKH SUHVVXUH LQ WKH UHVHUYRLU LV UHGXFHG WKH URFN DQG IOXLGV FRQQDWH ZDWHUDQGFUXGHRLOZLOOH[SDQGZLWKWKHFUXGHRLOH[SDQVLRQEHLQJWKHPDLQ GULYLQJIRUFHDVLWLVW\SLFDOO\WLPHVODUJHUWKDQWKHZDWHUEULQHH[SDQVLRQ

Figure 3.5:2LOUHFRYHU\PHFKDQLVPVHTXHQFH$GDSWHGIURP$KPHGF

Solution gas (depletion) drive: 1DWXUDO SURGXFWLRQE\ VROXWLRQ JDV GULYH LV FDXVHG E\ JDV OLEHUDWLRQ IURP WKH FUXGH RLO ZKHQ WKH UHVHUYRLU SUHVVXUH LV

Basic Concepts of Oil Recovery

UHGXFHG EHORZWKH EXEEOHSRLQW SUHVVXUH *DV EXEEOHV ZLOO EH OLEHUDWHGLQWR WKHPLFURVFRSLFSRUHVSDFHVDQGH[SDQGDQGLQWKLVZD\IRUFHWKHRLORXWRI WKHSRUHVSDFHV

Gas-cap drive: 5HVHUYRLUV ZLWK JDVFDSV JHQHUDOO\ VKRZ VORZ GHFOLQH LQ UHVHUYRLUSUHVVXUHGXHWRWKHJDVFDS¶VDELOLW\WRH[SDQG7KHDYDLODEOHIRUFHV WRSURGXFHRLOLQJDVFDSGULYHDUHH[SDQVLRQRIWKHJDVFDSJDVDQGOLEHUDWHG VROXWLRQJDV

Water drive: 5HJDUGOHVVRIZDWHUVRXUFH WKLVQDWXUDOGULYHHIIHFWLVFDXVHG E\ZDWHUPLJUDWLQJ LQWRWKHSRUHVSDFHVRIWKHRLOGLVSODFLQJLW

Gravity drainage: 7KLV PHFKDQLVP RFFXUV DV D UHVXOW RI WKH GLIIHUHQW GHQVLWLHVRIWKHUHVHUYRLUIOXLGV

Combination drive: 7KHPRVWFRPPRQQDWXUDOGULYHPHFKDQLVPZKHUHERWK ZDWHU DQG JDV DUH DYDLODEOH WR GLVSODFH RLO WRZDUGV WKH ZHOOV 7ZR W\SHV RI FRPELQDWLRQ GULYLQJ IRUFHV DUH XVXDOO\ SUHVHQW LQ WKLV W\SH RI UHVHUYRLU 6ROXWLRQJDVGULYHDQGZHDNZDWHUGULYHRU6ROXWLRQJDVGULYHZLWKVPDOO JDVFDSDQGZHDNZDWHUGULYH

7KH WRWDO RLO UHFRYHU\ IURP SULPDU\ UHFRYHU\ PHFKDQLVPV LV XVXDOO\ LQ WKH UDQJH RI ± 22,3 EXWIRU FHUWDLQ H[FHSWLRQDO UHVHUYRLUV WKH XOWLPDWH UHFRYHU\ PD\ UHDFK 22,3 ZDWHU GULYH DQG 22,3 JUDYLW\

GUDLQDJH$KPHG 0F.LQQH\

3.3.2 Secondary recovery

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

VHFRQGDU\PRGHLVXVXDOO\LQWKHUDQJHRI±22,3*UHHQ :LOOKLWH D0XJJHULGJHHWDO

3.3.3 Tertiary recovery – Enhanced oil recovery

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qUH *UHHQ :LOOKLWHD$OO(25PHWKRGVKDYHD FRPPRQ WDUJHWRILQFUHDVLQJWKH YROXPHWULF PDFURVFRSLF VZHHS HIILFLHQF\ DQG LPSURYLQJ WKH GLVSODFHPHQW PLFURVFRSLFHIILFLHQF\7KHYROXPHWULFVZHHSLVLQFUHDVHGE\UHGXFLQJWKH PRELOLW\ UDWLR EHWZHHQ WKH GLVSODFLQJ DQG WKH GLVSODFHG IOXLG ZKLOH WKH PLFURVFRSLFHQWUDSPHQWFRXOGEHORZHUHGZKHQWKHLQWHUIDFLDOWHQVLRQ,)7 EHWZHHQWKHGLVSODFLQJDQGGLVSODFHGIOXLGVLVUHGXFHG7KLVJLYHVDORZHU6_RU DQGWKXVDKLJKHUXOWLPDWHRLOUHFRYHU\=RORWXNKLQ 8UVLQE

(25FDQEHORRNHGXSRQDVDVXEVHWRILPSURYHGRLOUHFRYHU\,25ZKLFK LPSOLHV LQFUHDVLQJ WKH UHFRYHUHG DPRXQW RI RLO E\ DQ\ PHDQV LQFOXGLQJ VHFRQGDU\ UHFRYHU\ ZDWHUIORRGLQJ JDV LQMHFWLRQ LQILOO GULOOLQJ FRQIRUPDQFHFRQWURORUKRUL]RQWDOZHOOV6WRVXUHWDO7KRPDV

3.3.4 General description and characterisation of EOR processes

$ ODUJH QXPEHU RI GLIIHUHQW (25 PHWKRGV KDYH EHHQ HPSOR\HG RYHU WKH

\HDUVZLWKDYDU\LQJGHJUHHRIVXFFHVV(25PHWKRGVFDQEHXWLOLVHGIRUPRVW FUXGH RLO TXDOLWLHV EH LW OLJKW FUXGH KHDY\ FUXGH RU WDU VDQGV 7KH (25 WHFKQLTXHDSSOLHGPXVWPDWFKWKHUHVHUYRLUJHRORJ\DQGIOXLGSURSHUWLHVLWLV VXSSRVHGWRUHFRYHU$JHQHUDORYHUYLHZRIGLIIHUHQW(25PHWKRGVLVJLYHQ LQ)LJXUHDQGDVFDQEHVHHQWKH\DUHURXJKO\GLYLGHGLQWRWZRJURXSV WKHUPDOPHWKRGVDQGQRQWKHUPDOPHWKRGVZLWKVHYHUDOVXEVHWFDWHJRULHV

Basic Concepts of Oil Recovery

7KHUPDOPHWKRGVKDYHEHHQXWLOLVHGDQGGHYHORSHGVLQFHWKHVDQGDUH WKXV WKH PRVW DGYDQFHG DQG ILHOG DSSOLHG PHWKRGV 7KH\ ZRUN EHVW IRU UHFRYHU\RIFUXGHVZLWKDORZ$3,JUDYLW\YDOXHOLNHKHDY\FUXGHRLOV±

ƒ$3,DQGWDUVDQGV”ƒ$3,$3,$PHULFDQ3HWUROHXP,QVWLWXWHLVD GLPHQVLRQOHVVJLYHQLQGHJUHHVYDOXHPHDVXULQJKRZKHDY\DQRLOSURGXFWLV UHODWLYHWRZDWHUZKHQLWLVKLJKHUWKDQLWLVOLJKWHUWKDQDQGZLOOIORDWRQ ZDWHUDQGEHORZLWZLOOVLQN(UQHVWHWDO7KHUPDOPHWKRGVVXSSO\

KHDWWRWKHUHVHUYRLUDQGWKXVOHDGWRFUXGHRLOYLVFRVLW\GHFUHDVHDQGIXUWKHU DEHWWHUPRELOLW\UDWLR2WKHUHIIHFWVSUHVHQWFDQEHFRPSDFWLRQURFNDQGIOXLG H[SDQVLRQDQGVWHDPGLVWLOODWLRQ7KRPDV

Figure 3.6:6FKHPDWLFFODVVLILFDWLRQRI(25PHWKRGV$GDSWHGIURP7KRPDV

1RQWKHUPDO PHWKRGV DUH EHWWHU VXLWHG IRU OLJKWHU FUXGH RLOV ZKLFK KDYH UHODWLYHO\ ORZ YLVFRVLWLHV DQG WKXV KLJKHU $3, YDOXHV ! ƒ $3, 6SHLJKW 7KHWZRPDLQREMHFWLYHVIRUQRQWKHUPDOWHFKQLTXHVDUH/RZHULQJ WKH,)7DQGLPSURYHWKHPRELOLW\UDWLR7KRPDV$WKLUGDSSURDFK

LVWRFKDQJHWKHUHVHUYRLUZHWWDELOLW\DPHWKRGWKDWLVDLPLQJWRGHVRUEFUXGH RLOIURPWKHSRUHVXUIDFHVRIWKHRLOUHVHUYRLU150RUURZ

%DVHG RQ VWXGLHV RQ FDWLRQLF VXUIDFWDQWV LQ FDUERQDWH URFNV 6WDQGQHV HW DO ZDV DEOH WR GHYHORS D QHZ PHWKRG IRU FKDQJLQJ WKH ZHWWLQJ SURSHUWLHV LQ UHVHUYRLUURFN RQO\ E\ PRGLI\LQJ WKHFKHPLFDO FRPSRVLWLRQ RIWKHIORRGLQJ IOXLG 7KH UHVXOW ZDV QDPHG ³6PDUW :DWHU´ DQG WKH PHWKRG FRPSULVHV ZHWWDELOLW\ DOWHUDWLRQ ZLWKRXW ORZHULQJ WKH FDSLOODU\ IRUFHV VLJQLILFDQWO\

ZKLFKPD\LQFUHDVHRLOSURGXFWLRQ7KHFRPSRVLWLRQRIWKHIORRGLQJIOXLGFDQ EH WDLORUHG DIWHU UHVHUYRLU DQG FUXGH RLO SURSHUWLHV DQG WKH PHWKRG LV HFRQRPLFDOO\ YLDEOH DV SUHSDUDWLRQ LV VLPSOH DQG QR H[SHQVLYH FKHPLFDOV QHHGVWREHDGGHG7RU$XVWDG6WDQGQHV $XVWDG6NXOH6WUDQG HWDO7KLVLVYHU\DGYDQWDJHRXVDVPDQ\(25PHWKRGVDUHOLPLWHGE\

WKHLU KLJK DSSOLFDWLRQ FRVWV 6PDUW :DWHU PD\ DOVR KDYH SRWHQWLDO LQ FRPELQDWLRQ ZLWK RWKHU IORRGLQJ DJHQWVPHWKRGV HVSHFLDOO\ LQ VDQGVWRQH IRUPDWLRQV

Basic Concepts of Oil Recovery

4 Fundamentals of Porous Systems, Surface and Colloid Chemistry

:DWHURLODQGJDVIORRGLQJLQVLGHDSRURXVPDWHULDOZLOOEHVXEMHFWWRVHYHUDO GLIIHUHQWIRUFHVWKHPRVWLPSRUWDQWRQHVEHLQJFDSLOODU\IRUFHVYLVFRXVIRUFHV DQG JUDYLW\ IRUFHV 7KH ZHWWLQJ SURSHUWLHV DQG VXUIDFH IRUFHV PXVW DOVR EH WDNHQ LQWR FRQVLGHUDWLRQ ZKHQ SODQQLQJ D ZDWHUIORRG ,Q WKLV VHFWLRQ WKHVH PDLQIDFWRUVZLOOEHGHVFULEHGLQUHODWLRQWR(25XVLQJ6PDUW:DWHU

4.1 Displacement forces

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

4.1.1 Displacement efficiency

7KHRLOUHFRYHU\IURPDQ\GLVSODFHPHQWSURFHVVLVGHSHQGHQWRQWKHUHVHUYRLU YROXPHWKDWLVLQFRQWDFWZLWKWKHLQMHFWHGIOXLG7KHYROXPHWULFGLVSODFHPHQW VZHHSHIILFLHQF\E_VLVDTXDQWLWDWLYHPHDVXUHRIWKLVFRQWDFW,WFDQDOVREH WHUPHG PDFURVFRSLF HIILFLHQF\ DQG LV GHILQHG DV WKH UHVHUYRLU IUDFWLRQ SRUH YROXPH39LQFRQWDFWZLWKWKHIOXLGLQMHFWHGE_VLQDGLVSODFHPHQWSURFHVVLV WKXVDIXQFWLRQRIWLPH*UHHQ :LOOKLWHF

7KH RYHUDOO RU JOREDO GLVSODFHPHQW HIILFLHQF\ E LQ DQ\ RLO GLVSODFHPHQW IURP WKH UHVHUYRLU LV GHILQHG DV WKH SURGXFW RI WKH PDFURVFRSLF DQG WKH PLFURVFRSLFGLVSODFHPHQWHIILFLHQFLHVDQGLVJLYHQLQ(TXDWLRQ

E = E_DE_V