1. Carbon Dioxide Ocean Sequestration Using Gas Hydrate

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*^,†**

136-701 5 1

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305-701 373-1

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151-742 !" #$9 % 56-1 (2002& 12' 16( )*, 2003& 1' 10( +,)

Carbon Dioxide Ocean Sequestration Using Gas Hydrate

Huen Lee*^,†, Chul Soo Lee^† and Joo M. Kang**

Department of Chemical and Biological Engineering, Korea University, 1, Anam-dong 5(o)-ga, Seongbuk-gu, Seoul 136-701, Korea

*Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, 373-1, Guseong-dong, Yuseong-gu, Daejeon 305-701, Korea

**School of Civil, Urban and Geo-System Engineering, Seoul National University, San 56-1, Sillim 9(gu)-dong, Gwanak-gu, Seoul 151-742, Korea (Received 16 December 2002; accepted 10 January 2003)

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Abstract−Gas hydrate is a special kind of inclusion compound that can be formed by capturing gas molecules to water lattice in high pressure and low temperature conditions. The hydrate crystal structures were different depending on a kind of guest molecules. Recently, gas hydrates have attracted the attention of many investigators from all areas of natural gas production and environmental science from a fact that this compound could be formed from only host water and guest gas molecules. The most attrative application of hydrates is to dispose of carbon dioxide in the form of solid hydrates in the ocean to reduce atmo- spheric carbon dioxide concentration and mitigate global warming. Therefore, this paper summarized present research works concerning the carbon dioxide hydrate and suggested the connection between these results and the strategies for carbon dioxide sequestration. In addition, general topics and research trends related to carbon dioxide hydrate are presented with focusing on carbon dioxide ocean sequestration to resolve the global warming problems.

Key words: Carbon Dioxide, Gas Hydrate, Ocean Sequestration, Global Warming

1.

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†To whom correspondence should be addressed.

E-mail: hlee@mail.kaist.ac.kr

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\úûü, wÒûü \úûü(clathrate hydrate) Ã Q n Ý1 k F0 Òj ~

æ E {þ =°X, Ì £ æ% {þ z ~ k {4 ¾·\ þæ: ì". Ò \úûü

O{þ4 ~ F(hydrogen-bonded solid lattice)2 v ` Fig. 1. Schematic diagram of carbon sequestration[2].

Fig. 2. The cavities in gas clathrate hydrate[6, 8] (a) Pentagonal Dodecahe- dron(5¹²), (b) Tetrakaidecahedron(5¹²6²), (c) Hexakaidecahedron (5¹²6⁴), (d) Irregular Dodecahedron(4⁴5⁶6³), (e) Icosahedron(5¹²6⁸).

Table 1. Storage capacity for storage options [4]

Storage options Storage capacity (GtC)

Ocean 1,400-2×10⁷

Aquifers 87-2,700

Depleted gas reservoir 140-310

Depleted oil reservoir 40-190

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~F(host molecule) æ ¤ 6 G6 ~F (guest molecule) ä 4 Ì¹"[6]. w Ò \úûü

!à "#\ð j, {Ì 4 !à1 Þ~

Ò \úûü ò~". ÐA Ò \úûü {Ì (crystal structure) O {þk æF(hydrogen-bonded water molecule) \ ¹ ")~(polyhedra) ¦H(cavity)4 Ì

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ç, ¶· %'Ê ¦H £ 5¹², 5¹²6², 5¹²6⁴, 5¹²6⁸, 4³5⁶6³

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& Ò ñ, ~F z {¹". F >:

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" K ~F )*(distortion) ( ¦H G6 +\ç, ( 0.76 " ª1 K F ß n(attractive force)

¦H ¤(stability): TH\ +".

\úûü Ì -I1 1965* McMullen Jeffrey[8] X-Ä

c(X-ray diffraction: XRD) +Ì \ ,-.4ç, +Ì

/0(ethylene oxide) ". Ì -I1 46s æ

F 2s 5¹²¦H 6s 5¹²6²¦H: Û ò~(cubic) {

k2 Ì\ç, F(lattice) >1 12Å"(Fig. 3). ®, ,

(carbon dioxide) 1O(hydrogen sulfide) 2 \

úûü(simple hydrate) Ì -I: ". \úûü Ì -II

1965* Mark× McMullen[9] XRD +Ì \ ,-.4ç,

+Ì2 ]z 3üX\ú4(tetrahydrofuran)/1O

". Ì -II 136s æF 16s 5¹²¦H 8s 5¹²6⁴¦H : Û {k2 Ì"(Table 2). F "=5ú(diamond) k2 ç, 17.3 Å"(Fig. 4). 0.76 1 R (: Û

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(nitrogen), ÓÏ -(iso-butane) o ~FG 2 \

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K²: £\¸". ^í4 u6ì-(n-butane)" F G1 Ò \úûü2 #\ +" %'´ µ". $wj 1987

* Ripmeester o[11]1 ?F H© |(NMR spectroscopy)j X-Ä ìc(X-ray powder diffraction) o +Ì \ Ì -H ¾·2 ,A , 1996* Udachin Lipkowski[12] \

{(single crystal) c Fd &@". 34s æ

F 3s 5¹²¦H, 2s 4³5⁶6³ ¦H 1s 5¹²6⁸ ¦H: Û {

k2 Ì\ Ì -H ÞA(hexagonal) {k2

!4ç, È ¦H 5¹²1 {þØ(connecting layer): \ ]

\ ): H£"(Fig. 5). Ì -H ¤ ]\

" ä Ã ~F aÌ¹"[6]. ñ, ® 1O× B1 ª1 FG1 ª1 ¦H(5¹², 4³5⁶6³) G6ç, 7.4 " CDE

(neohexane) B1 FG1 ¦H(5¹²6⁸) 6 }~ {

Ì ¤¹".

Fig. 3. Crystalline lattice of gas hydrate, Structure-I[6].

Fig. 4. Crystalline lattice of gas hydrate, Structure-II[6].

Fig. 5. Crystalline lattice of gas hydrate, Structure-H[6, 13].

Table 2. Hydrate crystal structures[6, 8, 10, 11, 13].

Hydrate crystal structure I II H

Cavity small large small large small small large

Description 5¹² 5¹²6² 5¹² 5¹²6⁴ 5¹² 4³5⁶6³ 5¹²6⁸

No. of cavities/unit cell 2 6 16 8 3 2 1

Average cavity radius(Å) 3.95 4.33 3.91 4.73 3.91^c 4.06^c 5.71^c

Variation in radius^a(%) 3.4 14.4 5.5 1.73 not available

Coordination number^b 20 24 20 28 20 20 36

aVariation in distance of oxygen atoms from center of cage

bNumber of oxygens at the periphery of each cavity

cEstimates of structure H cavities from geometric models

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=

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m=1

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(5)

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J: \úûü ¤8F: GH\ ]

+Ì v6 !". Fig. 7 j O !t H(pore) ª

=:Ou n1 Ý= z ¶: Ú". }z: O

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n: Ýð \ z ¶: ð 3".

g, \úûü #: z\ zT× íð DA' #

: ×` vÊT(promoter) !". vÊT propylene oxide,

ethtylene oxide, THF o cyclic ethersG ". G: o ý \ Q2 wÀ n1 hA \¬ O !

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2-3.

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\Y KÄ4 'z¸ N ä a a !".

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|\ ; ¶º @S4 &B 6}". «X

¶: ~©\ ]\ ~ T¤". \úûü

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(slurry) m}- ¶ & !". )\) \úûü

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¥S". ñ, \úûü æ: æ ) æ: }-

2 {\ a a ¹" 3".

Scanlon Fennema[34] EO \úûü(Ì -I)× THF \úû Fig. 7. Hydrate phase equilibria of CO₂+water mixtures in silica gel

pores[31].

Fig. 8. Gas hydrate formation process.

Fig. 6. Hydrate phase equilibria of CO₂+H₂O+MgCl₂ systems[28].

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k ~ 0: \ \úûü #

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Iz t | z ".

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| z n6Ê Miller index× 2θ: \ \

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[40]. FO Q ýO =V× B jb O !".

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Y ¦H £h: N O ! , ¦H £h1 "

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2-4-2. NMR

Ò \úûü NMR: c1 Canada, NRC(National Fig. 10. X-ray powder diffraction pattern of pure CO₂ hydrate(struc-

ture I).

Fig. 9. Hydrate formation kinetics of carbon dioxide and water mix- ture at 274.15 K and 30 bar, 20 bar[39].

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z Xe ý¹ Ì -I, Ì -II, Ì -H \úûü2 Ì\

Ú"[44].

® \úûü K M ¦H ¹ ® F ¹³C NMR

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hydration number2 N O !".

Ì I:

Ì II:

θ_s θ_l1 MM ª1 ¦H ¦H £h: j ,

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". (1 Ì -I, II K MM w +ÌFG z ? 4ç, ^í4 Ì -I z 1,297 J/mol, Ì -II

z 883.8 J/mol (: "[6, 46, 47].

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, F r¦ F£r Ì -I ª1 ¦H Ì -II ¦H <

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jð ¹". ¹²CO₂ K NMR sepctrum JK 1 z

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Ð: ¢Àº CP(Cross Polarization): \ spectrum: czP".

F z Ì I ª1 ¦H: <K + \

34 %'´ µ4j ÂÆ Ripmeester× Ratcliffe[48] ¹²⁹Xe

13C NMR: Iz F Ì -I Ì -II ª1 ¦H:

< O !à: ,£ Ì -H ~ W O !" \Ú

". G1 =1,297 J/mol (: \ ] I mFE Ò ü¡ )4 ¦H £h", θ_s/θ_l=0.32, hydration number

=7.0 X (: T\Ú".

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isotropic line4 jÿ4ç, ¦H <Ê F

δ_xx=100.2× δ_zz=182.7 chemical shfit tensor2 powder pattern : !". chemical shift tensor ¦H <Ê

F isotropic chemical shift2 "à B N O !".

δ

chemical shift anisotropy "à B".

∆=δ_iso−δ_zz=−55.3

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2-4-3. Raman |

Raman |1 " c| "z x a ª ,g\ç z c x !6 1990* G6× \úûü +Ì "

l\ð !". Sum o[49]1 , Q k \úûü

: C\¬ O ! ¥¦ m: qcð ¤\ "l \

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/ 0 c Üý: Ú". ® K ~ k(33.6 bar) 2917.6 cm⁻¹ \j C: í) Ì -I \

úûü2 K 2,905 cm⁻¹ × 2,915 cm⁻¹

ª1 o ä 2s 2 ð ¹". ® F Ì -I \úûü ¦H(2,905 cm⁻¹) ª1 ¦H(2,915 cm⁻¹):

ä <K ¥S". $% , Ò ü¡ ä ¦H zh\

)" Ì I-\úûü ] Ì ¦H ª1 ¦ H §O"(3:1) Æy".

® -% ~ k ä s (1285.8 cm⁻¹, 1388.8 cm⁻¹)× $ ¨ ª1 ä s (1265.7 cm⁻¹, 1409.9 cm⁻¹)) v6´ !"(Fig. 12). \úûü F4

ð ) ª1 ä s ä s (1275.7 cm⁻¹, 1381.1 cm⁻¹) þ©ð ¹". × M dþÒ \

úûü K Ì -II2 \ 34 %'´ !Y XC Ò ü¡ Ì -II ª1 (1273.9 cm⁻¹) Ì -I $3(1275.7 cm⁻¹)" 1 wavenumber ¦ 3: j O !". XC Ò ü¡

]2 Iz \úûü Ì 2 ? N O !".

\úûü ® \úûü× -% XC Ò ü

¡ MM ¦H ª1 ¦H zh\ 2 ÌN O p".

«X, XC Ò ü¡: Iz F M ¦H £h

2 n: O p". $wj, Uchida o[51]1 × æ XC × z2 \ «X 7.24-7.68 µ_W⁰

∆ RT

--- 3ln 123[ ( –θ_{l CH}_, ₄)+ln 1( –θ_{s CH}_, ₄)] –

=

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∆ RT

--- ln 117[ ( –θ_{l CH}, 4)+2ln 1( –θ_{s CH}, 4)] –

=

µ_w⁰

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1

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=

Fig. 11.¹³C NMR CP spectrum of pure CO₂ hydrate at 243 K.

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\úûü hydration number2 n".

® \úûü hydration number 5.8-6.3 B |

&p i ^ (: í) \úûü K B | «X h gQ2 3: j O !". Table 3 "l | z B¹ \úûü hydration number2 %\Ú".

ÂÆ XC 2 @,4 n 3 Üz´ \

úûü !à ì \úûü : @ , XC 2 Iz &\ 3 Üz.". Kawamura o[52]1

−8.7^oC, 16 bar !à ì: ~× yv

\úûü }_ : XC Ò ü¡: Iz &\Ú

". , ý «X íù ÊÎ4 z \úû

ü Q4 \ 3: j O !". {

B1 Ò 0: z n1 {× ¦^ 9:

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3.

3-1. ! "#

Ò \úûü 2O æ v F Ì "l F G &6 Ð4 z Ð F2 ÄÅ4 %\ J s~ ù Ü D1 +ÌFG z T¤ !". `

ª ! 31 j ® o Ì QR Ò× «

¬, MO o O: DM: ¸\ æ:G"[55-57].

Kang Lee[57] t} 1 T® jD Ò

2 ÄÅ4 %\ H: T¤\Ú". Ò ^í

4 15-20 mol% × 5-9 mol% , j¯

: Q\ : o4 v6Ê". «X, , }% : i

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× : dþÒ \úûü #: \

2 %N O ! qr H: TzP". H1 THF O: \ × 2O æ: \ ä

Fig. 12. Raman spectra of CO₂ in gas(25.5 bar and 293.15 K), pure CO₂ hydrate(sI, 27.3 bar and 273.45 K) and CO₂+CCl₄ hydrate(sII, 26.0 bar and 280.25 K)[50].

Fig. 13. Pressure-composition diagram for hydrate-based gas separation from flue gas(two stages with promoter)[57].

Table 3. Hydration number of CO₂ hydrate obtained from several methods

Method N Reference

Theoretical(L-J 6-12) 6.82 53

Theoretical(Kihara) 7.26 53

Pressure drop 6-7.8 54

XRD 6.2 40

NMR 7.0 48

Raman spectroscopy 7.24-7.68 51

(9)

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Fig. 14. Schematic diagram of the hydrate-based CO₂ recovery process[57].

(10)

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sure, (c) Schematic diagram of carbon dioxide injection into methane hydrate formation[3, 4].

Fig. 16. The effect of injection flowrate on the formation temperature of CO₂ hydrate at constant pressure(25 bar)[64].

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