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Prof. Sukumar Laik
Department of Petroleum Engineering
Indian School of Mines, Dhanbad
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Burning Ice!
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Milestones
1823:-1934-Scientific Curiosity
1934:- “Plugging” Natural Gas Pielines
19!5:-Natural Gas e"ist naturally ineart#$s crust
1999-till %ate: &esearc# on e"loration
an% e"loitation of gas #y%rate an%
Pro%uction 'ec#nology
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Hydrates - What arethey?
Gas #y%rates are soli% co(oun%s of gas an%
)ater in )#ic# gas (olecules are trae% )it#in
t#e crystalline structures of fro*en )ater+
'#ey rese(,le )et sno) an% (ay e"ist at
te(eratures a,oe t#e free*ing oint of
)ater+
'#ey ,elong to a for( of co(le"es .no)n as
clat#rates+
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Chemistry of
HydrateFormation
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Types of Hydrates
'#e follo)ing gases )#en co(,ine% )it#
)ater un%er t#e rig#t con%itions are .no)n
to ro%uce #y%rates:
Natural gas (olecules ranging fro(
(et#ane to iso,utane
0y%rogen sulfi%e
Car,on %io"i%e
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Structure-I
•Guest gases: CH4, C2H6,
CO2, H2S
•Size of gases: d
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Structure of Methane drates
,
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'#e caities in Gas 0y%rates
a Pentagonal o%eca#e%ron
, 'etra.ai%eca#e%ronc 6rregular o%eca#e%ron
% 0e"a.ai%eca#e%ron e 6cosa#e%ron
'#e sc#e(atic %ra)ing of one tye ofnatural gas clat#rate structure in )#ic#
(et#ane (olecule is encage% ,y a
lattice of )ater (olecules+
a , c
% e
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Stability of Hydrate
Structure he guest &olecules offer energeticall3 fa$ora*le$an der aals interactions %ith the %ater &oleculessurrounding the&, and &a#e ossi*le the
cr3stallization of these ne% for&s5 Considera*le ressure &a3 *e reuired, ho%e$er, to ersuade the&olecules into the $oids5
7ll the *onds in gas h3drates are h3drogen *onds5ater8s readiness to &a#e these *onds is resonsi*lefor the sta*ilit3 of gas h3drates5
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"he phase beha#iour of hdrocarbon and $ater sstem is significantl
different from that of normal hdrocarbon mi%ture.
&as hdrates e%ist under a limited range of temperature and pressure
conditions.
Gas graity c#art for re%iction of
t#ree-#ase 7-0- ressure an%te(erature at* 1945+
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0y%rate ; 7i
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Stability Zones of Gas Hydrates
Left: velocity 'increase' in the hydrated sediments
above the BSR and 'drop' in free-gas bearing
sediments belo! Right: BSR shoing large
amplitude! opposite polarity seismic event "r"t
seafloor reflection"
"he hdrate stabilit 'one in
subsea sediments+
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Locating and studying HydratesSeveral methods.
1+ Seis(ic 'ec#ni
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?'#e gas #y%rate for(ation an% #ence %issociation are influence% ,y t#e
resence of %ifferent c#e(icals+
?So(e of t#ese acts as #y%rate in#i,itor an% so(e as ro(oter
?'#e stu%ies on t#e effects of in#i,itors an% ro(oter on #y%rate for(ation
an% %issociation are of ut(ost i(ortance in or%er to %eelo t#e roer
e"loitation tec#nology+
?'#e in#i,itors are a%%e% to lo)er t#e #y%rate for(ation te(erature )#ic# in
turn facilitate t#e %issociation of #y%rate+
?'#ere are ,asically t)o %ifferent tyes of in#i,itors na(ely:
i t#er(o%yna(ic in#i,itors : (et#anol (onoet#ylene glycol @AG an%
%i-et#ylene glycol AG + ii .inetic in#i,itorsBanti-agglo(erators: al.ylarylsulfonic aci% an% its salts
al.yl glycosi%es etc+Bsurfactants
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Determination of HydrateFormation Temperature and
Pressure'#e stes for %eter(ining t#e #y%rate for(ation
te(erature at a gien ressure are as
follo)s:
1 ssu(e a #y%rate for(ation te(erature2 eter(ine n for eac# co(onent+
3 Calculate ynBn for eac# co(onent+
4 Su( t#e alues of ynBn+
5 &eeat stes 1-4 for a%%itional assu(e%
te(eratures until t#e su((ation of ynBn is
e
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Prevention of HydrateFormation
'#e er(anent solution for #y%rate ro,le(s is%e#y%ration of t#e gas to a sufficiently lo) %e) oint t#ete(erature at )#ic# t#e gas is saturate% )it# )ateraor at a gien ressure
t t#e )ell site t)o tec#ni
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Gas Hydrates ! Future
Sour"e of #ner$y
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Non-Renewable EnergySources Conentional
Petroleu(
Natural Gas
Coal
Nuclear
>nconentional e"a(les
Eil S#aleNatural gas #y%rates in (arine se%i(ent
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ld
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World EnergyConsumtion
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2!
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(h &as
drates)
Or anic Carb n Distributi n
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Organic Carbon Distribution
*ig. istri,ution of organic car,on in eart# e"clu%ing
Gas H drates ! Potential So r"e of
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Gas Hydrates% ! Potential Sour"e of#ner$y&as hdrates are $idel distributed in permafrost regions
and beneath the sea in sediment of outer continentalmargins.
+ccording to the .S. geological Sur#e, the estimatedglobal natural gas hdrate reser#es are in the range from-/ to 0 -1 trillion cubic feet, $hich is t$ice aslarge the combined fossil fuel resources.
+t conditions of standard temperature and pressure 2S"P3,one #olume of saturated methane hdrate ma contain asmuch as -45 #olumes of methane gas 26#en#olden, -7703."his large gas8storage capacit of gas hdrates ma
represent an important source of natural gas.- m0 hdrate 9 -45 m0 S"P &as : .1 m0 (ater
Gas hydrates with their abundant resource is emergingas a potential cleaner fuel resource.
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Locations of kno$n and inferred gas hdrate occurrences in oceanic sediment
of outer continental margins and permafrost regions 2 6#en#olden, -7703.
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ni(als #ae een learne%
#o) to “eat” #y%rates for
energy
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'otal conentional NG-
3-3/ 'C@
>neen %istri,ution:
&ussia 33F @i%%le
Aast 33F Cana%a
@e"ico5F
orl% consu(tion ofNGH2+4 'C@
NG0 esti(ates
)orl%)i%e: 1-
4 'C@ (ean
esti(ate:25'C@
NG0 %istri,ute% eenly
Aen if 1F is
recoera,le 2'C@
Con$entional 0G $s 0GH
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! "on"ern "limate "han$e
Beond energ interests, methane gashdrates ma also pla a role in global
$arming. E#en slight $arming could freesignificant amounts of methane, a potentgreenhouse gas.
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Te"hnolo$y of Gas Hydrate
Produ"tion Gas recoery fro( #y%rates is c#allenging
,ecause t#e gas is in a soli% for( an% ,ecause#y%rates are )i%ely %iserse% in #ostile rctic an%%ee (arine eniron(ents+
'#e %eco(osition reaction of tyical naturallyoccurring (et#ane #y%rate can ,e reresente% ,y:C04 ? !02Esoli% → C04gas ; !02Eli
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Te"hnolo$y of Gas HydrateProdu"tion
he &echanis& of roduction of gas h3drates is *ased on&ainl3 three o*9ecti$es5
=ring t#e ressure an% te(erature con%itionsaroun% #y%rate articles outsi%e t#e #y%rate-
sta,ility *one+
Sustain t#e energy re
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Te"hnolo$y of Gas Hydrate Produ"tion
Seeral recoery rocesses #ae ,een suggeste% t#at can ,e %ii%e%
,roa%ly into t#ree categories: Depressuri'ation "hermal Stimulation
an% Inhibitor in;ection+
Schematic representation of the three8phase e
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Te"hnolo$y of Gas Hydrate Produ"tion
eressuri*ation is consi%ere% to ,e t#e (ost econo(ically ro(ising(et#o% for t#e ro%uction of natural gas fro( gas #y%rates+
'#e @essoya.#a gas fiel% in nort#ern &ussia is co((only use% as an
e"a(le of a #y%rocar,on accu(ulation fro( )#ic# gas #as ,een ro%uce%
fro( #y%rates ,y si(le reseroir %eressuri*ation+
Sc#e(atic of roose% gas #y%rate ro%uction (et#o%: 2a3 thermal in;ectionI 2b3
depressuri'ation> 2c3 inhibitor in;ection.
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Recent Status of &as hydrates
ariety of gas #y%rate researc# rogra(s are currently un%er)ay
in %ifferent arts of t#e )orl% for econo(ic ro%uction of gas#y%rates+
6n 1999-2 t#e Jaan National Eil Cororation )it# fun%ing fro(@inistry of 6nternational 'ra%e an% 6n%ustry @6'6 %rille% a series ofgas #y%rate test )ells in t#e Nan.ai 'roug# off t#e sout#ern coastof Jaan an% %iscoere% %istri,ution of (et#ane #y%rate insan%stone layers+
6n 21 @6'6 #as starte% “ Jaan$s @et#ane 0y%rate A"loitationProgra(” a 1!-year rogra( in )#ic# (et#ane #y%rate is %efine%
as a future energy resource t#at is e"ecte% to e"it in largea(ounts offs#ore aroun% Jaan+
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'e"ent Status of Gas hydrates'esear"h
Cana%a #as a long #istory of gas #y%rate researc# t#at,egins in t#e 19/$s+ Su,se+S+ Geological Surey>SGS co(lete% a four-(ont# e"e%ition for t#e
occurrence of gas #y%rates in t#e offs#ore of 6n%ia+
'#e EA Gulf of @e"ico Joint 6n%ustry ProDect J6P is anaggressie (ulti(illion-%ollar gas #y%rate researc# rogra(focuse% on t#e >S Gulf of @e"ico+
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Synt#esis
C#aracteri*ation of
Gas 0y%rates
' h G H d t i th
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'esear"h on Gas Hydrate in theDept( of Petroleum #n$ineerin$) *SM+niversity)*,D*!
P#otogra# of A"eri(ental Set-u
'esear"h on Gas Hydrate in the Dept of
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'esear"h on Gas Hydrate in the Dept( of
Petroleum #n$ineerin$) *SM Dhanbad inetic Stu%ies on Gas 0y%rate Kor(ation
an% eco(osition #ae ,een erfor(e%+
'e(erature an% ressure trace for for(ation an% %eco(osition of et#ane#y%rates
H d t i th d
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Hydrates in the oenedautoclave reactor
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&ate of gas consu(tion %uring nucleation at %ifferent ressure+
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Affect of stirring on consu(tion of et#ane gas
%uring #y%rate for(ation at 1!+!/ ,ar
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Concetual (o%el of (ass transfer fro( gas #ase to crystal surface
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#e Gas Hydrate $uto %lave $pparatus
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Nucleation
Gro)t#
Cooling
P r e s s u r e 2 @ P a 3
'e(erature:3
Kor(ation
issociation
Fi$ure ( 'emerature and ressure trace formethane hydrate
formation and dissociation in SSW with (.))* '#
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2 4 ! 8 1 12
-+5
+
+5
+1
+15
+2
+25
+3
+35
/nduction ti&e:
H3drate Onset
H3drate Gro%th
ti:t
o)t
s
tot
s
G a s C o n s u & t i o n ( & o l e s "
i&e(&in"
'ure %ater
Fi$ure ( Rate of gas consumtion duringmethane
h drate formation
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