SPE

SPE 21112

Computation in Gas Hydrate Formation

by Alexandre Mussumeci* - PETROsRAs/CENPES

* SPE member

Cap,right 1890. Sol::Iety of Petroleum Eng.....'"

TN. _
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",~lected lor pr.....ntaIIon by an SPE Program
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Pennlsalon 10 copy Is reslrtcted 10 an abstract 01 nol more ....n 300 wonla. 111_ may IlOl be copied. TIla abBIr8CI shoutd contain
Is pr-.rad. Wrlla P........- MaMgaf. SPE. P.O. 1lGIlll33836. RlclIardson.

the etudy of hydrlte formation 9/lnlld. momllntum.

pertlcularly when Hemmerschlmldt prov,ed that
ABSTRACT tha plpe"ne clogging probleme typlcell~
encountered during winter months were caueed b~
A new method to predict Incipient gae the formation of hydretes rether then of Ice,
hydr'ate f-ormetlon I n systems contal nl ng an as hed been thought previOusly. Innumerous
aqueous phase In the ebsence or presence ot researchers 800n begen stUdying thiS Phenomenon
Inh"bltor.~ls proposed. and prOduced a numbar Of predictive methods
Dalled on theories ranging from simple empirical
The method which IS based on the correlations to the detal led microscopic stud~
statistical termodynamlc model of van der Waals of Intermolacular forces.
& Platteeuw for clathrates Is Implemented In a
compu tat I,onal code. Due to BraZil's climate, epeclflcally to
Its high temperatures, hydrate formation In
Result~ ot severe I elmulatlons are analysed patroleum facl I Itles had never presented a
and comp,ltr"ed with experimental dlta from 67 eer I OUII probl em. However, wi th the 8teed~
systlms'o~' the II tarature and Petrobras fie I dll. edvence of prOduction activities Into deeper
obtalnlng~~ood IIgreament between calCulated Ind and deeper watere, the possl blllty~ of lOw
obllerved dissociation prellllures, Chiefly In seaf loor temperatures caus I ng hYll.rates "to form
multlcomRonent hydrocarbon eYlltems. I ns I de pipe I I nes nee Inc reased substaht I ell y.
Owing to Its good performance. the method Although the literature prssen~s a number
can be appl led as a robust tOOl In process of predictive methods, at the tlmll.. t.hat these
design or In field operations In which gas were proposed they were only compared' against
hydrate equilibrium calculations are necessary. experlmentsl data on simple gas systems. Their
eppllcetlon to more complex 9as srstll~s, SUCh
es neturel 9as, may lead to serious errors.
INTRODUCTION
Tha purpose of this study was to optimize
'as hydrates (or simply hydratas) Ire process design and operational procedures
Ice-like ,crystalline compoundll that torm when concarned with the formation of natural gas
weter and gas come Into contact, nOrmally at hydrates, by providing relleble predictions of
lOW temperetures and high pressures. Hydrates the cond I t Ions under wh I ch the ph,nomenon wi II
~elong ~oa peculiar group of substancss known occur and which Include the presence of
as clathrates, WhiCh are compounds containing inhibitors. A new predictive me~hoi based on
two or ~ore componants Joined not by an van der WaalS end Platteeuw's theory Is
ordinary' chamlcal bond but by the complets proposed ena Imp I emented I n fORTRAN ANS I 77
encloe~r~ of one typa of moleCUle Inside I computational cOde. The reSUlts of severe I
suitable structure formed by another mOlacule. simulations are analyzed end co~parea With the
experimental data on multlcomponent mixtures
Since tha disCOvery of the first hydrate, available In the literature or obtained In
studies on these compounds have been puraly Brezilian 011 fields.
ecademlc Ind thU8 restricted to the eclentlflc
community. With the development of the US SOME ASPECTS Of THE CRYSTALLINE
petroleum Industry starting In the thirties,
STRUCTURE Of HYDRATES

References and I I IUstratlons at end of paper. Hydrates crystallize Into two types of
structure, known es I and II. The
 SPE 21112
crletllilizatiol' ba"I!;;;!i)' ct,!>el1d!os 01\ the size 1, 2 . . . n, which Ict 85 the clathrllte's
of the trappec IT'oiecule. Sma!! m'llecules host lattice.
crystllill ze Into Struc,ture I en~ lergs
molecules, In'to Str!1cture 1t. The numbH of cllgas of type" per molecule
Q denoted by
IS In the' case of v" .
A St un I t c e !! i 1> 1> h O\'in I n fig. 1.
r uc tu r a I
It contains ~S molecules th~t form two types hydroqulnones. v=1/3; for Structure I hydrates,
v a =1/23 and v z =3/23; lind for Str~cture I I
of clIges. The smal I cegss ~re IDcated at the
vertices and center of tbe eel I unit and each hydrates, va =2/17 and v z =1/17.
Is compo~ed of cO water moleculer ielG Qut in
the shape of a pentagona' dodecahedron. Tne six These con5lderlltlon~ were takan Into
remaining wllter molecules ir' tht ~Illt cell form account In designing the model:
bridges between tnese 'oaecaneoro~s, tnereby
cre6tl ns IC secon~ ty!'e of cags, ca II e~ e ! arse - The cages are spher I ca I.
cage. The latter con5ists of a tttr3decahe~ron
With twelue psntBgcnB Bides an6 two opposite - The t rap pe d mo lee u I e rna y 1Il0 ve,' f r eel y
hexagona I 6! oes\, within the cage.
These are the ccmpotltian cnaracterlstics
- Each cage mllY contain a maximum of one
for a Struc~u'! i n.dri~e:
gas molecule.
The trapped gas moleculas do not
2 sma I i ;;&gee Co 2C ei 3. SS'! Interact.
c,
- The gas molecules are smal I enough thllt
f! I ergc CS:BS " 24 11 "J.31}~ they tio not distort the lattice.
2'." 2

- It Is assumed that the Internal partition

Where zaBnd Z2lndl~ete the number Df oxysen function of the trapped gas mOlecul~s IS the
8 toms 5 u rr 0 {j n din S ',(~; e two pes 0 f Cage s, wn I I e t. same as that of the gas moleCUles In the gas
Baand 3 z lndiC&te the average distance between phase and with ideal gae behavior.
these atoms ano the centers of the cag6s. The - Only van der Waals forces are Important
sma II cages are ~e",r! V spl1er I ca I end hsve 6 I n des c rib I n 9 the gas -wa t e r I nt e r 1I to:tJil n
free dlamet~i of approximatel, 5.11. The large
cages arc slightly flattened, since tile
distance between the oxygen atoms end the - AI I polllr forces lire presumadt~ be built
center of tt.. cage i~m) fonges from 4.041 to Into the h,drogen bridges of the lattice of
the h'llrate.
"l.BS'i. Their 'frr.e diameter Is !lp~ror,imlltall'
5. B 'A. DEVELOPING THE METHOD
The moleCUles of the gases that form
Structur" I hydrates usual: y occupy both In equilibrium, the chemical potential of
types l)f clIge5. If all C1:l9~5 were filled, the the water I n the liquid (L) or eolld (01) phllse
hydrate compo5itlc~ ~ouid be M.59/4H20. should be equal to the chemlcel potential
of the water In the hydrllte phase (HL that Is,
Tne hydrate unit cell that crystal II zes
Into Structure 11 is quite compler. (Flg.1). . .......... ( 1 )
Its composition ch~racterlstics are:
IntrodUClng~, which Is the chamlclli
136 water moleCUles
potent I a I of the water 1 n the hyd rete with 1I1 I
16 sma i I cages !~ 20 3,91'& cages empty (metastable phBse ~), and defining
H 13 H
A/.l = iJ - fJ e . . . (2)
7
.'Z 28 .~. 73~ '" '" v

we can tnen write

The 8mal I cages are distorted pentagonal
dodecaheOrons, with the distance between the
~H ' . (3)
oxygan atoms and t~ center of a cage ranging v
from 3.77'1 to 3.9S'K, Their average fr:;~
dlametar Ie only around 5.01. Tne large cages Calculating /i#.lH
are nearly sph~rlcal. with oxygen atome l~cut'j "
at the v~rtice3 of tne heKadeca~edron ~',e r
free diameter 15 IL7 A. The first term of Eq. 3 Is calCUlated b,
uSing a modification of the aKPlesslon deduced
1~ruc~wr~ Ii d1'ates Drs 1or~n~a[nlv by by van der Waals and Platteeuw; that 15,
molecules tao large tc be Bccommcdated In
5tru:tura I. ThiS ~eans tllat t~EEe moleCUles . . . . . . . . . (.1}
,,~., ~'7ily C""l;'. -~hE ;
sa;:i3S Structure
II, sin c eSt r u c t tl rei i sma J i cas e:5 are sma I I e r
t han S t r uc t u rei sma I I c s gas. wh ere R 1st hega 5 con 5 tan t, Tis the a bsol ute
temperature, and v mk IS the number of type mk
ASPECTS qF THE MOD~"i~~_QL,li; ,~~NOHENO~
ca~ p~r w2te" molecule In the lattice
[wnere m IS tnl size of the cage (1=smal I,
A t~ermostatist ca~ ,< c,athrate 2= I .. rge) and k : 5 the type Of structure
forma~'0" was dss;gnsj, ~Q~ J~ langmUir's (1=!, 2=11);." a fraction of tyP&mJc clIgas
Ideal lo:al;z0,~ ,3j~,J"pt; .,.~,~ mode I OCCliP I ad by ~um(J[:1er: 't 1. i s '
co =.);Jet5 a c!athr9te c~ .~n6l5t i 09 of a
~OleCUle 0 that 70rms 2 and a number of
., vu CMkL It
>:tlS'i:" ,:e 0 has . . . . . . . . . . (5)
n" a~j may under ~-Crnkj I j
d c' ,ner In the J

f.orm The DttH~: 15

-1 :ages of ~ypes
IS the Langmu I r adsorption

'~"==",'_'~C ,=~.~, ,,-- -J

SPE 211Jj~ ALEXANDRE MUSSUMEG I 3
constant for the hydrate-forming component L The langmuir constant can .also be
I n the type mI< csge, and where f j Is the calCUlated by using the empirical (elation,
fugac I ty of component j I n the gas mi xture. va I I d for a temperature range of 250 to 300 K.

Substituting 5 In 4 and rearranging, ..... '..' .. , ( 12)

iJ: = RT{ l
m
"'mk In ( 1 + 2'
J
Gmkj fJ (6) where A ,nd B
constants.
are e~perlmentall y adjusted

The fugac I ty of component j I n the gas In the computer code that has been deVised,
mixture Is calculated by USing Eq. 7. Eq.12 Is uBed whenever the temperature under
stUdy Is within Its range of vallllity. only
. . . . . . . . . . . . (7) when the temperature exceedS thiS range IS Eq.
8 used to calculate the langmuir constant. ThiS
procedure saves a tremendous amount of computer
where Yj Is the molar fraction of component time yet does not Jeopardize the aCcuracy of
In the gas phase; Is "'j
the fugacity the final result.
coeff I c I ent of component j I n the gas ml xture, lastly. { Is a constant OJ proportlona.llty,
calculated by using the Peng-Roblnson equation Introduced by Ng and Robinson to Improve the
of state; and P Ie the total absolute pressure results obtained In pradlctlng equilibrium
of the system. The binary Interaction when there Is a binary Interaction between the
coefficients k. . In the Peng-Roblnson equation molecules of the gas mixture. The constant Is
l.. " J
of state were taken from Gmehllng at al. a function of the concentration Of the moleCUle
of the most volatile hyllrate- forming component
The langmul r constant macroscoplcall y and of a binary Interaction factor ~. It Is
represents the microscopic-level Interaction expressed as
of gae-water molecules In the cage. Using
the lenarll-Jones-Oevonslll re cell mollel, van
der Waale and Platteeuw2 ehowed that the
{ = nj {1 + 3(0..-1)Yz - 2(01.-1 )j"a}
J J J J
(13)

langmuir constant can be written as (without

!lubscrlpts) where OJ I s the I nteract Ion factor for the
Z least volatile molecule lind eaCh one of the
C(T> = ,,"/kT [ex p [-W( r )/kTJ r dr ....... (8)
most volati Ie molecules forming hydrate j , and
where V j Is the molar fraction of compone'nt j ,
where Tis the abso I ute temperature, k Is The values of 0 were e~perlmentallY adjusted
Boltzmann's constant, end W(r) Is the potential and are shown In Table "I,
of a spherl call y symmetrl cal cell.
Ga I cui a tin g iJL,o
"cKoy and SlnanOgluShowed that the Klhara
spherical-core potential IS the Dest predictor The second term of Eq. 3 Is calculated by
of dissociation pressures for approximately using the variation In potential In response to
II pher I c a I I y mo lee u 1 e s . changes In temperature and pressure, With the
composition held constant; that Is,
The Klhara spherical-core potential 15
defined ae d( ~T) =
h
- Iff'" + liT dP
v . . . , . . . . . . (14)

5 28
. . . . (9)
When Ice and hydrate co-eXist, Eq. 14
becomes
r > 2a
where & Is the characteristic energy, a Is the
core radius, and C + 2a is the coil islon
diameter. Eq. S descrlDes the Interaction of
R T
iJ(T
..,

R
0
,P0 )
T0
01
r I
0
/i ho.
R ~
" dT +

the gas molecule and a water molecule In the IP /iv..,

cage. Adding together al I gas-wateI
dP - In r v ~
v
. . . . (15)

Interactions In the cel I, ~cKOY and Sinanogiu

o R T
arrived at the cel i potential; that IS,
where R 18 the gas constant, and whllre iJ~
W( r) = (To'P o ) Is the variation ~etween the molar
c hem I II I pot e nt I a I 0 f the wa t e r I nth e hya rat e
phase With empty cages (phase ~) and the molar
...... , , , .... ( 10) c hem I c a I pot e ntie I 0.t the Ice ph a s e (p has eo) ,
at temperature To(O C) and pressureP.. (O atm).
o.
where The term t:..h refers to the variation
between the mOlar " enthelples of the water 1&
ph as e s ~ II ndO. Th i 5 va rI a t Ion I n en t ha I pY l>. hv
IS conslderell constant over temperature ana
and wh ere N = "I. 5. 10, II nd 11; z Is the pre ss ur e c han 9e 5. sin c e t ha va r I a t I o'n I nv 0 I ve s
coordlnatlor number (number of oxygen atoms a tranSition from a hypothetical crystal line
surrounding the cege); and R Is the radiUS of structure (phase~) to a raal crystal I Ina
the cege. structure (phase 01).

The physical properties of the hydrate The term /iva

v
refers to the variation
lattice ana the thermodynamic properties of the between the molar volume of the 01 water In
hydrates themselves are shown In Tables 1 and phases ~ and a. This variation /iv.., Is taken to
2. The values Of Klnar~potentlal parameters
(Parrish and prausnltz) are shown In Table be constant over changes In pressure and
3. temperature,
 4 COMPUTATION IN GAS HYDRATE FORMATION SPf 21112
The term r v refers to the Ictlvlty where M ?and N ere ellperlmentall~ adjusted
conatants for Ilach I nh I bl tor" and wllere x.
coefficient of the water and x"" to the molar
Is tile molar concentration of the Inhibitor In
fraction of the watar In the Iqueous phase. the aqueous phase.
If liquid water Ind hydrate co-exist, Tha Influence of dissolved gasas In the
expreeslon (14) becomes aqueous phase Is Ignored In cllculatlng the
activity coefficient of the water (r y ) and In
'"
---
~a.

R T
"
~a(T .p )
v

R T0
0

11/v )
0

J: 0
(Aha + Ah' )
v v

R T
2
dT + CalCUlating the freezing-point depression for
the wlter.
Owing to the presence of Inhibitors,. Eq. 23

J:
(Ava +
'" dP - In r", Xv . . . . . . . . . . (18) la used In calculating the freezl~g-polnt

R T depress I on for the water (ATo,).

2
ATo . Cl + C2)t + C3X + C'Ix (23)
where I1h'v and 11/v refer to the variations In " L L 1,.

the molar enthalpy and molar volume of the where Cl, &2. C3, 7and C'I Ire ellperlmentally
water caused by the phase change from 5011 d adjusted constants for eacll Inhibitor. and ~L
water (Ice) to liquid water; that Is,
Is the Inhibitor concentration (mola fraction)
I1h~ h~ - h~ and AV~ = v~ - v~ (17) I n the aqueous phase.

These values et Po Ind To Ire ahown In Ten typas of Inhibitors ware used:
methanol, ethanol, propanol, sodium Chloride,
Table 2. potassium chloride, calcium chloride, ammonia,
ethylene glycol, diethylene glvcol, and
Solving Eq. '5 blsed on the previously trleth~lene gl~col.
formullted hypotheaes,
Solving the Equilibrium
o

[~ - -']
f14.la. ~o Ahv
v v
+ + The equl I Ibrlum problem Is solved when Eq.
R T R T0 R To 3 Is satisfied.
AvO Since al I aquatlons Involved req~lre that
v
P - In r ",lIv .. ( , 8) pressure and temperature be known. the
RT temperature Is set Ind the dissociation
pressure of the hydrate Is estimated
Eq. 18 18 dlveloped almllarly. Iterltlvely. Dissociation pressures are
calculated for structures I and II; tlll!- lesser
The concentration of water In the aqueous of the two pressures Is the correct preisure.
phallll Xv Is calculatlld by ulling Eq. '9.
Ca I cu lations Ire performed. numerl ca II y.
This stUdV relied on the Pegasus method, which
II . (19) Is a secant method modified to spesd up
v
convergence. The procedure. Is only slightly
whllrll ljT la thll sum of the molar fractions of slower than the Newton method but offers the
advantege of not requiring the derivative of
the gases dissolved In the water, and where the function. Convergence 15 obtained With a
Ill. Is the molar fraction of Inhibitor dissolved mlxlmum of eight Iterations.
In the water.
Ths program was Implemented In FORTRAN ANSI
The molar fraction of each species j 77. It calculates dissociation pressures and
dissolved In the water Is clliculated by temperatures, the quantity of Inhibitor to be
using the Krlchevsky-KallarnovkllY equation. used, and the type of crystal line structure
formed by the hydrate.
I j
II. ............... (20)
(~ ~j)
J
H. ellp ANALYSIS OF RESULTS
J
and
Simulations were conducted bV using
H ellp <1. + BIT> . . . . . . . . . . . . . . . . . (21 ) Systems with end without Inhibitors, and
J J J
dissociation pressures were calculated for g8S
hydrates. In both cases. systems were
where II j Is the molar fraction of component classified 8S simple, binary, or
mUltlcomponent.
dissolved In the aqueous phase; I j Is the
fugac I ty of the component j I n the gas phase, The prasent study sought to check the new
calculated by using the Peng-Roblnson equation method against a representative number of
of st~te; Hj Is the Henry constant for the data. The choice of elmple and binary syetems
(totalling '19) wa5 Irbltrary and limited to the
gas; vj Is the partial molar volume of the moet common in the II terlture. Since data on
c omp 0 ne nt j; and A? and Bar e ell per I me nt a I I Y mu I tic omp 0 n e n t 5 l' 5 t ems, and e 5 pe c I a I I y o n
adjusted constlnts . Systsms slmila,' to natural gas, ars relatlvaly
scarce In the I terature and, furthermore,
The act!~lty coefficient of the water r v Is since thsse sy!tsmB J-e of marked Importance
~~ ... ~o be un ::y wnr'"=r the system under In the petroleum Indu~try, In effort was made
stud' 15 composed of , te and gas. Calculating to analyze as many as possible In this
I r... Inhibltus IH .. ?,fsent entailS the use case, 18.
I"': 'es e~pr"5s,.d', shown In Eq. 22. j

, In r ,i pte X~ + fie X: (22 )

SPE 21112 ALEXANDRE MUSSUMECI
Based on these 67 systems, the analyals of T Absolute temperature, K
this predictive method Is quite representative,
particularly when compared with previously V
L
v
V
CI
I' 1'10 I a r v 0 I ume s , cm' IIno I
published studies. fight multlcomponent gas W(r) " " z SpherICally aymatrlc cell
systems (five from the literature and three potential, ergs
trom the Campos Basin) are shown In Fig. 2
through 6 and In Tables 5 through 7. The xv z Mole traction of weter
remaining? systems are described In detail In Mole fraction of component
Mussumecl and are shown In a summsrlzed form Yj
below. Tables 8 snd g show the overal I zmlt Coordination number of cage
reSUlts ot the analysis of the method. type mk.
Gas Systems Anslyzed without Inhibitors

- al ng I e - 9 (C 1; C2; C3; Nz ; Hz S; Ar ;
K r; Xe; CO ) = Klhara potential, ergs
z
z Oepth ot Intermolecular
- binary - 32 (Cl-IC'! (10); Cl-Kr; potential weI I, ergs
CO z -C3 (11); Cl-Ar (2); 8
m1tl
Fraction of cagas type mt
Cl-C2; Cl-C3; C1-nC'!;
occupied by component I
Cl-CO z ; Cl-H z S;
Chemical potentials, cal/mol
C3-~ (3
z Number of cages type mt per

- multlcomponent - '" water molecule

z fugacity coefflclant
- total - 55
Gas Systema Analyzed with Inhibitor

- simple - 6 CI Solid watar (Ice) phase

(C I -C2 (2) 1 (j = Empty hydrate phase
- blnery - 2
f z Freezing point of water
- multi component - '! Hydrate phase
H
- total - 12 L Liquid water phase

CONCLUSIONS
Sub.crlpt.
A new method tor predicting hydrate
formation has been develiped. Baeed on tha work
of Parrish and Prausnltz, this method combines o z Property at Ice point
several thermodynlmlc models In dsscrlblng J, I z Gas components
phlses. The hydrate phase Is modeled by ualng
the tharmostatlsticil ~dal conceived by van m z Cage type (1=smal I ;2=large)
der Waals Ind Platteeuw ;the gls phase, using z Structure type (1=1;2=11)
the Peng-ROblnson equltlon of stlte; Ind the
aqueous phlse With Inhibitor, using Mlrgules w Water
expressions, ?Wlth coefficients adjusted z Inhibitor
experimentally.
The method describes the behevlor of
multlcomponant hydrocarbon systems qUite REFERENCES
satlstactorlly, whether or not Inhibitors Ire
present. The excellent agreement With Hammerechlmldt, E.G.: -format'on of Gas
experimental data mikes the method In Hydratee In Natural Gas Tranpmlsslon
Important new tool In process design and In L1nes,- Ind. Ent/. C"-. 26 (1934'B51.
optimizing petroleum Industry operational
routines concerned with hydrlte formation. 2. van der Waals, J.H. and Platteeuw, J.C.:
-Clathrate So I uti ons, - Advan.. C,..... Phys. 2
(1959) 1. '
NOMENCLATURE
3. Gmeh I I ng, J. and Onken, U. :Vapor L(qu(d
Equ(l(brium Data Collection. DECHEMA
z Klhara core radius, i Chemistry Date Sarles (1977), v.l.
i
- Langmu I r constant, atm-
41. McKoy, V. end Sinenoglu, 0.: -Theory ot
FugaCity of component l or Dlssocatlon Pressures at Some Gas
In the gas mixture, Itm Hydrates,- J. C"-. Ph.ys. 38 (1963) 2946.

= Molar enthalples, cal/mol 5. Parrleh, W.R. Ind Preusnltz, J.I'I.:

"DISSOCiation Pressuree at Gae Hydrates
Boltzmann's constlnt, 1,38 Formed by Gas MI xtures, -Ind. Ent/. C1vHn.
x 1 0 -leS a r g I K Proc 0.. o.u.lop. " (1972) 26.
P Total pressure, atm
Radial coordinate, ~ 6. Ng, H. J. and Robinson, D.B.: -The
Measurement and Prediction of Hydrete
R z Gas constant, 0.08205 formation In Liquid Hydrocarbon-Water
atm.l/mol.K Systems,- Ind. Ent/. C1vnR.. F'UTId.am.. 15 (1976)
R Cell radius, ~ 293.
6 COMPUTATION IN GAS HYDRATE fORMATION SPE 21112
7. Mussumecl, A.: Resllsrch Center, PBtrobras,
RID de Janeiro. Personal Communication on
Unpublished Work. 51 METRIC CONVERSION fACTORS
psi x 6.894757 E+03 = P8scal<Pa)
8. Blrroso, L.C. et aL: Catcuto ~rico,
bar x 1.0 E+05 = pascal CPa)
E~ltore HARBRA Ltda., Sao Paulo (1987) 117.
cil x 4.186 E+OO = ]oule(J)
atm x 1.013250 E+05 = pascal(Pa)
9. McLeo~ Jr., H.O. In~ Campbell, J.H.,
II r g x l . 0 E-07 = ] 0 u I e ( J )
'Natura I Gas Hy~rates st Pressures to
angstrom x 1.0 E-l0 = meter(m)
10,000 psla,' J. Petro Thecn. (J u ne 1961>
590.

10. Wilcox, W.I. et aL: Net u r 8 I Gas

Hy~r8tes,' Ind. En6. eM"'- 33 (1941) 662.

11. Ng, H.J. Ind Robinson, O.B.: GPA Research

R.port RR-66 (1983).

TABLE ~ - BINARY INTERACTION FACTORS

TABLE 1 - SO~ PAOPERTIES OF HYDRATE LATTICES
PAIR
SMALL
STRUCTURE I
LAROW:
STRUCTURE I I
....A1.oL. LAaOll:
'"
No- of C I V I tie a I METHANE-ETHANE 1,02
un I t ce I I 2 6 16 8 METHANE-PROPANE 1, DO
METHANE-ISOBUTANE 1,02
Cav'ty rldlUs (1) 3,975 ~,300 3,910 ~,730 METHANE-ETHYLENE 0,99
METHANE-ARGON 0.98
Coor~ln.tlol 1 (1) 28 20 28 COZ-PROPANE 1,12
N2 -METHANE 1,03
*-ARGON 0,96
HZ-PROPANE 1,05
PROPANE-PROPENE 0,98

TABLf 2 - THfIlMODYIUHI C PROPERTIES OF EMPTY HI ORATEs TABLE 5 - PESCADA FIELD DATA

5:TRUCTURIL 1 ETaUCTURIL U
PRESSURE (BAR)
a
J1- Ii"
, cli/mol 302 211 TEHPERATURE(oC) EXPERIMENTAL THIS WORK
"
ht'i - ht:J. , cal/mol 275 193 ~.8 9.26 10.17
" "
vt'i_
vv
a
, cc/mol 3.0 :3."l 'D. , 17 .53 19.95
" 15.1 33.69 :35.~3
h~- ht:J.
w
, cIl/mol 1"l36 ''''36
19.9 73.77 76.02
cpL
. _ (l
CP" ' cIl/lIlO I 9.11-0.03360 - 273 _15) 2~.8 229.31 220.3'"
- Prop.rt, It .... . 0 at. To . o c 30.2 529.7B ~77 .29
AVERAGE ERROR . 1. B6
"

TABLE 6 - BONITO f I ELl! DATA

HBlE 3 - KIHARA PARAMETERS fOR WATER-GAS I NTERACT IONS "
PRESSURE (BAR)
Gas 2a ,1 0',1 e/k,oK
TEMPERATURE(oC) EXPERIMENTAL THIS WORK
Hethane 0,600 3,2388 153.17
Ethane 0,800 3,3180 17'l,97 3.1 B.36
Ethylene 9. ''''
0,9"'0 3,2910 172.87
Propane 1,360 3,3030 200,9~ 5.9 12.2'1 13.19
Propene 1,30C :,230'1 202,~2 -<--"._-
Cyclopropane 1 ,000 3,~559 210,58 9.2 17.B'" lB.85
Isobutane 1,600 3, 1 2~'l 220,52
Nitrogen 0,700 3,6'~2 127,95 11 .8 26.1'1 27.31
0Ygen 0,720 2,7673 166,37 1 - - ' - - - - - ' ._.,
r:~ D -':!-., 2,~681 169,09 15,1 39.03 "'0.02
h>:S D. 3,1558 205,85 ,..----<
~-~on 86.59
2,9"l3'" 170,50 19.9 88.98
':!ton '1(, 2,9739 198,3'1
_ _ _ _'u.',_._
3, 1906 201,3'" AVERAGE ERROR ".61 'It

~, -
.......~."" ..
 SPE 21 I 12 7

TABLE 7 - BICUDD FIELD DATI TABLE S - AVERAGE ERROR Of' THE HETHOO FOR
-_..-._-_.. --_._----, GASeOUS SYSTEI'IS WITHOUT INHIBITION
pnEBSURE (BARl '
r-------+----------.------ 5 YS TEMS ERROR
TEHPERATURE(oC) EXPER!MENHL i 'HIS WORK
I------+---~._- SiNGLE (9 ) '1,61'10

~======:=:=:======~=====1=~_:._:3_7__L 1:::~
r
9.2 17 .26
i
i
------,
18.57
I
BINARY (32)
HULTIC. (14\)
6,98'10

7,B7'Io

11.9 25.28 26.81 TABLE 9 - AVERAGE ERROR OF THE HETHOO fOR

GASEOUS SYSTEMS WITH INHIBI~ioN
15. I 37.65 39.32

19.9 8'1.11 . : 85.19

---
SYSTEMS ERROR
AVERAGE ERROR; 5.50 "!> .-J SINGLE (6 ) " ,68\
BINARY (2) '1,85\

MUL TIC. ('I) 6,9'1'10

a b
FIG.Ol -UNIT CELL OF A HYDRATE OF STRUCTURE I (a) AND II ( b).
R'---------------------------,
GA~~~ON
(molar rrac~ion~
I
Cl - O.oot'lO

./
C2 - 0.0660
C3 - 0.0190
iC4
nCo/, -

*
111"

oo
AVERAGE ERROR
4.48 Yo

o '- -L ._..._J... ..._ _...I..- - - '_ _._ _-L _

292 296 300 304

TEMPERA TURE (K)
FIG.O2 -HYDRATE FORMATION CONDITIONS FOR MULTICOMPONENT
9
GAS MIXTURE. EXPERIMENTAL DATA OF McLEOD AND CAMPBELL
 SPE 21112
~ooo .--------------------------.,

GAS COMPOS! TI ON
(molar fraclion)
3500
C1 - 0.8836
C2 - 0.0682
C3 - 0.0254
3000 nC4 - O.OO9Q
iC4 - 0.0033
05+ - 0.0101

r::::=::::J
1000

500
AVERAGE ERROR
15.35 ~

Ol-- --L --L -L ...L..-------I

275 280 285 290 295 300

TEMPERATURE (K)
FIG.OJ -HYDRATE FORMATION CONDITIONS FOR MOLTICCJM1>OMENT
IO
GAS MIXTURE. EXPERIMENTAL DATA OF WILCOX et ai

4000 .----------'------------~_',__---..,

GAS COMPOSI TI ON
(mol .... f ....clion)
C1 - 0.8401
C2 - 0.0647
C3 - 0.0357
ne4 - 0.0114
iC4 - O.OOQQ
05+ - 0.0078
Nz - 0.0064

..
_
EXPERIMENTAL
CALCULATED

...

1000

500
AVERAGE ERROR
5.01 "

o --'- .L- ....JIL-- ...1- ~

275 280 285 290 295 .300

TEMPERA TURE (K)
F1G.04 -HYDRATE FORMATION CONDITIONS FOR MULTICOMPONENT GAS
lO
MIXTURES. EXPERIMENTAl. DATA OF WILCOX et al
 SPE 21112 9
200 ; - - - - - - - - - - - - - - - - - - - - - - - - - - - ,

GAS COHPOSI TI ON
(molar frac~ion)
*
175 C1 - 0.8413
ca - 0.0467
C3 - 0.0234
150 nC4 - 0.cog3
nCS - 0.cog3
N. - 0.0700

~:::::i 100

~
~ 75

50

25
AVERAGE ERI<OR
a.a3 "
0'-------.1.-----'------'-- '-- --'
265 270 275 280 285 290
1'P~(P"P1 TrrRP (V]
FIG. 05 -RYDHATB POtlMATIOII COIIDIl'IOIIB Fa- IIUL'l'ICOMPOllml'l' cas
MIXTURES WITH KE'l'HANOL (10\ wt.). DATA OF NG AND ROBINSON 11.

225 r-----------------------,
GAS CONPOSI TI ON
200 (molar frae~ion)
C1 - 0.71eo
ca - 0.0473
175 C3 - 0.01Q.4
nC4 - 0.0079
nCS - 0.0079
COz - 0.1419
Nz - 0.06Q6

75
*
50

25
AVERAGEERROR
.... 1 Q Y.

0'-- '-- '-- '-- --''-- --'

260 265 270 275 280 285
TEMPERATURE (K)
FIG.06 -HYDRATE FORMATION CONDITIONS FOR MULTICOMPONENT GAS
11
MIX'rtJRES WITH METBAllOL (20% wt.). DATA OF NG AND ROBINSON