SECTION 20

Dehydration
Nat ur al gas and associat ed condensat e ar e oft en produced
from t he r eser voir sat ur at ed (in equilibr ium) wit h wat er. In
addit ion, t he gas and condensat e oft en cont ain CO
2
and H
2
S
which might requir e r emoval. This is fr equent ly accomplished
wit h aqueous solut ions such as amines, pot assium car bonat e,
et c. which sat ur at e t he gas or condensat e wit h wat er. Liquid
hydr ocarbons may also cont ain wat er downst ream of product
t reat ers or upon r emoval from under ground st orage.
Dehydrat ion is t he process used t o r emove wat er fr om nat u-
r al gas and nat ural gas liquids (NGLs), and is requir ed t o:
prevent for mat ion of hydrat es and condensat ion of fr ee
wat er in pr ocessing and t ranspor t at ion facilit ies,
meet a wat er cont ent specificat ion, and
prevent cor rosion
Techniques for dehydrat ing nat ur al gas, associat ed gas con-
densat e and NGLs include:
Absorpt ion using liquid desiccant s,
Adsorpt ion using solid desiccant s,
Dehydr at ion wit h CaCl
2
,
A = ar ea, ft
2
B = const ant in Equat ion 20-9
C = const ant in Equat ion 20-9
C
p
= heat capacit y, Bt u/(lb F)
C
g
= gravit y corr ect ion fact or for wat er cont ent
C
s
= salinit y corr ect ion fact or for wat er cont ent
C
ss
= sat urat ion cor rect ion fact or for sieve
C
T
= t emper at ure corr ect ion fact or
D = diamet er, ft
d = depr ession of t he wat er dewpoint or t he gas hy-
drat e freezing point , F
EOS = Equat ion of St at e
F
s
= sizing paramet er for packed t ower s, lb / (ft sec)
G = mass velocit y, lb /(ft
2
hr )
H = lat ent heat of vapor izat ion, Bt u/lb
K
vs
= vapor/solid equilibrium K-value
L = lengt h of packed bed, ft
L
g
= glycol flow rat e, U.S. gal./h r
L
MTZ
= lengt h of packed bed mass t ransfer zone, ft
L
s
= lengt h of packed bed sat urat ion zone, ft
m = mass flow rat e, lb/hr
MTZ = mass t ransfer zone
MW = molecular weight
MW
I
= molecular weight of inhibit or
N = number of t heoret ical st ages
P = pr essure drop, psi
q = act ual gas flow r at e, ft
3
/min
Q = heat dut y, Bt u/hr
Q
hl
= regener at ion heat loss dut y, Bt u/gal.
Q
r
= reflux heat dut y, Bt u/gal.
Q
s
= sensible heat , Bt u/gal.
Q
si
= dut y requir ed t o heat mole sieve t o regener at ion
t emperat ur e, Bt u
Q
st
= dut y requir ed t o heat vessel and piping t o regen-
erat ion t emperat ur e, Bt u
Q
tr
= t ot al r egenerat ion heat dut y, Bt u
Q
v
= vaporizat ion of wat er heat dut y, Bt u/gal.
Q
w
= desorpt ion of wat er heat dut y, Bt u
S
s
= amount of molecular sieve requir ed in sat ur at ion
zone, lb
T = t emper at ure, F
T
r g
= regener at ion gas t emper at ure, F
v = vapor velocit y, ft /sec
V = superficial vapor velocit y, ft /min
W = wat er cont ent of gas, lb/MMscf
W
r
= wat er r emoved per cycle, lb
x = mole fract ion in t he liquid phase
X = mass fract ion in t he liquid phase
y = mole fract ion in t he gas phase
z = compressibilit y fact or
= specific gr avit y
= viscosit y, cp
= densit y, lb/ft
3
Subscripts
i = inlet
o = out let
l = liquid
v = vapor
t = t ot al
CO
2
= carbon dioxide
H
2
S = hydrogen sulfide
HC = hydrocar bon
s = solid phase
L = lean inhibit or
R = rich inhibit or
I = inhibit or
H
2
O = wat er
H = hydrat e
rg = regener at ion
f = feed
p = permeat e
i = any component in a mixt ur e
FIG. 20-1
Nomenclature

20-1
Dehydr at ion by r efr iger at ion,
Dehydr at ion by membr ane permeat ion,
Dehydr at ion by gas st r ipping, and
Dehydr at ion by dist illat ion
WATER CONTENT OF GASES AND LIQUIDS
Water Solubi lit y i n Li quid Hydrocarbons
Fig. 20-2 is based on experiment al dat a and shows t he solu-
bilit y of wat er in sweet hydrocar bon liquids. In sour hydrocar -
bon liquids, wat er solubilit y can be subst ant ially higher.
GPA RR-62
1
provides wat er solubilit y dat a for select ed hy-
drocar bons in bot h sweet and sour syst ems. Equat ions-of-
St at e (EOS) may be used t o est imat e wat er solubilit ies in
hydr ocarbon syst ems. GPA RR-42
2
pr ovides a comparison of
exper iment al versus calculat ed values using a modified So-
ave-Redlich-Kwong (SRK) EOS. Result s fr om EOS met hods
should be used wit h caut ion and verified wit h exper iment al
dat a when possible.
Solubilit ies of hydr ocarbons in wat er ar e, in gener al, consid-
erably less t han wat er in hydr ocarbons. Some exper iment al
dat a is available in GPA RR-62. Yaws, et. al.
3
pr ovide a gener al
cor relat ion which may be used t o est imat e t he solubilit y of
over 200 hydr ocarbons in wat er.
Water Cont ent of Gase s
The sat urat ed wat er cont ent of a gas depends on pr essure,
t emperat ur e, and composit ion. The effect of composit ion in-
creases wit h pr essure and is part icular ly impor t ant if t he gas
cont ains CO
2
and/or H
2
S. For lean, sweet nat ural gases con-
t aining over 70% met hane and small amount s of heavy hydr o-
car bons, gener alized pressur e-t emperat ur e corr elat ions are
suit able for many applicat ions. Fig. 20-3
4
is an example of one
such corr elat ion which has been widely used for many year s
in t he design of sweet nat ural gas dehydrat or s. It was first
published in 1958 and was based on exper iment al dat a avail-
able at t hat t ime. The gas gr avit y corr elat ion should never be
used t o account for t he pr esence of H
2
S and CO
2
and may not
always be adequat e for cert ain hydrocar bon effect s, especially
for t he pr edict ion of wat er cont ent at pressur es above 1500
psia. The hydrat e format ion line is approximat e and should
not be used t o predict hydrat e format ion condit ions.
The following examples are provided t o illust rat e t he use of
Fig. 20-3:
Example 20-1 Det er mine t he sat urat ed wat er cont ent for a
sweet lean hydr ocarbon gas at 150F and 1,000 psia.
Fr om Fig. 20-3,
W 220 lb/MMscf
For a 26 molecular weight gas,
C
g
0.98 (Fig. 20-3)
W (0.98)(220) 216 lb/MMscf
For a gas in equilibrium wit h a 3% brine,
C
s
0.93 (Fig. 20-3)
W (0.93)(220) 205 lb/MMscf
Water Cont ent of High CO
2
/H
2
S Gases
Bot h H
2
S and CO
2
cont ain mor e wat er at sat ur at ion t han
met hane or sweet nat ural gas mixt ures. The relat ive amount s
vary consider ably wit h t emper at ure and pressur e. Fig. 20-4
6
and 20-5
7
display sat urat ed wat er cont ent of pur e CO
2
and
H
2
S, respect ively, at various t emper at ures and pr essures. Fig.
20-6 shows t he sat urat ed wat er cont ent s of pure CH
4
, CO
2
and
select ed mixt ures vs. pressur e at 100F. Fig. 20-7
5
exhibit s t he
sat ur at ed wat er cont ent of pure CH
4
, CO
2
and a 95% CO
2

5% CH
4
mixt ur e vs. pr essure at 100F. Sever al significant ob-
ser vat ions can be made from t hese figur es and ot her available
dat a.
1. Sat urat ed wat er cont ent of pur e CO
2
and H
2
S can be sig-
nificant ly higher t han t hat of sweet nat ur al gas, part icu-
larly at pressur es above about 700 psia at ambient t em-
per at ures.
2. Corr ect ions for H
2
S and CO
2
should be applied when t he
gas mixt ur e cont ains more t han 5% H
2
S and/or CO
2
at
pressur es above 700 psia. These cor rect ions become in-
creasingly significant at higher concent rat ions and
higher pr essures.
3. The addit ion of small amount s of CH
4
or N
2
t o CO
2
or H
2
S
can dramat ically reduce t he sat urat ed wat er cont ent
compared t o t he pure acid gas.
Acid gas wat er cont ent is a ver y complex subject . The dat a
and met hods present ed her e should not be used for final de-
sign. Fig. 20-4, 20-5, 20-6 and 20-7 are all based on experimen-
t al dat a. A cursor y st udy of t hese figures r eveals t he
complexit ies involved. An accurat e det er minat ion of wat er
cont ent r equires a careful st udy of t he exist ing lit erat ur e and
available exper iment al dat a. In most cases addit ional exper i-
ment al dat a is t he best way t o ver ify pr edict ed values. Even
t he most sophist icat ed EOS t echniques may give result s of
quest ionable reliabilit y.
Below 40% acid gas component s, one met hod of est imat ing
t he wat er cont ent uses Eq 20-1 and Fig. 20-3, 20-8, and 20-9.
8
W y
HC
W
HC
+ y
CO
2
W
CO
2
+ y
H
2
S
W
H
2
S
Eq 20-1
Not e t hat Fig. 20-8 and 20-9 provide values for what is
t er med t he effect ive wat er cont ent of CO
2
and H
2
S in nat ur al
gas mixt ur es for use only in Eq 20-1. These ar e not pure CO
2
and H
2
S wat er cont ent s.
Anot her met hod for est imat ion of t he sat ur at ed wat er con-
t ent of acid gas mixt ur es up t o 6000 psia uses Fig. 20-10 and
20-11.
9
Wit h gases cont aining CO
2
, t he CO
2
must be convert ed
t o an equivalent H
2
S concent r at ion. For pur poses of t his
met hod, it is assumed t he CO
2
will cont r ibut e 75% as much
wat er t o t he gas mixt ur e, on a molar basis, as H
2
S.
Example 20-2 Det er mine t he sat ur at ed wat er cont ent of an
80% C
1
,

20%

CO
2
mixt ure at 160 F and 2000 psia. The exper i-
ment ally det er mined wat er cont ent was 172 lb/MMscf.
Method One
W
HC
167 lb/MMscf (Fig. 20-3)
W
CO
2
240 lb/MMscf (Fig. 20-9)
W (0.80)(167) + (0.20)(240)
182 lb/MMscf
20-2
FIG. 20-2
Solubility of Water in Liquid Hydrocarbons
20-3
FIG. 20-3
Water Content of Hydrocarbon Gas
20-4
FIG. 20-4
Water Content of CO
2
FIG. 20-5
Water Content of Hydrogen Sulfide
FIG. 20-6
Experimental Values for Water Content of Acid Gases
FIG. 20-7
Saturated Water Content of CO
2
- Rich Mixtures at 100F
20-5
FIG. 20-8
Effective Water Content of H
2
S in Natural Gas Mixtures vs. Temperature at Various Pressures
FIG. 20-9
Effective Water Content of CO
2
in Natural Gas Mixtures vs. Temperature at Various Pressures
20-6
Method Two
Fir st t he composit ion must be convert ed for use wit h Fig.
20-10.
y
H
2
S
( pseudo ) (0.75)(y
CO
2
) (0.75)(0.20) 0.15
W 0.49 bbl/MMscf (Fig. 20-10)
Densit y of wa t er 350 lb/bbl
(0.49)(350) 172 lb/MMscf
Fig. 20-12 compar es t he t wo met hods pr esent ed for sat u-
r at ed wat er cont ent det er minat ion of high CO
2
/H
2
S gas mix-
t ur es wit h some of t he available experiment al dat a. The last
four dat a point s shown in Fig. 20-12 indicat e t he dangers in-
volved wit h ext r apolat ion t o higher CO
2
or H
2
S cont ent s. In
one case, t he est imat ed wat er cont ent agr ees wit hin 11% of
t he exper iment al value. In anot her case, t he exper iment al
value is over 6 t imes t he est imat ed wat er cont ent .
Water Cont ent in t he Hydrate Re gi on
Fig. 20-3 is based on the assumpt ion t hat t he condensed water
phase is a liquid. However, at t emperatures below t he hydrat e
t emperat ure of the gas, t he condensed phase will be a solid
(hydrate). The water cont ent of a gas in equilibrium with a hy-
drate will be lower than equilibrium wit h a met ast able liquid.
This is acknowledged in t he Warning in Fig. 20-3.
Hydr at e format ion is a t ime dependent process. The r at e at
which hydr at e cryst als for m depends upon sever al fact or s in-
cluding gas composit ion, presence of cr yst al nucleat ion sit es
in t he liquid phase, degr ee of agit at ion, et c. During t his t ran-
sient hydrat e format ion period t he liquid wat er pr esent is
t er med met ast able liquid. Met ast able wat er is liquid wat er
which, at equilibr ium, will exist as a hydr at e.
GPA RR-45
11
, 50
10
and 80
12
present exper iment al dat a show-
ing equilibrium wat er cont ent s of gases above hydrat es. Dat a
from RR-50 is present ed in Fig. 20-13. For comparat ive pur -
poses, t he met ast able wat er cont ent of a sweet gas fr om Fig.
20-3 is also shown. Wat er cont ent of gases in t he hydrat e r e-
gion is a st r ong funct ion of composit ion. Fig. 20-13 should not
be ext r apolat ed t o ot her composit ions.
When designing dehydr at ion syst ems (par t icularly TEG
syst ems) t o meet ext remely low wat er dewpoint specificat ions,
it is necessar y t o det ermine t he wat er cont ent of t he gas in
equilibr ium wit h a hydrat e using a cor relat ion like t hat pr e-
sent ed in Fig. 20-13. If a met ast able corr elat ion is used, one
will over est imat e t he sat urat ed wat er cont ent of t he gas at t he
dewpoint specificat ion. This, in t urn, may r esult in a dehydr a-
t ion design which is unable t o meet t he requir ed wat er r e-
moval. Wher e experiment al dat a is unavailable, ut ilizat ion of
a sound t hermodynamic-based cor relat ion can pr ovide an es-
t imat e of wat er cont ent in equilibrium wit h hydrat es.
Water Cont ent Me asureme nt
Specificat ions for water cont ent measurement are given in GPA
Publicat ion 2140. These include the Valve Freeze Met hod, t he Bu-
reau of Mines Dew Point Test er, and t he Cobalt Bromide Met hod.
Cobalt bromide color change occurs at about 25-30 ppmw.
Ther e are several commercial inst r ument s available for
monit oring wat er cont ent based on ot her principles. Measur -
ing wat er cont ent s of less t han 20 ppmw or making dewpoint
det erminat ions at less t han 40F can be very difficult.
FIG. 20-10
Calculated Water Content of Acid Gas Mixtures
to 2000 psia
FIG. 20-11
Calculated Water Content of Acid Gas Mixtures
to 6000 psia
20-7
Mixture T, F P, psi g
Wate r Conte nt lb/MMscf
Expe ri mental Eq 20-1
Fi g. 20-10 &
20-11
11% CO
2
/89% C
1
100 2000 40.6 42 39.2
11% CO
2
/89% C
1
160 1000 286 277 287
20% CO
2
/80% C
1
100 2000 40.6 43 44.1
20% CO
2
/80% C
1
160 1000 282 278 287
8% H
2
S/92% C
1
130 1500 111
105
112
27.5% H
2
S/72.5% C
1
160 1367 247 258 273
17% H
2
S/83% C
1
160 1000 292
278
290
C
1
/CO
2
/H
2
S
30%/60%/10% 100 1100 81
72
NA
C
1
/CO
2
/H
2
S
9%/10%/81% 100 1900 442
72
NA
5.31% C
1
/94.69% CO
2
77 1500 109.2
38
NA
5.31% C
1
/94.69% CO
2
122 2000 164.6
105
NA
FIG. 20-12
Comparison of Experimental vs. Calculated Water Contents for Acid Gases
FIG. 20-13
Water Content of 5.31% C
3
/94.69% C
1
Gas in Equilibrium with Hydrate
20-8
HYDRATES IN NATURAL GAS SYSTEMS
A hydrat e is a physical combinat ion of wat er and ot her small
molecules t o produce a solid which has an ice-like appear -
ance but possesses a different st ruct ure t han ice. Their for ma-
t ion in gas and/or NGL syst ems can plug pipelines, equipment ,
and inst rument s, rest rict ing or int er rupt ing flow.
Ther e are t hr ee recognized cr yst alline st ruct ures for such
hydr at es. In bot h, wat er molecules build t he lat t ice and hy-
drocar bons, nit rogen, CO
2
and H
2
S occupy t he cavit ies.
Smaller molecules (CH
4
, C
2
H
6
, CO
2
, H
2
S) st abilize a body-cen-
t er ed cubic called St r uct ur e I. Larger molecules (C
3
H
8
, i-
C
4
H
10
, n-C
4
H
10
) form a diamond-lat t ice called St ruct ure II.
Normal par affin molecules lar ger t han n-C
4
H
10
do not for m
St r uct ur e I and II hydr at es as t hey are t oo lar ge t o st abilize
t he lat t ice. However, some isoparaffins and cycloalkanes
larger t han pent ane ar e known t o for m St ruct ure H hy-
drat es.
13
Gas composit ion det ermines st ruct ure t ype. Mixed gases
will t ypically for m St ruct ure II. Limit ing hydrat e number s
(rat io of wat er molecules t o molecules of included gaseous com-
ponent ) are calculat ed using t he size of t he gas molecules and
t he size of t he cavit ies in H
2
O lat t ice.
From a pr act ical viewpoint , t he st r uct ur e t ype does not af-
fect t he appear ance, pr opert ies, or pr oblems caused by t he hy-
drat e. It does, however, have a significant effect on t he
pressur e and t emperat ur e at which hydr at es form. St ruct ure
II hydrat es ar e more st able t han St r uct ur e I. This is why gases
cont aining C
3
H
8
and i-C
4
H
10
will form hydr at es at higher t em-
per at ures t han similar gas mixt ur es which do not cont ain
t hese component s. The effect of C
3
H
8
and i-C
4
H
10
on hydrat e
for mat ion condit ions can be seen in Fig. 20-15. At 1000 psia,
a 0.6 sp. gr. gas (composit ion is shown in Fig. 20-18) has a
hydr at e for mat ion t emper at ure which is 12-13F higher t han
pur e met hane.
The pr esence of H
2
S in nat ural gas mixt ur es r esult s in a
subst ant ially war mer hydr at e format ion t emper at ure at a
given pr essure. CO
2
, in general, has a much smaller impact
and oft en reduces t he hydrat e for mat ion t emperat ur e at fixed
pressur e for a hydrocar bon gas mixt ure.
The condit ions which affect hydrat e format ion ar e:
Primary Consi de rati ons
Gas or liquid must be at or below it s wat er dew point or
sat ur at ion condit ion (NOTE: liquid wat er does not have
t o be present for hydrat es t o form)
Temper at ure
Pr essure
Composit ion
Se condary Conside rations
Mixing
Kinet ics
Physical sit e for cr yst al for mat ion and agglomer at ion
such as a pipe elbow, orifice, t her mowell, or line scale
Salinit y
In general, hydr at e for mat ion will occur as pressur e in-
creases and/or t emper at ure decr eases t o t he for mat ion condi-
t ion.
FIG. 20-14
Conditions for Hydrate Formation for Light Gases
FIG. 20-15
Pressure-Temperature Curves for
Predicting Hydrate Formation
20-9
Predi ct i on of Sweet Nat ural Gas Hydrat e
Condi ti ons
Fig. 20-14, based on experiment al dat a, present s t he hy-
drat e pr essure-t emper at ure equilibr ium cur ves for pure
met hane, et hane, propane, and for a nominal 70% et hane 30%
propane mix.
Fig. 20-15 t hrough 20-17, based on gas gr avit y, may be used
for fir st appr oximat ions of hydrat e for mat ion condit ions and
for est imat ing per missible expansion of sweet nat ur al gases
wit hout t he format ion of hydr at es.
The condit ions at which hydr at es can form ar e st rongly af-
fect ed by gas composit ion. Composit ions used for t he const ruc-
t ion of Fig. 20-15 t hrough Fig. 20-17 are given in Fig. 20-18.
The gases are sat urat ed wit h wat er.
Example 20-3 Find t he pressur e at which hydrat e for ms for
a gas wit h t he following composit ion. T = 50F.
Component
Mole
Fr act ion
Mole Wt
lb per lb-mol
of Mixt ure
C
1
0.784 16.043 12.58
C
2
0.060 30.070 1.80
C
3
0.036 44.097 1.59
iC
4
0.005 58.124 0.29
nC
4
0.019 58.124 1.10
N
2
0.094 28.013 2.63
CO
2
0.002 44.010 0.09
Tot al 1.000 20.08
Mole wt . of gas mixt ure = 20.08

MW
gas

MW
a ir

20.08
28.964
0.693
Fr om Fig. 20-15 at 50F
P = 320 psia for 0.7 gr avit y gas
Example 20-4 The gas in Example 20-3 is to be expanded from
1,500 psia t o 500 psia. What is the minimum initial temperature
t hat will permit the expansion wit hout hydrat e formation?
The 1,500 psia initial pressure line and the 500 psia final pres-
sure line int ersect just above t he 100F curve on Fig. 20-17. Ap-
proximately 112F is t he minimum initial temperature.
Example 20-5 How far may a 0.6 gravit y gas at 2,000 psia and
100F be expanded without hydrate format ion?
On Fig. 20-16 find the intersect ion of 2,000 init ial pressure line
with t he 100F init ial temperature curve. Read on t he x-axis t he
permissible final pressure of 1100 psia.
Example 20-6 How far may a 0.6 gravit y gas at 2,000 psia and
140F be expanded without hydrate format ion?
On Fig. 20-16, the 140F init ial temperature curve does not in-
t ersect t he 2,000 psia initial pressure line. Therefore, t he gas may
be expanded to atmospheric pressure wit hout hydrat e format ion.
Condit ions predicted by Fig. 20-15 through 20-17 may be sig-
nificantly in error for composit ions other than those used t o derive
t he charts. For more accurate det ermination of hydrate format ion
condit ions, t he following procedures should be followed. In addi-
t ion, Fig. 20-16 and 20-17 do not account for liquid water and liquid
hydrocarbons present or formed during t he expansion. These can
have a significant effect on t he out let temper at ure from t he pr es-
sur e reduct ion device.
See Caut ion on Fig. 20-15.
FIG. 20-16
Permissible Expansion of a 0.6-Gravity Natural Gas
Without Hydrate Formation
See Caut ion on Fig. 20-15.
FIG. 20-17
Permissible Expansion of a 0.7-Gravity Natural Gas
Without Hydrate Formation
20-10
Hydrate Predi ct i on Base d on Composi ti on
for Swe et Gases
Several corr elat ions have pr oven useful for pr edict ing hy-
drat e for mat ion of sweet gases and gases cont aining minimal
amount s of CO
2
and/or H
2
S. The most r eliable ones r equire a
gas analysis. The Kat z met hod
14,15
ut ilizes vapor solid equilib-
r ium const ant s defined by t he Eq 20-2.
K
vs
y/x
s
Eq 20-2
WARNING: Not good for pure component s only mixt ures.
The applicable K-value corr elat ions for t he hydrat e forming
molecules (met hane, et hane, propane, isobut ane
16
, normal bu-
t ane
17
, carbon dioxide, and hydr ogen sulfide) ar e shown in Fig.
20-19 t o 20-25. Normal but ane cannot for m a hydrat e by it self
but can cont r ibut e t o hydr at e for mat ion in a mixt ure.
For calculat ion pur poses, all molecules t oo large t o form hy-
drat es have a K-value of infinit y. These include all normal
par affin hydrocar bon molecules lar ger t han nor mal but ane.
Nit rogen is assumed t o be a non-hydr at e for mer and is also
assigned a K-value of infinit y.
The K
vs
values ar e used in a dewpoint equat ion t o det er -
mine t he hydr at e t emper at ure or pr essure. The calculat ion is
it er at ive and convergence is achieved when t he following ob-
ject ive funct ion (Eq 20-3) is sat isfied.

i 1
i n
(y
i
/ K
vs
) 1.0 Eq 20-3
Example 20-7 Calculat e t he pressur e for hydr at e for ma-
t ion at 50F for a gas wit h t he following composit ion.
Component
Mole
Fr act ion
in Gas
at 300 psi at 400 psi
Kvs y/Kvs Kvs y/Kvs
Met hane 0.784 2.04 0.384 1.75 0.448
Et ha ne 0.060 0.79 0.076 0.50 0.120
Pr opane 0.036 0.113 0.319 0.072 0.500
Isobut ane 0.005 0.046 0.109 0.027 0.185
n-But ane 0.019 0.21 0.090 0.21 0.090
Nit r ogen 0.094 * 0.000 * 0.000
Carbon dioxide 0.002 3.0 0.001 1.9 0.001
Tot al 1.000 0.979 1.344
* Infinit y Int er polat ing linear ly, y/Kvs = 1.0 at 305 psia
Prudence should be exer cised when some higher molecular
weight isoparaffins and cert ain cycloalt anes are pr esent as
t hey can form St ruct ure H hydr at es.
The experiment ally observed hydrat e-format ion pr essure at
50F was 325 psia.
Example 20-8 The gas wit h t he composit ion below is at
3500 psia and 150F. What will be t he hydrat e condit ions when
t his gas is expanded?
Component Mole Fract ion
C1 0.9267
C2 0.0529
C3 0.0138
iC4 0.0018
nC4 0.0034
nC5 0.0014
Tot al 1.0000
Soluti on Ste ps:
1. Make sever al adiabat ic flash calculat ions at different
pressur es and plot on a pr essure versus t emper at ure
gr aph. (See Fig. 20-26)
Init ial
Pressure,
psia
Init ial
Temperat ur e,
F
Final
Pr essur e,
psia
Final
Temper at ure,
F
3500 150 300 38
3500 150 400 45
3500 150 500 52
3500 150 600 58
3500 150 700 64
2. Assume some t emperat ur e and pr edict t he hydrat e for -
mat ion pr essure for t his gas using t he solid-vapor K-
dat a. Plot t he result s on Fig. 20-26. Sample calculat ions
for 200 and 300 psia are provided below. This calculat ion
has been r epeat ed for 400, 500, 800 and 1000 psia t o de-
velop Fig. 20-26.
T = 40F y
200 psia 300 psia
Kvs y/Kvs Kvs y/Kvs
C1 0.9267 2.25 0.4119 1.75 0.5295
C2 0.0529 0.50 0.1058 0.205 0.2580
C3 0.0138 0.055 0.2509 0.030 0.4600
iC4 0.0018 0.0225 0.0800 0.0105 0.1714
nC4 0.0034
C5 0.0014
Tot al 1.0000 0.8486 1.4189
y/K
vs
1.0 @227 psia
3. The int ersect ion of t he lines in Fig. 20-26 will be t he point
at which hydr at es st ar t t o for m. In t his example, t he r e-
sult is 500 psia and 52F.
Note: Fig. 20-16 would predict permissable expansion only t o
a pressur e ar ound 700 psia.
The Kat z corr elat ion is not recommended above 1000-1500
psia, depending on composit ion. Predict ion of hydrat e for ma-
t ion condit ions at higher pr essures requir es t he use of ot her
met hods. Sloan, et .al.
18
present an alt er nat e set of K
vs
values
which, in general, ar e valid t o 4000 psia. McLeod & Campbell
19
pr esent exper iment al hydr at e da t a for nat ur a l gas mixt ur es
up t o 10,000 psia a s well as a cor r elat ion for est imat ing
high pr essur e hydr at e for mat ion condit ions. Blanc &
Tour nier-Lasser ve
20
pr ovide exper iment a l hydr a t e dat a t o
14,500 psia a nd compa r e pr edict ion cor r ela t ions wit h ex-
per iment al da t a.
Mole Fr act ion
C
1
0.9267 0.8605 0.7350
C
2
0.0529 0.0606 0.1340
C
3
0.0138 0.0339 0.0690
iC
4
0.0018 0.0084 0.0080
nC
4
0.0034 0.0136 0.0240
nC
5
0.0014 0.0230 0.0300
Sp. Gr . 0.603 0.692 0.796
FIG. 20-18
Gas Compositions Used for Fig. 20-15 through 20-17
20-11
FIG. 20-19
Vapor-Solid Equilibrium Constants for Methane
FIG. 20-20
Vapor-Solid Equilibrium Constants for Ethane
20-12
FIG. 20-21
Vapor-Solid Equilibrium Constants for Propane
20-13
FIG. 20-22
Vapor-Solid Equilibrium Constants for Iso-Butane
FIG. 20-23
Vapor-Solid Equilibrium Constants for N-Butane
FIG. 20-24
Vapor-Solid Equilibrium Constants for Carbon Dioxide
FIG. 20-25
Vapor-Solid Equilibrium Constants for Hydrogen Sulfide
20-14
Hydrate Predi ct i ons for Hi gh CO
2
/H
2
S
Content Gase s
The Kat z met hod of pr edict ing hydr at e format ion t emper a-
t ur e gives r easonable r esult s for sweet nor mal paraffin hydr o-
car bon gases. The Kat z met hod should not be used for gases
cont aining significant quant it ies of CO
2
and/or H
2
S despit e
t he fact t hat K
vs
values ar e available for t hese component s.
Hydrat e for mat ion condit ions for high CO
2
/H
2
S gases can vary
significant ly from t hose composed only of hydr ocarbons. The
addit ion of H
2
S t o a sweet nat ur al gas mixt ur e will gener ally
incr ease t he hydr at e for mat ion t emper at ure at a fixed pr es-
sur e.
21

A met hod by Ba ille & Wicher t for pr edict ing t he t emper a -
t ur e of high H
2
S cont ent ga ses is shown in Fig. 20-27
22
. This
is ba sed on t he pr inciple of a djust ing t he pr opa ne hydr at e
condit ions t o a ccount for t he pr esence of H
2
S as illust r at ed
in t he following exa mple.
Example 20-9 Est imat e t he hydr at e for mat ion t emper a-
t ur e at 610 psia of a gas wit h t he following analysis using Fig.
20-27.
Component mol %
N
2
0.30
CO
2
6.66
H
2
S 4.18
C
1
84.27
C
2
3.15
C
3
0.67
iC
4
0.20
nC
4
0.19
C
5+
0.40
MW = 19.75 = 0.682
Soluti on Ste ps:
1. Ent er left side of Fig. 20-27 at 600 psia and proceed t o
t he H
2
S concent rat ion line (4.18 mol%)
2. Pr oceed down vert ically t o t he specific gravit y of t he gas
( = 0.682)
3. Follow t he diagonal guide line t o t he t emperat ur e at t he
bot t om of t he graph (T = 63.5F).
4. Apply t he C
3
corr ect ion using t he inser t at t he upper left .
Ent er t he left hand side at t he H
2
S concent rat ion and
proceed t o t he C
3
concent rat ion line (0.67%). Pr oceed
down ver t ically t o t he syst em pr essure and r ead t he cor -
r ect ion on t he left hand scale (2.7F)
Note: The C
3
t emper at ure corr ect ion is negat ive when on t he
left hand side of t he gr aph and posit ive on t he r ight hand side.
T
H
63.5 2.7 60.8F
Fig. 20-27 was developed based on calculat ed hydrat e con-
dit ions using t he Peng-Robinson EOS. It has pr oven quit e ac-
cur at e when compar ed t o t he limit ed amount of exper iment al
dat a available. It should only be ext rapolat ed beyond t he ex-
per iment al dat a base wit h caut ion.
Fig. 20-28
23
pr esent s exper iment a l hydr a t e for mat ion
da t a for t hr ee mixt ur es of met hane, pr opane and hydr ogen
sulfide. Result s of select ed hydr a t e pr edict ion met hods ar e
a lso shown.
The addit ion of CO
2
t o pur e met hane will slight ly incr ease
t he hydrat e t emperat ur e at a fixed pr essure.
24
However, t he
addit ion of CO
2
t o a t ypical sweet nat ural gas mixt ure will oft en
lower t he hydr at e format ion t emper at ure at a fixed pr essure.
Fig. 20-29 is pr ovided t o por t r ay t hese composit ional effect s.
The hydrat e curves for four gas composit ions are shown. These
were generat ed using a commer cial hydrat e progr am employ-
ing t he Peng-Robinson EOS. The four gas composit ions are:
Sweet Gas (0.6 sp. gr . gas from Fig. 20-18)
Sweet Gas cont aining 10% CO
2
Sweet Gas cont aining 10% H
2
S
Sweet Gas cont aining 10% CO
2
and 10% H
2
S
Not e t hat H
2
S significant ly increases t he hydr at e t emper a-
t ur e of a sweet nat ural gas. In t his example, at 1000 psia, t he
addit ion of H
2
S (10 mol%) t o a sweet gas mixt ur e increases t he
hydr at e t emper at ure by 15F. On t he ot her hand, CO
2
has a
minor effect on t he hydrat e format ion t emper at ure and
slight ly decreases t he hydrat e t emperat ur e for bot h t he
sweet and sour gases in t his case.
EOS-based comput er programs are probably t he most con-
sist ent met hod of predict ing hydrat e for mat ion t emper at ures
t oday. Accuracy when compared t o experiment al dat a is usu-
ally t 2F. This is gener ally adequat e for design.
Hydrate Inhi bi ti on
The for mat ion of hydr at es can be prevent ed by dehydrat ing
t he gas or liquid t o eliminat e t he for mat ion of a condensed
wat er (liquid or solid) phase. In some cases, however, dehydr a-
t ion may not be pr act ical or economically feasible. In t hese
cases, inhibit ion can be an effect ive met hod of pr event ing hy-
drat e format ion.
Inhibit ion ut ilizes inject ion of one of t he glycols or met hanol
int o a process st r eam where it can combine wit h t he condensed
aqueous phase t o lower t he hydrat e format ion t emperat ur e at
a given pr essure. Bot h glycol and met hanol can be r ecover ed
wit h t he aqueous phase, regener at ed and reinject ed. For con-
t inuous inject ion in ser vices down t o 40F, one of t he glycols
FIG. 20-26
Solution Sketch for Example 20-8
20-15
FIG. 20-27
Hydrate Chart for Gases Containing H
2
S
20-16
usually offer s an economic advant age ver sus met hanol r ecov-
ered by dist illat ion. At cryogenic condit ions (below 40F)
met hanol usually is pr eferr ed because glycols viscosit y makes
effect ive separat ion difficult .
Et hylene glycol (EG), diet hylene glycol (DEG), and
t riet hylene glycol (TEG) glycols have been used for hydrat e
inhibit ion. The most popular has been et hylene glycol because
of it s lower cost , lower viscosit y, and lower solubilit y in liquid
hydr ocarbons.
Physical proper t ies of t he most common glycols and glycol-
wat er mixt ur es ar e given in Fig. 20-30 t hr ough Fig. 20-41.
Tabular informat ion for t he pure glycols and met hanol is pr o-
vided in Fig. 20-42
.
Composi tion, mol % Expe ri mental Data
18
Pre di cte d Tempe rature ,F
C
1
C
3
H
2
S
Tempe rature ,
F
Pressure,
psia
Fi g. 20-15 Eq 20-3 Fi g. 20-27
88.654 7.172 4.174 0.649 40.3 102.4 NA 36.6 41.8
88.654 7.172 4.174 0.649 51.8 205.8 41 47.2 52.3
88.654 7.172 4.174 0.649 57.6 293.5 45 52.2 57.3
88.654 7.172 4.174 0.649 64.4 488.3 53 58.9 65.2
81.009 7.016 11.975 0.696 50.7 118.5 34 41.2 51.4
81.009 7.016 11.975 0.696 67.1 408 53 58.9 70.7
60.888 7.402 31.71 0.823 55.6 99.5 37 44.7 55.8
60.888 7.402 31.71 0.823 66.4 209.5 47 59.6 68.5
60.888 7.402 31.71 0.823 75.7 371 55 67.5 76.6
60.888 7.402 31.71 0.823 82.0 620 62 75.3 83.6
FIG. 20-28
Experimental vs. Predicted Hydrate Conditions for Gases Containing C
1
, C
3
, and H
2
S
FIG. 20-29
Hydrate Formation Conditions for Sweet Gas Showing Effects of CO
2
and H
2
S
20-17
To be effect ive, t he inhibit or must be pr esent at t he very
point where t he wet gas is cooled t o it s hydr at e t emper at ure.
For example, in refrigerat ion plant s glycol inhibit or s ar e t ypi-
cally spr ayed on t he t ube-sheet faces of t he gas exchanger s so
t hat it can flow wit h t he gas t hr ough t he t ubes. As wat er con-
denses, t he inhibit or is present t o mix wit h t he wat er and pr e-
vent hydr at es. Inject ion must be in a manner t o allow good
dist r ibut ion t o ever y t ube or plat e pass in chiller s and heat
exchanger s oper at ing below t he gas hydrat e t emper at ure.
The inhibit or and condensed wat er mixt ur e is separ at ed
from t he gas st ream along wit h a separat e liquid hydrocar bon
st ream. At t his point , t he wat er dewpoint of t he gas st ream is
essent ially equal t o t he separat ion t emperat ur e. Glycol-wat er
solut ions and liquid hydrocar bons can emulsify when agit at ed
or when expanded from a high pressur e t o a lower pr essure,
e.g., J T expansion valve. Careful separ at or design will allow
near ly complet e r ecovery of t he dilut ed glycol for regener at ion
and r einject ion. Fig. 20-43 shows a flow diagr am for a t ypical
EG inject ion syst em in a r efrigerat ion plant .
The regenerat or in a glycol injection syst em should be operated
t o produce a regenerated glycol solution t hat will have a freezing
point below t he minimum t emperat ure encount ered in the sys-
t em. This is t ypically 75-80 wt %. Fig. 20-44 shows t he freezing
point of various concent rat ions of glycol wat er solut ions.
The minimum inhibit or concent r at ion in t he fr ee wat er
phase may be approximat ed by Hammerschmidt s equat ion.
25
d
2335 X
I
MW
I
(1 X
I
)
Eq 20-4
Eq 20-4 should not be used beyond 20-25 wt % for met hanol
and 60-70 wt % for t he glycols. For met hanol concent rat ions
up to about 50%, the Nielsen-Bucklin equation
26
provides bet ter
accuracy:
d 129.6 ln(x
H
2
O
) Eq 20-5
Not e t hat x
H
2
O
in Eq 20-5 is a mole fr act ion, not a mass frac-
t ion. Fig. 20-45 pr ovides t he conversion from mass per cent
met hanol t o mole fr act ion wat er.
Maddox et.al.
27
pr esent s a met hod of est imat ing t he r e-
quir ed inhibit or concent r at ion for bot h met hanol and EG. The
met hod is it erat ive but converges easily aft er a few it erat ions.
Figs. 20-46 t hr u 20-50 provide a compar ison of var ious in-
hibit or cor relat ions wit h exper iment al dat a.
28,29,30
Experimen-
t al dat a at ver y high inhibit or concent rat ions is limit ed.
Once t he r equired inhibit or concent r at ion has been calcu-
lat ed, t he mass of inhibit or requir ed in t he wat er phase may
be calculat ed fr om Eq 20-6
m
I

X
R
m
H
2
O
X
L
X
R
Eq 20-6
The amount of inhibit or t o be inject ed not only must be suffi-
cient t o prevent freezing of the inhibit or wat er phase, but also
must be sufficient t o provide for t he equilibrium vapor phase
cont ent of the inhibit or and t he solubilit y of t he inhibit or in any
liquid hydrocarbon. The vapor pressure of met hanol is high
enough t hat significant quant it ies will vaporize. Met hanol va-
porizat ion losses may be est imated from Fig. 20-51.
31
Fig. 20-51
is ext rapolat ed above 700 psia. Recent st udies indicate Fig. 20-
51 may underest imate vapor phase met hanol losses at higher
pressures. Glycol vaporizat ion losses are generally very small
and are typically ignored in calculat ions.
Inhibit or losses t o t he hydrocar bon liquid phase ar e more
difficult t o predict . Solubilit y is a st r ong funct ion of bot h t he
wat er phase and hydr ocarbon phase composit ions. Fig. 20-52
present s experiment al dat a
32,33,34
showing solubilit y of
met hanol in a paraffinic hydr ocarbon liquid as a funct ion of
t emperat ur e and met hanol concent rat ion. Met hanol solubilit y
in napht henic hydr ocarbons is slight ly less t han paraffinic,
but solubilit y in ar omat ic hydr ocarbons may be four t o six
t imes higher t han in paraffinic.
Solubilit y of EG in t he liquid hydr ocarbon phase is ex-
t r emely small.
29
A solubilit y of 0.3 lb per 1000 gal. (U.S.) of
NGL is oft en used for design purposes. However, ent r ainment
and ot her physical losses may r esult in t ot al losses signifi-
cant ly higher t han t his.
Example 20-10100 MMscf/d of nat ur al gas leaves an off-
shore plat for m at 100F and 1200 psia. The gas comes onshore
at 40F and 900 psia. The hydrat e t emper at ure of t he gas is
65F. Associat ed condensat e pr oduct ion is 10 Bbl/MMscf. The
condensat e has an API gr avit y of 50 and a MW of 140. Calcu-
lat e t he amount of met hanol and 80 wt % EG inhibit or requir ed
t o pr event hydrat e format ion in t he pipeline.
Soluti on Ste ps:
Methanol
1. Calculat e t he amount of wat er condensed per day
from Fig. 20-3, W
in
53.0 lb / MMscf
W
in
9.5 lb / MMscf
W 43.5 lb / MMscf
Wat er condensed = (100)(53 9.5) = 4350 lb/day
2. Calculat e r equired met hanol inhibit or concent r at ion
from Eq 20-4 and 20-5.
d = 25F MW = 32
Solving for X
I
,
X
I
= 0.255, Eq 20-4
X
I
= 0.275, Eq 20-5 (use t his value in subse-
quent calculat ions)
3. Calculat e mass r at e of inhibit or in wat er phase (assume
100% met hanol is inject ed)
m
I

X
R
m
H
2
O
X
L
X
R

(0.275) (4350)
(1 0.275)
1650 lb/day
4. Est imat e vapor izat ion losses from Fig. 20-51.
@40F and 900 psia, losses = 1.05
lb/MMscf
wt % MeOH
daily losses = (1.05)(100)(27.5) = 2890 lb/day
5. Est imat e losses t o hydrocar bon liquid phase fr om Fig.
20-52.
@40F and 27.5 wt % MeOH, x
MeOH
0.2 mol%
lb mols of con d e n sa t e p e r d a y

100 MMscf
day
_

10 bbl
MMscf
_

(350)(0.78) lb
bbl
_

1 lb mol
140 lb
_

,
1950 lbmols/day
lb mols methanol (1950)(0.002)
3.9 lb mols/day
lb met hanol = (3.9)(32) = 125 lb/day
Tot al met hanol inject ion rat e = 1650 + 2890 + 125
= 4665 lb/day
20-18
FIG. 20-30
Densities of Aqueous Ethylene Glycol Solutions
FIG. 20-31
Densities of Aqueous Diethylene Glycol Solutions
FIG. 20-32
Densities of Aqueous Triethylene Glycol Solutions
FIG. 20-33
Viscosities of Aqueous Ethylene Glycol Solutions
Figures 20-30 t hrough 20-41 ar e repr oduced fr om Ga s Cond i t i oni ng Fa ct Book, 1962, wit h per mission fr om
The Dow Chemical Company and subject t o all warr ant y disclaimer s t her ein.
20-19
FIG. 20-34
Viscosities of Aqueous Diethylene Glycol Solutions
FIG. 20-35
Viscosities of Aqueous Triethylene Glycol Solutions
FIG. 20-36
Heat Capacities of Aqueous Ethylene Glycol Solutions
FIG. 20-37
Heat Capacities of Aqueous Diethylene Glycol Solutions
20-20
FIG. 20-38
Heat Capacities of Aqueous Triethylene Glycol Solutions
FIG. 20-39
Thermal Conductivity of Ethylene GlycolWater Mixtures
FIG. 20-40
Thermal Conductivity of Diethylene GlycolWater Mixtures
FIG. 20-41
Thermal Conductivity of Triethylene GlycolWater Mixtures
20-21
Met hanol left in t he gas phase can be r ecovered by conden-
sat ion wit h t he r emaining wat er in downst ream chilling proc-
esses. Likewise, t he met hanol in t he condensat e phase can be
r ecover ed by wat er by downst ream wat er washing.
80 wt%EG
1. Calculat e requir ed inhibit or concent r at ion fr om Eq 20-4.
d = 25F MW = 62
Solving for X
I
, X
I
= 0.40
2. Calculat e mass rat e of inhibit or in wat er phase.
m
I

(0.40)(4350)
(0.8 0.4)
4350 lb / day
Vapor izat ion and liquid hydr ocarbon losses are negligible.
Inhibit or losses r epr esent a significant oper at ing cost and can
cause pr oblems in downst r eam pr ocess unit s. Efficient inhibi-
t or separ at ion should be provided.
GAS DEHYDRATION
Glycol Dehydrati on Syste ms
In t hose sit uat ions where inhibit ion is not feasible or prac-
t ical, dehydr at ion must be used. Bot h liquid and solid desic-
cant s may be used, but economics fr equent ly favor liquid
desiccant dehydrat ion when it will meet t he r equired dehydr a-
t ion specificat ion.
Liquid desiccant dehydr at ion equipment is simple t o oper -
at e and maint ain. It can easily be aut omat ed for unat t ended
oper at ion; for example, glycol dehydr at ion at a remot e
product ion well. Liquid desiccant s can be used for sour gases,
but addit ional precaut ions in t he design ar e needed due t o t he
solubilit y of t he acid gases in t he desiccant solut ion. At very
high acid gas cont ent and r elat ively higher pressur es t he gly-
cols can also be soluble in t he gas.
Glycols are t ypically used for applicat ions where dew point
depressions of t he order of 60 t o 120F are requir ed.
Diet hylene glycol (DEG), t r iet hylene glycol (TEG), and
t et raet hylene glycol (TREG) ar e used as liquid desiccant s, but
TEG is t he most common for nat ur al gas dehydr at ion.
Ethyl ene
Gl ycol
Di ethyl ene
Gl ycol
Tri ethyle ne
Gl ycol
Tetraethyl ene
Gl ycol Methanol
For mula C2H6O2 C4H10O3 C6H14O4 C6H18O5 CH3OH
Molecular Weight 62.1 106.1 150.2 194.2 32.04
Boiling Point * at
760 mm Hg, F 387.1 472.6 545.9 597.2 148.1
Boiling Point * at 760
mm Hg, C 197.3 244.8 285.5 314 64.5
Vapor Pr essur e at
77F (25C) mm Hg 0.12 <0.01 <0.01 <0.01 120
Densit y
(g/cc) at 77F (25C) 1.110 1.113 1.119 1.120 0.790
(g/cc) at 140F (60C) 1.085 1.088 1.092 1.092
Pounds Per Gallon
at 77F (25C) 9.26 9.29 9.34 9.34 6.59
Fr eezing Point , F 8 17 19 22 144.0
Pour Point , F 65 73 42
Viscosit y in cent ipoise
at 77F (25C) 16.5 28.2 37.3 44.6 0.52
at 140F (60C) 4.68 6.99 8.77 10.2
Sur face Tension at
77F (25C), dynes/cm 47 44 45 45 22.5
Refr act ive Index
at 77F (25C) 1.430 1.446 1.454 1.457 0.328
Specific Heat
at 77 F (25C) Bt u/(lbF) 0.58 0.55 0.53 0.52 0.60
Flash Point , F (PMCC) 240 255 350 400 53.6
Fir e Point , F (C.O.C.) 245 290 330 375
Not e: These pr oper t ies ar e labor at or y r esult s on pur e compounds or t ypical of t he product s, but should not be confused wit h, or
r egar ded as, specificat ions.
* Glycols decompose at t emper at ur es below t heir at mospheric boiling point . Appr oximat e decomposit ion t emper at ur es are:
Et hylene Glycol 329F Tr iet hylene Glycol 404F
Diet hylene Glycol 328F Tet r aet hylene Glycol 460F
FIG. 20-42
Physical Properties of Selected Glycols and Methanol
20-22
Good pr act ice dict at es inst alling an inlet gas scr ubber, even
if t he dehydrat or is near a pr oduct ion separat or. The inlet gas
scrubber will prevent accident al dumping of lar ge quant it ies
of wat er (fr esh or salt y), hydrocar bons, t r eat ing chemicals or
cor rosion inhibit or s int o t he glycol cont act or. Even small quan-
t it ies of t hese mat erials can r esult in excessive glycol losses
due t o foaming, reduced efficiency, and increased maint e-
nance. Int egr al separat or s at t he bot t om of t he cont act or are
common.
Following t he process flow in Fig. 20-53, t he regener at ed
glycol is pumped t o t he t op t ray of t he cont act or (absorber).
The glycol absor bs wat er as it flows down t hr ough t he cont ac-
t or count er cur rent t o t he gas flow. Wat er-rich glycol is removed
from t he bot t om of t he cont act or, passes t hrough t he reflux
condenser coil, flashes off most of t he soluble gas in t he flash
t ank, and flows t hr ough t he r ich-lean heat exchanger t o t he
r egenerat or. In t he r egenerat or, absorbed wat er is dist illed
from t he glycol at near at mospheric pr essure by applicat ion of
heat . The regener at ed lean glycol flows t hrough t he r ich-lean
and glycol cooler exchanger for cooling befor e being r ecircu-
lat ed t o t he cont act or by t he glycol pump.
Evaluat ion of a TEG syst em involves fir st est ablishing t he
minimum TEG concent r at ion requir ed t o meet t he out let gas
wat er dewpoint specificat ion. Fig. 20-54 shows t he wat er dew-
point of a nat ural gas st r eam in equilibr ium wit h a TEG solu-
t ion at var ious t emperat ur es and TEG concent r at ions. Fig.
20-54 can be used t o est imat e t he r equired TEG concent r at ion
for a part icular applicat ion or t he t heoret ical dewpoint depr es-
sion for a given TEG concent r at ion and cont act or t emper a-
t ur e. Act ual out let dewpoint s depend on t he TEG cir culat ion
r at e and number of equilibrium st ages, but t ypical approaches
t o equilibr ium are 10-20F. Equilibr ium dewpoint s ar e rela-
t ively insensit ive t o pressur e and Fig. 20-54 may be used up
t o 1500 psia wit h lit t le err or.
FIG. 20-43
Typical Glycol Injection System
FIG. 20-44
Freezing Points of Aqueous Glycol Solutions
20-23
FIG. 20-45
Mol Fraction H
2
O vs. Weight % Methanol
FIG. 20-46
Hydrate Inhibition with Ethylene Glycol: Hammerschmidt vs. Experimental Data
28
20-24
FIG. 20-47
Hydrate Inhibition with Methanol: Hammerschmidt vs. Experimental Data
28
FIG. 20-48
Hydrate Inhibition with Methanol: Nielsen & Bucklin vs. Experimental Data
28
20-25
FIG. 20-49
Hydrate Inhibition with Methanol: Nielsen & Bucklin
26
vs. Experimental Data
28
FIG. 20-50
Hydrate Inhibition with Methanol: Maddox et al.
27
vs. Experimental Data
28
20-26
Fig. 20-54 is based on equilibrium dat a published by Parrish, et .
al.
35
Sever al equilibrium cor relat ions
36,37,38,39,40
have been
present ed since 1950. Pr evious edit ions of t he GPSA dat a book
present ed an equilibrium corr elat ion based on t he work of
Wor ley
38
. In general, t he corr elat ions of Worley,
38
Rosman
39
and Parr ish
35
agree reasonably well and are adequat e for most
TEG syst em designs. All are limit ed by t he abilit y t o measure
accurat ely t he equilibr ium concent r at ion of wat er in t he vapor
phase above TEG solut ions. The Parr ish cor relat ion has been
included in t his edit ion because equilibrium wat er concent r a-
t ions in t he vapor phase were det er mined at infinit e dilut ion
(essent ially 100% TEG). The ot her corr elat ions use ext rapola-
t ions of dat a at lower concent rat ions t o est imat e equilibrium
in t he infinit e dilut ion region.
Please not e t hat t he equilibr ium wat er dewpoint s on t he
ordinat e of Fig. 20-54 are based on t he assumpt ion t he con-
densed wat er phase is a met ast able liquid. At low dewpoint s
t he t r ue condensed phase will be a hydr at e. The equilibrium
dewpoint t emper at ure above a hydr at e is higher t han t hat
above a met ast able liquid. Therefor e, Fig. 20-54 pr edict s dew-
point s which are colder t han t hose which can act ually be
achieved. The differ ence is a funct ion of t emper at ure, pr essure
and gas composit ion but can be as much as 15-20F (see Fig.
20-13). When dehydr at ing t o ver y low dewpoint s, such as t hose
r equired upst r eam of a refr iger at ion process, t he TEG concen-
t rat ion must be sufficient t o dry t he gas t o t he hydr at e dew-
point .
Once t he lean TEG concent r at ion has been est ablished, t he
TEG circulat ion rat e and number of t rays (height of packing)
must be det ermined. Most economical designs employ
cir culat ion rat es of about 2-5 gal. TEG/lb H
2
O absorbed. The
r elat ionship bet ween circulat ion rat e and number of equilib-
r ium st ages employs t he absor pt ion calculat ion t echniques set
out in Chapt er 19. This has been done for TEG syst ems wit h
t he r esult s present ed in Figs. 20-55 t hr ough 20-59.
Conversion from equilibr ium st ages t o act ual t rays can be
made assuming an overall t r ay efficiency of 25-30%. For pack-
ing, Height of Packing Equivalent t o a Theor et ical Plat e
(HETP) var ies wit h TEG circulat ion rat e, gas r at e, and gas
densit y but a value of about 60 inches is usually adequat e for
FIG. 20-51
Ratio of Methanol Vapor Composition to Methanol Liquid Composition
20-27
planning purposes. When t he gas densit y exceeds about 6 lb/ft
3
(generally at ver y high pressur es), t he above conver sions may
not provide sufficient packing height and number of t r ays.
Also when t he cont act or t emper a t ur e is less t ha n about
60F, t he incr eased viscosit y of t he TEG ca n r educe mass
t r ansfer efficiency, a nd t emper at ur es in t his r a nge should be
a voided.
Typical t r ay spacing in TEG cont act ors is 24 inches. Ther e-
for e, t he t ot al height of t he cont act or column will be based on
t he number of t rays or packing requir ed plus an addit ional
6-10 ft t o allow space for vapor disengagement above t he t op
t ray, inlet gas dist ribut ion below t he bot t om t ray, and r ich gly-
col sur ge volume at t he bot t om of t he column. Bubble cap t rays
have hist orically been used in glycol cont act ors due t o t he low
liquid r at es ver sus gas flow, but st ruct ured packing is finding
accept ance. Gener ally, st ruct ured packing allows a signifi-
cant ly smaller cont act or diamet er and a slight ly smaller con-
t act or height .
Cont act or diamet er is set by t he gas velocit y. Sizing is iden-
t ical t o t hat out lined for separ at ors in Sect ion 7. Recom-
mended values for K-fact or s and C-fact or s are shown in Fig.
20-60.
St ruct ured packing vendor s fr equent ly quot e an F
s
value for
sizing glycol cont act ors, where F
s
is defined in Eq 20-7.
F
s
v
v
Eq 20-7
Values of F
s
= 2.5 t o 3.0 will gener ally pr ovide a good est i-
mat e of cont act or diamet er for st ruct ured packing.
Example 20-1130 MMscf/d of a 0.65 sp gr nat ural gas ent er s
a TEG cont act or at 600 psia and 100F. Out let wat er cont ent
specificat ion is 7 lb H
2
O/MMscf and t he TEG cir culat ion rat e
is 3 gal TEG/lb H
2
O. Est imat e t he cont act or diamet er and
number of bubble cap t rays or height of st r uct ur ed packing
r equired t o meet t his r equirement . Assume z = 0.92.
Soluti ons Steps:
1. Est imat e r equired TEG concent r at ion fr om Fig. 20-54
FIG. 20-52
Solubility of Methanol in Paraffinic Hydrocarbons
32, 33,34
vs. Temperature at Various Methanol Concentrations
FIG. 20-53
Example Process Flow Diagram for
Glycol Dehydration Unit
20-28
FIG. 20-54
Equilibrium H
2
O Dewpoint vs. Temperature at Various TEG Concentrations
FIG. 20-55
Water Removal vs. TEG Circulation Rate at Various TEG Concentrations (N = 1.0)
20-29
FIG. 20-56
Water Removal vs. TEG Circulation Rate at Various TEG Concentrations (N = 1.5)
FIG. 20-57
Water Removal vs. TEG Circulation Rate at Various TEG Concentrations (N = 2.0)
20-30
FIG. 20-58
Water Removal vs. TEG Circulation Rate at Various TEG Concentrations (N = 2.5)
FIG. 20-59
Water Removal vs. TEG Circulation Rate at Various TEG Concentrations (N = 3.0)
20-31
H
2
O Dewpoint = 24F, which fr om Fig. 20-3 is equiva-
lent t o a wat er cont ent of 7 lb H
2
O/MMscf @600 psia)
Assume a 10F appr oach t o equilibr ium
@T = 100F, lean TEG concent r at ion 98.8 wt %
2. Est imat e number of t heor et ical st ages.
Calculat e wat er removal efficiency
W
in
W
out
W
in

90 7
90
0.922
Fr om Fig. 20-56 (N = 1.5) at 3 gallon TEG/l b H
2
O and
99.0 wt % TEG
(W
in
W
out
)/W
in
= 0.885
Fr om Fig. 20-57 (N = 2.0) at 3 gallon TEG/l b H
2
O and
99.0 wt % TEG
(W
in
W
out
)/W
in
= 0.925
use N = 2.0
2 t heor et ical st ages 8 bubble cap t r ays @24 inch t ray
spacing
2 t heoret ical st ages 10 ft of st r uct ur ed packing
3. Size t he cont act or
Bubble caps, 24 inch t ray spacing:
Fr om Sect ion 7
G C [
v
(
L

v
)]
0.5
576 [2.0(69.9 2.0)]
0.5
6712 lb / ft
2
hr
m

30 000 000 scf

d
_

1 lb mol
379.5 scf
_

(0.65)(28.97) lb
lb mol
_

1 d
24 hr
_

,
62 000 lb/hr
A
m
G

62 000
6712
9.2 ft
2
D

4 A

,
0.5

(4)(9.2)
3.14
_

,
0.5
3.4 ft
For St ruct ured packing:
D

C
Bubble cap
C
St ructured packing
_

,
0.5
(D
Bubble cap
)

576
1200
_

,
0.5
(3.4) 2.4 ft
TEG will t ypically absor b about 1 scf of sweet nat ural gas
per gallon of glycol at 1000 psia and 100F. Solubilit ies will be
consider ably higher if t he gas cont ains significant amount s of
CO
2
and H
2
S.
The solubilit y of pur e CO
2
in a 96.5 wt % TEG solut ion is
shown in Fig. 20-61.
41
The solubilit y of pur e H
2
S in pur e TEG,
is shown in Fig. 20-62.
42
For gas mixt ures, t he solubilit y of H
2
S
and CO
2
can be est imat ed by ent ering t he gr aph at t he part ial
pressur e of t he component . The act ual solubilit y will t ypically
be somewhat less t han t his est imat ed value.
Heavier paraffin hydr ocarbons are essent ially insoluble in
TEG. Ar omat ic hydrocar bons, however, ar e very soluble in
TEG, and significant amount s of ar omat ic hydrocar bons may
be absorbed in t he TEG at cont act or condit ions. This may pr e-
sent an environment al or safet y hazard when t hey ar e dis-
char ged from t he t op of t he r egenerat or.
Vapor-liquid equilibr ium const ant s (K-values) for benzene,
t oluene, et hylbenzene, and o-xylene in TEG solut ions ar e pr e-
sent ed in RR-131.
43
This dat a indicat es t hat at t ypical cont ac-
t or condit ions approximat ely 10-30% of t he aromat ics in t he
gas st r eam may be absor bed in t he TEG solut ion. Based on t he
dat a in RR-131 at 1000 psia, 100F and a TEG circulat ion rat e
of 3 gal TEG/lb H
2
O absorbed, t he appr oximat e percent age
absorpt ion of aromat ics from t he gas int o t he r ich TEG are
calculat ed as:
Benzene 10%
Toluene 14%
Et hylbenzene 19%
O-xylene 28%
Aromat ic absor pt ion increases wit h increasing pressur e and
decreasing t emper at ure. Aromat ic absor pt ion is direct ly r e-
lat ed t o TEG circulat ion rat e. Higher circulat ion rat es result
in incr eased absor pt ion. Aromat ic absor pt ion is essent ially in-
dependent of t he number of cont act s in t he absorber so one
met hod of minimizing aromat ic absor pt ion is t o use t aller con-
t act or s and minimize TEG cir culat ion rat es.
Most of t he ar omat ic component s will be st ripped from t he
TEG solut ion in t he regener at or.
Flash t ank sizing should be sufficient t o degas t he glycol
solut ion and skim ent rained liquid hydr ocarbons, if necessar y.
A minimum r et ent ion t ime of 3-5 minut es is r equired for de-
gassing. If liquid hydrocar bons ar e t o be removed as well, r e-
t ent ion t imes of 20-30 minut es may be requir ed for adequat e
separ at ion. Flash t ank pr essures ar e t ypically less t han 75
psia.
Regenerat or sizing requir es est ablishing t he reboiler dut y
and, when high TEG concent r at ions are r equired, pr oviding
sufficient st r ipping gas.
A quick est imat e of reboiler dut y can be made using Eq 20-8.
Q (1500) (L
g
) Eq 20-8
Eq 20-8 is appr oximat e and usually gives values which are
higher t han t he act ual dut y. A more r igor ous det erminat ion of
r eboiler dut y is shown in Example 20-12.
Example 20-12 Det er mine reboiler dut y for condit ions in
t he previous example. Assume t he r ich TEG t emper at ure en-
K factor,
ft/sec
C factor,
ft/hr
Bubble Cap Tr ays
20 inch spacing 0.14 504
24 inch spacing 0.16 576
30 inch spacing 0.17 612
Packing
St ruct ured 0.3 t o 0.4* 1080-1440*
Random
1 inch Pall r ings 0.13 t o 0.18 468-648
2 inch Pall r ings 0.19 t o 0.26 684-936
* Depending on packing densit y and vendor
FIG. 20-60
Recommended Sizing Parameters for TEG Contactors

20-32
FIG. 20-61
Solubility of CO
2
in 96.5% wt% TEG vs. Pressure at Selected Temperatures
39
FIG. 20-62
Solubility of H
2
S in Pure TEG vs. Pressure at Selected Temperatures
40
20-33
t er ing t he regener at or is 300F and t he reboiler t emper at ure
is 400F.
Glycol Reboiler Dut y: Basis 1 gal. TEG
Sensible Heat :
Q
s
m C
p
t

(9.3 lb)
gal.

0.665 Bt u
lb F
_

,
(400F 300F)
618 Bt u /gal.
Vapor izat ion of Absorbed H
2
O:
Q
v
(H
vap
) (W )

970 Bt u
lb H
2
O
_

1 lb H
2
O
3 gal. TEG
_

,
323 Bt u /gal.
Condenser Dut y @25% Reflux Rat io:
Q
r
(0.25) (Q
v
) 81 Bt u /gal.
Tot al Dut y Including 10% Heat Loss:
Q
r
(618 + 323 + 81) (1.1) 1124 Bt u /gal.
Boiling of TEG at 400F and 1 at mosphere will provide
about 98.6 wt % glycol. Regenerat ion at higher alt it ude will
r esult in higher concent rat ions at 400F or a reduced regen-
erat ion t emperat ur e at t he same concent r at ion.
ENHANCED GLYCOL CONCENTRATION
PROCESSES
Ther e are several principles and pr ocesses for obt aining
higher TEG pur it y t han 98.6 wt %, which is t he TEG pur it y
obt ained by r eboiling at 400F and at mospheric pr essure. All
met hods are based on t he principle of r educing t he effect ive
par t ial pressur e of H
2
O in t he vapor space of t he glycol r e-
boiler, and hence obt aining a higher glycol concent rat ion at
t he same t emper at ure.
The most common met hod for enhancement of t he glycol
concent rat ion has been by use of st r ipping gas or by means of
vacuum in t he r eboiler.
Ot her pat ent ed processes in use t o enhance t he glycol pur it y
and t her eby achieve a mor e st r ingent wat er dew point depr es-
sion are as follows:
DRIZO

The DRIZO t echnology is a glycol based gas dehydr at ion

process. The process makes use of a solvent which is vaporized
and used as a st ripping agent in t he st ripping column. The
vapor fr om t he glycol reboiler/st ill column is condensed in a
unit t oget her wit h t he vapor fr om t he st ripping column. The
solvent and all BTEX compounds are condensed in t his unit
before t he vapor is dischar ged t o at mosphere. The main ad-
vant ages of t his syst em ar e t hat all BTEX compounds ar e r e-
cover ed from t he vapor before being sent t o at mosphere, t hat
t he TEG purit y can be as high as 99.999 wt %, and no ext er nal
st ripping gas is r equired. The DRIZO t echnology may be
adapt ed t o exist ing unit s which need t o be upgraded due t o
new r equirement s for higher glycol purit y, or for bet t er emis-
sion cont r ol of BTEX and CO
2
.
CLEANOL+

The CLEANOL+ t echnology is a glycol based gas dehydr a-

t ion pr ocess. The process is cover ed by t wo pat ent s; one is dedi-
cat ed t o glycol pur it y enhancement , and t he ot her one t o
envir onment al pr ot ect ion against air pollut ion. Bot h pat ent s
apply t o t he syst ems st ripping gas unit . The pr ocess makes
use of a st ripping agent which is mainly composed of aromat ics
(BTEX) t r apped in t he glycol cont act or and collect ed fr om t he
overhead vapor from t he reboiler/st ill column. The BTEX and
some wat er are condensed from t he vapor. The liquid BTEX
and wat er ar e separ at ed, and t he r equired flow of dr y BTEX
is vaporized and inject ed int o t he st r ipping column. Any excess
BTEX is r ecover ed as condensat e. The condensed wat er con-
t aminat ed wit h BTEX is vaporized and r ecycled for r ecovery
of BTEX, and t he clean wat er is dischar ged for disposal. The
CLEANOL+ process can pr ovide a glycol pur it y of 99.99%. The
pat ent ed CLEANOL+ process may easily be added t o a con-
vent ional glycol r egenerat ion syst em. The pr ocess does not use
any ext ernal gas for st ripping and dischar ges no BTEX or CO
2
t hr ough t he vent syst em t o t he at mospher e.
COLDFINGER

The Coldfinger pr ocess t akes basis in a convent ional glycol

r egenerat ion unit . The main pr inciple of t his t echnology is t o
condense and collect wat er/hydrocar bons fr om t he reboiler va-
por phase and drain it away fr om t he r eboiler. A Coldfinger
condenser wit h a collect ing t ray is locat ed in t he vapor phase
of t he r eboiler in a convent ional glycol regener at ion syst em t o
accomplish t he higher glycol pur it y. The collect ed wat er/con-
densat e from t he Coldfinger condenser is collect ed in an accu-
mulat or from wher e it is per iodically pumped int o t he st ill feed
st ream. The Coldfinger pr ocess can achieve a TEG concent r a-
t ion of appr oximat ely 99.96 wt %. The Coldfinger process does
not make use of st ripping gas.
PROGLY

The PROGLY process is a vacuum based syst em. The main

differ ence bet ween t his syst em and a t radit ional vacuum sys-
t em is t hat t he vacuum is applied t o a very limit ed par t of t he
syst em. The vacuum is applied t o a vessel r eceiving vapor di-
r ect ly from t he r eboiler, t hus giving a reduced vacuum pump
size.
This process does not r equire t he reboiler t o be locat ed above
t he surge t ank, as is r equired for convent ional syst ems, hence
giving more flexibilit y for t he lay-out arr angement .
The pr ocess does not requir e any st r ipping gas, and a TEG
concent rat ion of 99.9% wt % can be achieved.
The pr ocess can be adopt ed t o an exist ing convent ional gly-
col r egenerat ion syst em.
A BTEX r ecover y unit can be added as part of t he syst em.
ECOTEG
The ECOTEG process is ver y similar t o t he st ripping gas
process, but t his process recycles t he st r ipping gas. The proc-
ess uses blower s t o r ecycle t he st ripping gas and t hereby r e-
duces t he vapor disposals t o t he at mospher e. The ECOTEG
process can achieve a TEG concent r at ion of appr oximat ely
99.98%.
Ranges of glycol concent rat ions wit h t he var ious enhance-
ment pr ocesses ar e list ed in Fig. 20-65.
20-34
FIG. 20-63
Simplified Process Flow Diagrams of Enhanced TEG Regeneration Systems
20-35
OTHER CONSIDERATIONS
Under convent ional dehydr at ion condit ions, 40 t o 60% of
met hanol in t he feed gas t o a glycol dehydrat or will be ab-
sor bed by t he TEG
44
. This will add addit ional heat dut y on t he
r eboiler and addit ional vapor load on t he regener at or. High
met hanol inject ion r at es and slug carr yover can cause flood-
ing.
Glycol losses can be defined as mechanical carr yover from
t he cont act or (normally 0.10 gallon/MMscf for st andard mist
eliminat or ) plus vapor izat ion from t he cont act or and regen-
erat or and spillage. Glycol losses, exclusive of spillage, r ange
from 0.05 gallon/MMscf for high pressur e low-t emper at ure
gases t o as much as 0.30 gal/MMscf for low pressur e, high
t emperat ur e gases. Excessive losses usually result fr om foam-
ing in t he absor ber and/or r egenerat or. Ant i-foam agent s are
somet imes used.
TEG vaporizat ion losses at t he cont act or are minimal unless
t he gas t emperat ur e exceeds about 120F. These losses are
mor e significant at lower pressur es. Tet raet hylene glycol
(TREG) has been used in some cases t o minimize desiccant
FIG. 20-64
Effect of Stripping Gas on TEG Concentration
TEG
Conc. wt%
Water De w Poi nt
De pressi on
Possible, F
Vacuum 99.2 t o 99.9 100 t o 150
COLDFINGER

99.96 100 t o 150

DRIZO

99.99+ 180 t o 220

St r ipping Gas 99.2 t o 99.98 100 t o 150
FIG. 20-65
Glycol Regeneration Processes
FIG. 20-66
Example Solid Desiccant Dehydrator Twin Tower System
20-36
losses in high t emper at ure, low pressur e syst ems. Vaporiza-
t ion losses at t he r egenerat or t ypically result from excessive
st ripping gas r at es and/or inadequat e r eflux.
Glycol losses in CO
2
dehydr at ion syst ems can be signifi-
cant ly higher t han in nat ur al gas syst ems part icular ly at pr es-
sur es above about 900 psia. This is due t o t he solubilit y of TEG
in dense phase CO
2
. Glycer ol
45
is much less soluble and has
been used successfully as a desiccant in some CO
2
dehydr at ion
syst ems.
Glycol becomes corr osive wit h prolonged exposure t o oxy-
gen. A dr y gas blanket on t he glycol sur ge t ank will help elimi-
nat e oxygen absorpt ion. Special precaut ions should be t aken
if oxygen is in t he gas t o be dehydr at ed. Thermal decomposi-
t ion of TEG can become a problem if TEG is heat ed t o t em-
per at ures above 400F.
A low pH accelerat es decomposit ion of glycols. Bases such
as t r iet hanolamine, bor ax, or sodium mercapt obenzot hiazole
may be added t o maint ain pH, but t hey should be added spar -
ingly.
SOLID DESICCANT DEHYDRATION
Ther e ar e several solid desiccant s which possess t he physi-
cal charact erist ic t o adsor b wat er fr om nat ural gas. These des-
iccant s generally ar e used in dehydrat ion syst ems consist ing
of t wo or mor e t ower s and associat ed r egenerat ion equipment .
See Fig. 20-66 for a simple t wo-t ower syst em. One t ower is
onst r eam adsor bing wat er fr om t he gas while t he ot her t ower
is being r egenerat ed and cooled. Hot gas is used t o drive off
t he adsorbed wat er from t he desiccant , aft er which t he t ower
is cooled wit h an unheat ed gas st r eam. The t owers are
swit ched before t he on-st ream t ower becomes wat er sat u-
r at ed.
Solid desiccant unit s gener ally cost mor e t o buy and operat e
t han glycol unit s. Ther efore, t heir use is t ypically limit ed t o
applicat ions such as high H
2
S cont ent gases, ver y low wat er
dewpoint r equirement s, simult aneous cont r ol of wat er and hy-
drocar bon dewpoint s, and special cases such as oxygen con-
t aining gases, et c. In processes where cryogenic t emper at ures
are encount er ed, solid desiccant dehydr at ion usually is pr e-
fer red over convent ional met hanol inject ion t o prevent hy-
drat e and ice for mat ion. Solid desiccant s are also oft en used
for t he drying and sweet ening of NGL liquids.
Desiccant s in common commer cial use fall int o one of t hr ee
cat egor ies:
Gels alumina or silica gels manufact ur ed and condi-
t ioned t o have an affinit y for wat er.
Alumina a manufact ur ed or nat ural occurr ing form of
aluminum oxide t hat is act ivat ed by heat ing.
Molecular Sieves manufact ur ed or nat urally occurr ing
aluminosilicat es exhibit ing a degree of select ivit y based
on cryst alline st r uct ur e in t heir adsorpt ion of nat ural gas
const it uent s.
Silica Gel is a generic name for a gel manufact ured from
sulfur ic acid and sodium silicat e. It is essent ially pur e silicon
dioxide, SiO
2
. It is used for gas and liquid dehydrat ion and
hydr ocarbon (iC
5
+) r ecover y from nat ural gas. When used for
hydr ocarbon removal, t he unit s are oft en called HRUs (Hydr o-
car bon Recovery Unit s) or SCUs (Short Cycle Unit s). When
used for dehydr at ion, silica gel will give out let dewpoint s of
approximat ely 70 t o 80F.
Alumina is a hydr at ed form of alumina oxide (Al
2
O
3
). It is
used for gas and liquid dehydrat ion and will give out let dew-
point s in t he r ange of 100F. Less heat is requir ed t o regen-
erat e alumina t han for molecular sieve, and t he regener at ion
t emperat ur e is lower. Molecular sieves give lower out let wat er
dewpoint s.
Molecular sieves are a class of aluminosilicat es and possess
t he highest wat er capacit y, will produce t he lowest wat er dew-
point s, and can be used t o simult aneously sweet en and dry
gases and liquids. Their equilibrium wat er capacit y is much
less dependent on adsor pt ion t emper at ure and r elat ive hu-
midit y. They also are usually more expensive.
Molecular sieve dehydrat or s ar e commonly used ahead of
NGL recovery plant s designed t o r ecover et hane. These plant s
t ypically oper at e at ver y cold t emperat ur es and requir e very
dry feed gas t o pr event for mat ion of hydr at es. Dehydrat ion t o
a 150F dewpoint is possible wit h molecular sieves. Wat er
dewpoint s less t han 150F can be accomplished wit h special
design and st r ict operat ing paramet er s.
Fig. 20-67 pr esent s t he impor t ant proper t ies of commercial
solid desiccant s. Fig. 20-68
46
shows st at ic equilibr ium capacit y
vs. relat ive humidit y.
The cont inuous process requir es t wo (or mor e) vessels wit h
one on-line removing wat er while t he ot her is being regener -
Desi ccant Shape
Bulk Density,
lb/ft
3
Parti cle Si ze
Heat
Capaci ty,
Btu/(lb F)
Approx. Mi ni mum
Moi sture Content of
Effluent Gas (ppmw)
Alumina Gel Alcoa H-151 Spher ical 52 1/4" 0.20 5-10
Act ivat ed Alumina Alcoa F-1 Gr anular 52 1/4"-8 mesh 0.1
Silica Gel Sor bead-R Spher ical 49 4-8 mesh 0.25 5-10
Silica Gel Sor bead-H Spher ical 45 3-8 mesh 0.25 5-10
Mole Sieve Davison-4A Spher ical 42-45 4-8 mesh or
8-12 mesh
0.24 0.1
Mole Sieve Linde-4A Ext ruded
Cylinder
40-44 1/8" or 1/16" 0.24 0.1
FIG. 20-67
Typical Desiccant Properties
20-37
at ed. Gener ally a bed is designed t o be on-line in adsor pt ion
for 8 t o 24 hours. When t he bed is t aken off-line, t he wat er is
r emoved by heat ing t he sieve t o 450F-600F, depending on
t he desiccant used and t he performance specificat ion. The r e-
gener at ion gas used t o heat t he bed is usually a slipst ream of
dry pr ocess gas. The r egenerat ion gas is ret ur ned t o t he proc-
ess aft er it has been cooled and t he fr ee wat er r emoved. Any
heat sour ce can be used including wast e heat from engines and
t ur bines. This is an import ant design considerat ion since heat
is oft en a major oper at ing cost .
Gas flow during adsorpt ion is t ypically downflow. This al-
lows higher gas velocit ies (t hus smaller diamet er t ower s) since
bed fluidizat ion is avoided. Regenerat ion gas flow is upflow
dur ing t he heat ing cycle. In t hat way, any r esidual wat er left
on t he desiccant will be at t he t op of t he bed and will not affect
t he effluent dewpoint when adsor pt ion is resumed. In addi-
t ion, upflow heat ing helps t o st rip any cont aminant s from t he
t op of t he bed ext ending desiccant life. Regener at ion gas flow
dur ing t he cooling cycle may be upflow if t he gas is complet ely
free of wat er. This saves t wo swit ching valves per t ower which
can significant ly r educe capit al cost s. If t he cooling gas con-
t ains wat er, cooling flow should be downflow t o avoid preload-
ing of t he desiccant at t he bot t om of t he bed wit h wat er.
Desi gn
The allowable super ficial velocit y t hr ough t he bed is t he first
par amet er t hat must be est imat ed. The pr essure drop t hr ough
t he bed is relat ed t o t he super ficial velocit y by a modified Er -
gun
47
equat ion:
P
L
B V + CV
2
Eq 20-9
Const ant s for Eq 20-9 ar e:
Par t icle Type B C
1/8" bead 0.0560 0.0000889
1/8" ext rudat e 0.0722 0.000124
1/16" bead 0.152 0.000136
1/16" ext rudat e 0.238 0.000210
Fig. 20-69 was derived fr om Eq 20-9 by assuming a gas com-
posit ion and set t ing P/L equal t o 0.333 psi/ft . The design
pressur e drop t hrough t he bed should be about 5 psi. A design
pressur e drop higher t han 8 psi is not r ecommended as t he
desiccant is fragile and can be cr ushed by t he t ot al bed weight
and pr essure dr op for ces. Remember t o check t he pr essure
drop aft er t he bed height has been det ermined. Once t he al-
lowable superficial velocit y is est imat ed, calculat e t he bed di-
amet er :
D

4 q
(V)
1
1
]
0.5
Eq 20-10
The next st ep is t o choose a cycle t ime and calculat e t he mass
of desiccant r equired. Eight t o t welve hour cycles are common.
Cycles of great er t han 12 hours may be just ified especially if
t he feed gas is not wat er sat ur at ed. Long cycles mean less
r egenerat ions and longer sieve life, but lar ger beds and addi-
t ional capit al invest ment .
Dur ing t he adsor pt ion cycle, t he bed can be t hought of as
oper at ing wit h t hree zones. The t op zone is called t he sat ur a-
t ion or equilibrium zone. The desiccant in t his zone is in equi-
libr ium wit h t he wet inlet gas. The middle or mass t r ansfer
zone (MTZ) is where t he wat er cont ent of t he gas is reduced
from sat ur at ion t o < 1 ppm. The bot t om zone is unused desic-
FIG. 20-68
Static Equilibrium Capacity vs. Relative Humidity for
Selected Solid Desiccants
43
FIG. 20-69
Allowable Velocity for Mole Sieve Dehydrator
20-38
cant and is oft en called t he act ive zone. If t he bed operat es t oo
long in adsor pt ion, t he mass t ransfer zone begins t o move out
t he bot t om of t he bed causing a breakt hr ough. At break-
t hr ough, t he wat er cont ent of t he out let gas begins t o incr ease
and will event ually reach feed gas wat er cont ent when t he
MTZ is complet ely displaced.
Bot h wat er capacit y and t he r at e at which solid desiccant s
adsor b wat er decline as t he mat er ial ages. The object of t he
design is t o inst all enough desiccant such t hat aft er t hree t o
five years, t he mass t ransfer zone will be at t he bot t om of t he
bed at t he end of t he adsor pt ion cycle.
In t he sat urat ion zone, molecular sieve is expect ed t o hold
approximat ely 13 pounds of wat er per 100 pounds of sieve.
New sieve will have an equilibr ium capacit y near 20%; 13%
r epresent s t he appr oximat e capacit y of a 3-5 year old sieve.
This capacit y needs t o be adjust ed when t he gas is not wat er
sat ur at ed or t he t emper at ure is above 75F. See Fig. 20-70 and
20-71 t o find t he corr ect ion fact ors for molecular sieve. To de-
t er mine t he mass of desiccant r equired in t he sat urat ion zone,
calculat e t he amount of wat er t o be removed during t he cycle
and divide by t he effect ive capacit y.
S
S

W
r
(0.13)(C
SS
)(C
T
)
Eq 20-11
L
S

(S
s
)(4)
(D
2
)(bulk densit y)
Eq 20-12
Molecular sieve bulk densit y is 42 t o 45 lb/ft
3
for spherical
par t icles and 40 t o 44 lb/ft
3
for ext ruded cylinders.
Even t hough t he MTZ will cont ain some wat er (approxi-
mat ely 50% of t he equilibr ium capacit y), t he sat urat ion zone
is est imat ed assuming it will cont ain all t he wat er t o be r e-
moved.
The lengt h of t he mass t ransfer zone can be est imat ed as
follows:
L
MTZ
(V/35)
0.3
(Z) Eq 20-13
Wher e: Z = 1.70 for 1/8 inch sieve
0.85 for 1/16 inch sieve
FIG. 20-70
Mole Sieve Capacity Correction for Unsaturated Inlet Gas
FIG. 20-71
Mole Sieve Capacity Correction for Temperature
FIG. 20-72
Inlet and Outlet Temperatures During Typical Solid Desiccant Bed Regeneration Cycle
20-39
The t ot al bed height is t he summat ion of t he sat urat ion zone
and t he mass t ransfer zone height s. Appr oximat ely six feet
free space above and below t he bed is needed t o insur e pr oper
gas dist r ibut ion.
A second met hod uses Eq 20-11, but r eplaces t he sat ur at ion
capacit y of 13% wit h an effect ive desiccant capacit y which
includes t he MTZ effect , t emperat ur e, and relat ive humidit y
cor rect ions. When using t his met hod, an effect ive capacit y of
8-10% is t ypically assumed. This met hod is adequat e for most
planning and feasibilit y calculat ions.
Re ge nerati on Calculat ions
The first st ep is t o calculat e t he t ot al heat requir ed t o desorb
t he wat er and heat t he desiccant and vessel. A 10% heat loss
is assumed.
Q
w

1800
Bt u
lb
_

,
(lbs of wat er on bed) Eq 20-14
Q
si
(lb of sieve)

0.24 Bt u
lb F
_

,
(T
r g
T
i
) Eq 20-15
Q
st
(lb of steel)

0.12 Bt u
lb F
_

,
(T
rg
T
i
) Eq 20-16
Q
hl
(heat loss) (Q
w
+ Q
si
+ Q
st
)(0.10) Eq 20-17
For det erminat ion of t he r egenerat ion gas rat e, calculat e t he
t ot al regener at ion load from Eq 20-18.
Q
t r
(2.5)(Q
w
+ Q
si
+ Q
st
+ Q
hl
) Eq 20-18
The 2.5 fact or cor rect s for t he change in t emperat ur e differ -
ence (out in) acr oss t he bed wit h t ime dur ing t he regener a-
t ion cycle.
The heat ing t ime is usually 50% t o 60% of t he t ot al regen-
erat ion t ime which must include a cooling period. Figure 20-72
shows a t ypical t emperat ur e profile for a regener at ion cycle
(heat ing and cooling). For 8 hour adsorpt ion cycles, t he regen-
erat ion normally consist s of 4 1/2 hours of heat ing, 3 hour s of
cooling and 1/2 hour for st andby and swit ching. For longer
cycles t he heat ing t ime can be lengt hened as long as a mini-
mum pr essure drop of 0.01 psi/ft is maint ained.
m
r g
(lb/hr)
Q
tr
(C
p
)(600F T
i
)(heat ing t ime)
Eq 20-19
Fig. 20-73 can be used t o est imat e t he r equired minimum
velocit y t o meet 0.01 psi/ft .
General Comme nts
The regener at ion cycle frequent ly includes depressur -
ing/repressur ing t o mat ch t he regener at ion gas pr essure
and/or t o maximize t he r egenerat ion gas volume t o meet t he
velocit y crit er ion. Some applicat ions, t er med pressur e swing
adsor pt ion, r egenerat e t he bed only wit h depr essurizat ion and
sweeping t he bed wit h gas just above at mospheric pr essure.
Moist ure analyzer s for ver y low wat er cont ent s requir e care
t o pr event damage t o t he probes. When insert ed int o t he beds,
sample pr obes and t emper at ure probes must be inst alled t o
r each t he cent er of t he gas phase.
Solid desiccant t owers ar e insulat ed ext er nally or possibly
int ernally. Int ernal refract ory requir es car eful inst allat ion
and curing, usually befor e t he desiccant is inst alled. It saves
ener gy but t he great est benefit is it can dr amat ically r educe
t he r equired heat ing and cooling t imes. This is oft en an im-
por t ant benefit for syst ems where r egenerat ion t imes ar e lim-
it ed. The pr imary disadvant age is t he pot ent ial for wet gas
bypassing t he desiccant t hr ough cracks and defect s in t he in-
sulat ion during t he adsorpt ion cycle.
FIG. 20-73
Minimum Regeneration Velocity for Mole Sieve Dehydrator
FIG. 20-74
Typical CaCl
2
Dehydrator
20-40
Bot t om bed support t ypically includes t hree t o five layer s of
iner t ceramic balls in gr aduat ed sizes (smallest on t op). On t op
of t he bed, a hold-down scr een is provided, again covered wit h
a layer of cer amic balls. In some cases, a layer of less expensive
desiccant can be inst alled on t he t op of t he bed t o cat ch con-
t aminant s such as free wat er, glycol, hydr ocarbons, amines,
et c. This may ext end t he bed life. Good inlet separat ion of en-
t rained cont aminant s is absolut ely essent ial for long desiccant
life.
Since solid desiccant s can produce dust , 1m filt er s ar e fr e-
quent ly inst alled at t he out let of t he dehydrat ion unit t o pr o-
t ect downst r eam equipment .
Operat ing perfor mance should be monit ored periodically t o
adjust adsorpt ion cycle lengt h so t hat adequat e dehydr at ion
is obt ained. Perfor mance t est s are scheduled on a rout ine ba-
sis, ranging from mont hly dur ing early operat ions t o six
mont hs or longer. The size of t he unit and fr equency of regen-
erat ion cycles also affect t he t iming of performance t est s.
Calcium Chloride
Calcium chloride (CaCl
2
) can be used as a consumable des-
iccant t o dehydrat e nat ur al gas. Solid anhydr ous CaCl
2
combines wit h wat er t o form various CaCl
2
hydr at es
(CaCl
2
XH
2
O). As wat er absorpt ion cont inues, CaCl
2
is con-
vert ed t o successively higher st at es of hydrat ion event ually
for ming a CaCl
2
br ine solut ion.
3/8 in. to 3/4 in. CaCl
2
pellet s are inst alled in a fixed bed much
like a dry desiccant t ower. Gas flow is upflow. The more efficient
designs ut ilize 3-4 t rays below t he solid bed t o pre-cont act t he gas
wit h t he brine solut ion. This removes a port ion of the wat er from
t he gas before contact wit h t he solid CaCl
2
and increases unit
capacit y. One such unit is shown in Fig. 20-74.
The solid CaCl
2
near t he bot t om of t he fixed bed will t ypi-
cally be CaCl
2
4H
2
O or CaCl
2
6H
2
O and t he CaCl
2
at t he t op
of t he fixed bed will be anhydrous CaCl
2
or CaCl
2
H
2
0. In t his
way t he gas cont act s successively dr ier CaCl
2
as it flows
upwar ds and in t heory leaves t he fixed bed in equilibr ium wit h
t he CaCl
2
at t he t op of t he bed.
Out let wat er cont ent s of 1 lb/MMscf have been achieved
wit h CaCl
2
dehydrat or s. Typical CaCl
2
capacit y is 0.3 lb CaCl
2
per lb H
2
0. Superficial bed velocit ies ar e 20-30 ft /min and
lengt h t o diamet er rat io for t he bed should be at least 3 t o 4:1.
CaCl
2
dehydrat or s may offer a viable alt er nat ive t o glycol
unit s on low r at e, remot e dry gas wells. The CaCl
2
must be
changed out periodically. In low capacit y high r at e unit s t his
may be as oft en as ever y 2-3 weeks. Br ine disposal r aises en-
vironment al issues. In addit ion, under cer t ain condit ions t he
CaCl
2
pellet s can bond t oget her t o for m a solid bridge in t he
fixed bed port ion of t he t ower. This result s in gas channeling
and poor unit per for mance.
Dehydrat i on by Refri gerati on
The dehydrat ion of nat ur al gas can also be achieved by r e-
frigerat ion and/or cr yogenic processing down t o 150F in t he
presence of met hanol hydrat e and freeze pr ot ect ion. The con-
densed wat er and met hanol st reams decant ed in t he cold proc-
ess can be regener at ed by convent ional dist illat ion or by a
pat ent ed process called IFPEX-1

.
In t he lat t er pr ocess illust rat ed in schemat ic form in Fig.
20-75
48
a slip st ream of wat er sat ur at ed feed gas st r ips essen-
t ially all t he met hanol in t he cold decant ed met hanol wat er
st ream or iginat ing in t he cold pr ocess at feed gas condit ions
t o r ecirculat e t he met hanol t o t he cold pr ocess. The wat er
st ream leaving t he st ripper cont ains gener ally less t han 100
ppm wt of met hanol. No heat is requir ed for t he process and
no at mospher ic vent ing t akes place.
Dehydrat i on By Membrane Pe rme at i on
Membranes can be used t o separat e gas st ream component s
in nat ural gas such as wat er, CO
2
and hydrocarbons according t o
t heir permeabilit ies. Each gas component ent ering t he separator
has a charact erist ic permeat ion rat e t hat is a funct ion of it s abil-
it y to dissolve in and diffuse t hrough the membrane.
The dr iving for ce for separ at ion of a gas component in a
mixt ur e is t he differ ence bet ween it s part ial pr essure acr oss
t he membrane. As pressur ized feed gas flows int o t he met al
shell of t he separ at or, t he fast gas component , such as wat er
and CO
2
, permeat e t hr ough t he membr ane. This per meat e is
collect ed at a reduced pr essure, while t he non-permeat e
st ream, i.e., t he dry nat ur al gas, leaves t he separ at or at a
slight ly lower pressur e t han t he feed.
The amount of met hane and ot her nat ural gas component s
in t he per meat e st r eam is dependent on pressur e dr op and t he
sur face area of t he membr anes. However, 510% of t he feed
st ream is a r ealist ic figur e. Dehydr at ion by membrane per -
meat ion is t her efore normally only considered for plant s t hat
can make use of low pr essure nat ural gas fuel.

FIG. 20-75
Example IFPEX-1

Dehydration Process Flow Diagram

20-41
LIQUID DEHYDRATION
Many liquid st r eams must be dehydr a t ed t o a llow fur t her
pr ocessing or meet r equir ement s of a ha ndling cha in t o a
dir ect consumer. Commer cia l pr opa ne must be dr y befor e
ent er ing t he fuel mar ket t o pr event fr eezing pr oblems as
t he liquid vapor izes at t emper at ur es below t he hydr at e
point , or even below t he fr eezing point of a ny fr ee wat er t ha t
ma y be pr esent .
The amount of wat er t hat can be in solut ion wit h light hy-
drocar bon liquid is very small, even at t he sat urat ion point .
Effect ive dr ying t o ver y low levels of moist ur e is usually r e-
quir ed. The solubilit y of wat er in liquid hydr ocarbons is pr e-
sent ed in Fig. 20-2. The desir ed maximum moist ur e level for
commercial propane is appr oximat ely 10 ppmw. However, liq-
uids exposed t o cr yogenic t emper at ures r equire virt ually all
t he moist ure be removed.
The wat er cont ent in light hydr ocarbon liquids can be det er -
mined by using r ecommended met hods in GPA Publicat ion
2140 (Cobalt Bromide or Freeze Valve met hods), or elect ronic
inst r ument s designed t o indicat e t he moist ure cont ent di-
r ect ly.
Gas Stri ppi ng
One simple met hod of dehydrat ing liquid hydrocar bons is
count er curr ent st ripping wit h a dr y gas. This met hod is cur -
r ent ly used t o dry condensat e pr oduced offshor e prior t o expor t
from t he product ion plat for m. The cont act or is usually t r ayed.
St r ipping gas rat es depend on t he condensat e r at e, t he amount
of ent r ained wat er in t he condensat e, st r ipper t emper at ure
and pressur e.
Advant ages of t his process are simplicit y and low capit al
cost . Disadvant ages include t he requir ement for a dry nat ur al
gas st r eam, and t he coincident al st ripping of some of t he vola-
t ile hydr ocarbons from t he condensat e. The st r ipping gas may
be r ecycled t o t he gas dehydr at ion unit or it can be used as fuel
gas.
Soli d De si ccant Dehydrat ion
Several solid desiccant pr ocesses ar e available t o dry liquid
hydr ocarbons.
Liquid velocit y is usually 3-5 ft /minut e t hrough solid desic-
cant beds wit h a minimum t ravel of at least 5 feet t o ensure
good dist ribut ion. Dir ect ion of flow can be upflow or downflow
in t he adsor pt ion cycle.
Special car e must be t aken in designing t he bed support s in
t he liquid dehydr at or vessels t o prevent desiccant loss, desic-
cant damage, and t o ensure pr oper dist r ibut ion. Layers of ce-
r amic balls are inst alled in decr easing size fr om t he suppor t
screen. The suppor t ball sizes may vary wit h t he t ype and size
of solid desiccant used but t he layers of support balls should
never be gr aduat ed in size mor e t han t wice t he diamet er of
t he balls being support ed.
The r egenerat ion of solid desiccant beds is very similar t o
gas dehydrat or s wit h t he following except ions:
Liquid dr aining and filling t ime must be allowed.
Pr essuring and depr essuring must be done carefully t o
avoid bed movement .
Adequat e bed cooling is r equired before liquid re-ent ry
t o minimize flashing.
It is import ant t o pr event movement of t he bed part icles t o
prevent at t r it ion t hat would requir e pr emat ure r eplacement .
Also, desiccant dust par t icles can cause downst r eam plugging,
equipment damage, and excessive filt er maint enance. Liquid
and vapor velocit ies must be cont r olled carefully and flashing
of liquids or acceler at ed blow-down rat es t hat would lift or
float all or port ions of t he bed should be avoided.
Desiccant bed life can be ext ended by doing several or all of
t he following act ivit ies:
Pr event t he desiccant part icles fr om moving.
Keep cont aminant s out of t he dehydrat ing port ion of t he
bed by upst r eam condit ioning or by providing a sacr ifi-
cial layer of less expensive desiccant t o act as a cat cher
of any compounds such as amine, glycol or oil.
Pr event overheat ing t he bed t o reduce t he format ion of
car bon during t he r egenerat ion cycle.
Analyze t he heat ing/cooling regener at ion t emper at ure
cycles t o minimize t he t ime t he bed is at elevat ed t em-
per at ures. This will also minimize energy requir ement s.
A t ypical heat ing/cooling regener at ion t emperat ur e cycle
plot is shown in Fig. 20-72, wit h a descr ipt ion of t he st age
act ivit ies. There ar e t ypically four (4) dist inct st ages in a nor -
mal cycle:
St age 1Fir st bed-heat ing st age
St age 2Desor pt ion st age
St age 3Second bed-heat ing st age
St age 4Bed-cooling st age
For a per iod of t ime aft er t he heat sour ce is int roduced int o
a desiccant bed being dehydrat ed, t he bed must be heat ed t o
a t emper at ure wher e t he wat er will st art t o be desor bed (St age
1). As t he wat er is desor bed (St age 2), t he bed t emper at ure
will usually rise only a few degrees because t he regener at ion
gas heat is ut ilized t o provide t he heat of vapor izat ion of t he
wat er being removed. The complet ion of t he wat er desor pt ion
st age is charact erized by a r apid increase in bed t emper at ure
measured as t he out let t emperat ur e. At t his point t he heat ing
may be discont inued while bed heat ing will cont inue fr om r e-
sidual heat in t he heat ing cycle (St age 3). As t he unheat ed
r egenerat ion gas st ream cont inues t o pass t hr ough t he bed,
t he bed will be cooled (St age 4).
At near ambient pr essures, r egenerat ion of silica gel and
alumina can be accomplished at 300F. Molecular sieve r e-
quir es 500-550F t o maint ain t he low dewpoint pot ent ial, and
t he higher t emperat ur es may incr ease desiccant life by pr o-
viding mor e complet e removal of adsor bed hydr ocarbons.
Capacit y and per formance dat a for new solid desiccant s are
usually pr esent ed based on a st at ic t est . Under oper at ing con-
dit ions (dynamic) t he performance dat a may be significant ly
differ ent . Typically t he effect ive capacit y at operat ing condi-
t ions is about one-half of t he capacit y at equilibr ium (st at ic)
condit ions for most solid desiccant s. This operat ing charac-
t er ist ic must be considered when designing a dehydrat ion sys-
t em and can be influenced by car eful design and good cont r ol
of operat ing paramet er s such as t emperat ur es, cont aminant
levels, r egenerat ion cycles, and desiccant select ion. Solid des-
iccant manufact urers should be consult ed for t he most cur rent
product infor mat ion and design crit er ia.
Molecular Si eve
Molecular sieve is not nor mally used for liquid dehydr at ion
because t he r equired level of wat er r emoval is usually moder -
at e and t he cost of molecular sieve is consider ably more t han
ot her t ypes of suit able desiccant s, such as act ivat ed alumina.
20-42
However, in ext reme cases wher e t he moist ur e cont ent of t he
liquid must be kept at an unusually low concent rat ion, mo-
lecular sieve should be considered.
Molecular sieve may be used for removing ot her undesirable
compounds, such as H
2
S, COS, mer capt ans, et c., from liquid
st reams. Dehydr at ion may be a secondary benefit of using t his
t ype of t r eat ing met hod.
Refer t o t he discussion of molecular sieve for gas dehydr a-
t ion elsewher e in t his Sect ion for more informat ion.
Act ivate d Alumi na
Ther e are sever al t ypes of alumina available for use as a
solid desiccant . Alumina is widely used for drying liquid prod-
uct st reams following gas processing, t r eat ing, or fr act iona-
t ion. Most alumina desiccant s will produce a dewpoint below
100F if applied pr operly. Alumina t ends t o adsor b heavy hy-
drocar bons which ar e difficult t o r emove during r egenerat ion.
Alumina is alkaline and is subject t o react ion wit h miner al
acids which are found in some well t reat ing fluids.
The design of a solid desiccant liquid dehydrat ion syst em is
similar t o a gas dehydrat ion syst em. An effect ive desiccant
capacit y of 4-5% is t ypically used in liquid dehydrat or design.
Calcium Chloride
Calcium chlor ide is used as a consumable desiccant . Solid
calcium chloride combines wit h wat er t o for m a brine solut ion.
Fr om one t o t wo pounds of wat er can be absorbed by a pound
of calcium chlor ide. Large liquid CaCl
2
dehydr at ors are usu-
ally oper at ed in a series t hat can be reversed wit h a moist ure
monit or locat ed bet ween t he beds. In t hat way when t he lead
sacrificial bed is exhaust ed, no wet product is pr oduced. The
exhaust ed CaCl
2
bed is t hen r echarged and t he vessels r e-
versed in service.
The bed size can be est imat ed using a super ficial velocit y of
3-5 ft /min and an L/D of 2.5 t o 4:1.
Calcium chlor ide dehydrat ion has become less popular be-
cause of t he environment al problem of disposing of t he pr o-
duced br ine.
Di sti llati on
Wet NGLs can be dehydr at ed by dist illat ion in specially de-
signed fract ionat ion columns. It will gener ally suffice t o wit h-
draw a sidest ream liquid dist illat e t hree t o four fr act ionat ion
t rays below t he t op of t he dist illat ion column t o assure a dry
product . Wat er in t he NGL feed is passed overhead and is de-
cant ed in t he over head r eflux dr um while reflux is r et urned
t o t he t op of t he column. Some ext r a cost s will be requir ed for
t he sidest ream liquid wit hdrawal and cooling, but t his can st ill
be t he most cost -effect ive manner t o achieve t he dehydr at ion
of propane and/or but ane LPG product s t o adequat e dryness
specificat ions. The bot t oms product of t he dist illat ion should
be bone dry.
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20-43
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Suggeste d Reading
1. Gas Condit ioning Fact Book, The Dow Chemical Company, Mid-
land, Michigan (1957, 1962)
2. Campbell, J ohn M., Gas Condit ioning and Processing, Vols. I &
II, 6
th
Edit ion, 2nd print ing (1988), Campbell Pet roleum Ser ies
3. Kat z. D.L., Cor nell , D., Kobayashi, R., Poet t man, F.H., Vary, J .A.,
Elenbaas, J .R., and Weinaug, Handbook of Nat ur al Gas Engi-
neer ing, 1959, McGraw-Hill, NY, NY
4. Sloan , J r., E. Dendy, Clat hr at e Hydr at es of Nat ur al Gases,
1990, Mar cel Dekker, Inc., NY, NY.
5. Rojey, A. and J affr et , C., Nat ur al Gas Pr oduct ion Processing
Tr ansport . Edit ions Technip 1995.
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