Why not use

f i

Ga~Processing evelopments D
o

, i

methanol for hydrate control?

Methanol systems can save money for installation and operation in turboexpander plants and be easier to operate besides
R. B. Nielsen and R.W.Bucklin, Fluor Engineersand Constructors, Inc., Irvine. Calif.
HYDRATEFOR~(ATION turboexpander in plants can be avoided more cheaply by using methanol than by using solid bed dehydration. Although the first turboexpander plant used methanol,I.2 most expander installations since then have used solid bed dehydration. The reasons are obscure. since methanol often grants greater ease of operation as well as lower capital and operating costs, especially when the water in the feed gas is low or when recompression is required. Natural gas generally contains water before processing. High pressure. low temperature. or both favor the combination of water with light gases (C I to G, paraffins and ole fins. carbon dioxide. and hydrogen sulfide) to form hydrates. Free water must always be present for hydrates to form. Hydrates (solid crystals resembling wet snow) cause problems by plugging pipelines. valves. and other process equipment. Therefore. proper equipment design requires accurate prediction of the limiting conditions at which hydrates are .formed anytime a gas stream containing hydrate formers and free water is cooled below 80F. HYDRATE DEPRESSION P t-:'

-25

-so

-75

(DJ , ,
;

-100

j .

,
!

Should bottom out at 0.835

-125 o .1 .2 .3 .4 ~moI% .5 .6 .7 .8 .9

Fig. 1-Water-methanol
1,000 900 800 700

system phase diagram.

600

I I

-.;
c(

lIS

(C)

500

II) III) lIS.

! :J

ci:

400

-.

,~n
11-

0It(, IrI";

Ieh,

"r I'i~.

Primary or polyfunctional alcohols, e.g.. methanol or glycols, are well known antifreeze agents used to depress the freezing point of water. Alcohols also depress the formation temperature of hydrates in a gas. Unfortunately. there is a tendency to confuse the two. Consider the phase diagram for water-methanol (Fig. 1).:' Ifa 25 wt% aqueous methanol solution (about 16 mole percent) is cooled without any hydrate-forming gases present, ice forms at - 20C (- 4F). Since pure water freezes at .32F. methanol depresses the ice point 32F - (- 4F). or 36F. while - 4F is defined as the depressed ice point. Consider the same 25 wt% methanol solution in contact with a typical natural gas at 1.000 psia. According to experiments. Ithis gas forms a h)'drate at 63F when in contact with pure water. In another experiment. the same gas at 1.000 psia formed a hydrate at 39F when in contact with a 25. wt% aqueous methanol solution..
...

300

200 10

20

30 40 so 60 Gas hydrare Oecompositiontemperature. OF

Fig. 2-Hydrate schmidt's data.

depression

of methanol solutions-Hammer-

The normal hydrate point is thus defined to be 63F while the depressed hydrate point is 39F and the hydrate depression is 63F (39F), or 24F. Fig. 2 summarizes this experimental data.

Hydrocarbon Processing. April1983

71

1.000 800 600

Hydrocarbon liquid iI~ ilquoou1 liquid ~'" .... ..J Upper quadruple-

L,

= \Vater-rich liquid phase L2 = Hydrocarbon-richliquidphase

400 300 Q. 200 c(

III "jij

Hydrate and aqueous solid

Hydrate and aqueous liquid

I Ii:

/I)

If a small amount of solute. such as methanol, is added to the water-rich phase, the line SL,G. the waterice-hydrocarbon ,'apor locus, is displaced a distance AT and the line L,HG. the water-hydrate-gas locus. is displaced a distance ~T', (Fig. 4). An inspection of Fig. 4 shows that ..\T', the hydrate depression, is less than 4T, the ice point depression. In fact, using Fig. 4 and the Clausius-Clapeyron equation it can be shown that the relationship between ~T, the freezing point depression of the water-ice line and:the depression of the water-hydrate line. ~T', is about: 4TI ==~T 4T
4TI 4H
~H 2

= To-T

(1- ~H2
~H1

(O
.

= To- TI = the heat transition S + G +::tH 1 = the heat of fusion for L, + G +::tH
=

10

20

30

40

50

60

Fig. 3-Water-ethane

Temperature, ~ systems phase diagram.

1,000 800 600

TI T To

=
=

hydrate-forming temperature ice-forming temperature normal quadruple point

I Hydrate
and aqueous solid

Upper Quadruple

'"

As 4H2 is less than ~H.. the hydrate depression of a given solution is always less than the ice point depression. There is a relationship between hydrate and ice formation, butfreezing CUT1'~S suchasFig. 1 can1lotbe used for desigu without S071le odification. m The Hammerschmidt equation. In the 1930s Hammerschmidt presented a semi-empirical equation for predicting hydrate depression of typical natural gases in contact with dilute aqueous solutions of antifreeze ~gents such as methanol or any glycol..' The equation
IS:

4001300"

:
III
ti
(I) GI

2001

I aqueous Hydrate

liquid and

(I)

Ii: 100 80

~T Gas and
aqueous liquid

100M - J\1"'

2.335""

where: M = the molecular weight of the antifreeze agent, e.g., methanol "' = the weight percent of the antifreeze agent in the solution 4T

,
(JSO \:
10 20 30 Temperature. 40 of

Withmethanol

= the

50

60

hydrate depression or the difference between the normal and depressed hydrate point in OF

Fig.4-Effect of methanoladditionof water-ethanesystem. !':ormal and depressed hydrate points (Fig. 2) are pressure dependent. but the difference between these two temperatures (hydrate depression) is pressure independent. Also, hydrate depression of a 25 wt% methanol solution, 24F, is less than ice point depression. which is 36F. hz general, the h.',d,'atedepressioniJ alwa)'.1i than the ice point ckpression. less A phase diagram illustrates this point. For example, if the hydrate locus for a typical natural gas ploued on a line P versus T diagram results in a phase diagram similar to that for the ethane-water system5 (Fig. 3), where: S = Ice phase H= Hydra.re phase G Hydrocarbon ,'apor phase
72 Hydrocarbon Processing, April1983

This equation originates in the relationship for the fl"eezing point depression of an ideal solution.6 ~T ==RT; In 1+ X ~H S) ( ,,'here: ~T
To

= the
=

freezing point depression

freezing point (absolute tempera-

the normal t u re )

~H N S R

= moles of solute (antifreeze = moles of solvent = the gas constant

the enthalpy of fusion per mole of solvent agent)

If the solution is dilute. N, is smaJlerthan S and the logarithm can be expanded in terms of J~'/S.
j 'b q

--

.:.f.,'.j..~.;.,~.:.~;,~",~:_,."~,,..'..?\':.'~~iml~1t%IJI~~~:~&~ti~~~t~~Ii~,~.I~(f~~~~f~ir~~m~Jf8l~1~!UI;I_t:4~~"~'.".;.~..~"*~...,,,~':.~;.: .,. .
: !.8 ,.

Gas-gas exchanger

Melhanc)l. hydrocarbon separator

Methanol storage

Waterwash tower

Methanol in;ection pump

Washed propane

HC gas

Propane

product

from depropanizer
Feed gas

Dissolved gas

He liquid to waterwash tower or

fractionation

Ventgas

o (
rI
I I

Methanol still
Reflux pump

I I I I 1
L

I J

----Free water knockout Flash drum

Filter

Excess water

:\

[~

FIg. 5- Typicalmell1ano1lnjedionandrecovery system,

:e .e

In

( +S )
I

.N

N =

I N

S - 2"S +"3s

( ) ( ) -. ....

I N

or

~T in of =

2,335W IOOM-MWI

For very dilute

solutions where N is very small, all pow-

ers of N IS above the first can be neglected and: N and ~T ==Rrl tJI ( S ) ' N = W.A1) S 100M-MW

The Hammerschmidt equation applies only to l)'Pit:al natural gases and to solute concentrationslessthan 0.20 mole fraction. Glycol injection systems operating down to

10F fall within these limitations.

a-

\Vhere 1\1.1 the molecular weight of the solvent and is the other variables are defined as before. Therefore: W ~T - MIR~ ~H ( IOOM-MW ) Using a typical natural gas and various dilute solutions, Hammerschmidt fitted this equation "to hydrate depression and solution concentration data to obtain:

Suprisingly, operating data show that the Hammerschmidt equation can be used to design glycol injection systems <:>perating at temperatures as low as - 40F or - 50F requiring about 0.4 mole fraction ethylene glyco1.5 The success of the equation at these conditions seems to be due to a number of compensating factors; of which the most important has to be the strong negative deviations from Raoult's law that water exhibits in glycol solutions. Equation for concentrated methanol. Since the Hammerschmidt equation can be expressed as: AT = - R~ In Xw;ucr AH
Hydrocarbon Processing, April 1983 73

he

M1RT~

~H

= 2335
'

-'......
Gas-gas exchanger Chiller

,f1{r

TABLE 1
Primary separator 172,580 H.C. gas .moIe/hr

Ij<

x..... Mole Fraction 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.8358

MeoH, M% 0.0 16.5 30.8 43.2 54.2 64.0 72.7 80.6 87.7 90.0.

AT,-c 0.0 7.6 16.1 25.7 36.8 49.9 66.0 86.7 115.9 129.r

T"F 0.0 13.7 28.9 46.2 66.2 89.8 118.8 156.0 208.6 233.58

Feed

1.BOO MMsdd 620 psia Methanol 9Owt% MeOH

Fig. 6-Sample calculations schematic. (7ZC)

. Hydrate locus based on gas leving primary separator . Primary separator . Final separator

. AAxoximalely 0.835 mole fraction

mechanOI or 90 WI % methanOl gives the maximum hydra1e depressiOn available since U)II.o..ilUations greater than this form solid methanol (See Figs. 1 and 7).

-25

(p

'.-......

..,:
-75

ICE
( - 73.3OC, 0.835)

tion is set at 90 wt%. The maximum hydrate depression recommended for design is the calculated depressed hydrate pointS plus 35F. Methanol injection control for expander outlet temperatures below 102C must be more accurate in order to keep the aqueous methanol concentration above the freezing line in the eutectic range. The recommended 35F safety margin for the maximum hydrate depression keeps the designer out of trouble in almost all situations. Operating temperatures colder than - 160F are possible, but the safety margin of 35F is often no longer a,'ailable, and the modified Hammerschmidt equation is no longer appropriate. A more exact form of the freezing point depression equation should be used.7 T I1H T 6.Cp ACp To

In('YX)=--1 RT ( To

+-

--1 T

+-In R

To

-100

TYPICAL METHANOL INJECTION SYSTEM In a typical methanol injection and recovery system (Fig. 5) for a cold oil absorption or tUrboexpander plant, feed gas passes through a free-water knockout drum and into a gas-gas exchanger with provisions for spraying methanol on the exchanger tubesheets. Methanol inhibitS hydrate formation as an aqueous methanol solution condenses in the exchanger and chiller. Methanol water solution is removed from the separator and sent to the methanol still for methanol recovery. A significant amount of methanol dissolves in the hydrocarbon liquid and a ppears in the propane product if the hydrocarbon liquid is fractionated. To recover dissolved methanol, water from the methanol still bottoms is used to wash either propane product or raw hydrocarbon liquid from the demethanizer. If raw liquid is recovered and fractionated at the same location, it is usually more economical to wash the propane. SAMPLE CALCULATION. The following discussion outlines the basic steps required to design a methanol hydrate control system in a turboexpander plant. Preliminary data. The methanol hydrate control system should be designed last.. The complete plant process should be set and minim u-m temperatures, liquid condensation rates, and gas and liquid compositions calculated. Then the amount of methanol and itS required concentration can be estimated.
~~

-'25

.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

XMeOH.mol %

Fig. 7-Hydrate depression-sample calculation.

so In (1+ ~)
A ~ No\\'

= -1n X.
T = - 2,335 I X M I n ~'ater

(I"Derefore, using earlier results:

MI

18.02 and Xwater= 1- XMeOH

Therefore: AT = -129.6 In (I-XMeOH), wherein I1T is in of is a form of the Hammerschmidt equation more appropriate for concentrated methanol solutions. Although this equation is an approximation, experience has shown that it can be used for design of methanol hydrate control systems operating as, low as - 160F. Hydrate depression. AT, obtained from the modified Hammerschmidt equation is shown in Table 1 as a function of methanol concentrations. This table can be used to set methanol concentration for hydrate control. In mo~t cases methanol concentra74 Hydrocarbon Processing, April1983

'f

100

..
MeOH c, ...
over 50 =naI %

1.8

...... ; .. 1

10

~~.
4
'0 E
2

t ;

.1

:I 1.0 at

g ~
o.~

i
CD

~ :a

6 4 2

1ii 0 en

:3

~ >

~ {1 ~ ~j .
0 .$

~ ~<i ~ 0 ~

-g 0.1 :3 i.

(0
1

Experimentaldata . Methanolin hydrocarbons Petrocanada I MethanoI-ethanebinary a Methanolin hydrOC8lbons I I I I

-120 -100

,
t

" Methanolnhydrocarbons oastal2117 ,,.. i C

"

/~II IJ

~$
I~'"

-#

tI

. Methanol inhydrocarbons Coastal8164 J I I . Waterin hydrocarbons Coastal2117 I g. I

.01

(!J I

I II
0

-80 -60 -40 -20 Temperature. ~

2D

60

100

J. P. Kahn, J. Cha. Eng data 9. no 1, pg 3 1967 B.Y.U. data

Fig. 9-Solubility of methanol in liquidhydrocarbons.

,001 -160-140-120-100 -80 -60 -40 -20 Temperature.OF 0 20 40 60
Gas analysis 93-9S mole % C, 5~%Ct 0-2 :note % C02 Standard conditions

Fig. 8-Water content of natural gas from60 to -160F (extrapolation of data in ref. 16).

, (-) \

)d
IS

:-

Consider a gas feed to an expander plant at 1.800 \.L\lscfd. The gas contains 2.25 Ib water/M~lscf. Other conditions are as shown in Fig. 6. Only the front end of the plant is shown here (Fig. 7) since downstream calculations are identical in priniciple to those required for the front end. The first step in determining the required methanol concentration leaving the primary separator is to calculate the hydrate point of the gas leaving the primary separator. With the gas composition leaving the separator and its pressure, either the Parrish-Prausnitz,8 the Katz,9.IOor the Peng-Robinson II methods can be used to calculate the hydrate point. In the case of the gas leaving the primary separator, the ParrishPrausnitz method gave a hydrate point of 45F or 7.2C. Next, the modified Hammerschmidt equation can be used to plot the depressed hydrate locus for various methanol concentrations (Fig. 7). Then set the required methanol concentration. In almost all instances, the methanol solution concentra:ion leaving the primary separator is set at 90 wt% or 0.835 mole fl&lction methanol because this concentration gives the greatest hydrate depression. For this example. set the methanol concentration at 90 wt% and plot conditions for the primary separator ( 100F or -73.3C and 0.835 mole fral:tion methanol). Note that this allows a s~lfety margin of about 39C or 70F in the primary separator (Fig. 7). As a check, conditions in the separator after the tur-

sc-F. 1 atm 0-2% ~ inoffgas

.. 10020

30 40

60 80

150

250

400

600

1,000

2.000

( I/Mole fractionMeOHin aqueous ~.jb MeOH~Mscf Fig. 1G-Methanol content of natural gas from 65 to - 2O'"F.

boexpander should be ploued on the same diagram. Here the separator is at 126F or - 87.~ and 410 psia. This provides (Fig. 7) a safety margin of at least 24C or 44F in this separator. Since 90 Wt% methanol has adequate safety margins in both separators, fix the primary separator methanol outlet concentration at 90 wt%.

Methanol injection rate. The rate of methanol injection depends on the amount of free water condensed from the natural gas after chilling. methanol solubility in the vapor phase, and amount of methanol which dissolves in the liquid hydrocarbon phase. The difference between the water content of the feed gas and the water content of the gas in the methaHydrocarbon Processing, Aprif 1983 75

----

..
2.500

. 4t

'4
'.. ,!

Gas analysis 93-95 mole % C,

J:{. 1'.

5 mole 0.. c2
0-2 mole0,. C02 Standard conditions 6O"F. 1 atm. ~2%
CIS

C02 in off gas

.it

! :J

= CD
2S.

600

u CIS 400

100

0.10 0.15 0.20

0.30 0.40

0.60 0.80 1 1.50 2 2.50 3 4 I:i 6 7 8 10 15 ( I/ Mole fraction MeOH in aqueous pha~~ft) MeOHloss I M MS C.F

20 25 30

40 50 60 7080

Fin-MethanOl

contentof naturalgas from 20 to -120F. represents the amount of BYU laboratory data. A conservative decision is to use the BYU data with a 20% safety margin or 0.24 moles

(I:h;'drocarbon separator free water condensed.

Assumethat 98 wt% methanol is injected into the gas

stream to control hydrate formation. This corresponds to a methanol purity easily obtained in a methanol generation still. Calculate the amount of methanol requi red, as follows: . Determine the amount of condensed water: Inlet water content

methanol/IOO moles hydrocarbon.

Outlet water content

= 2.25 Ib/MMscf = 0.012 Ib/MMscf

Next, determine methanol solubility in the hydrocarbon vapor phase (Figs. 10-12) at - 100F, 605 psia (Fig. 11). The value is: (0.83 Ib methanollMMscf)/mole fraction aqueous methanol Finally, using data from Table I, 90 wt% aqueous methanol = 0.835 mole fraction. Methanol in hydrocarbon vapor 98 wt% methanol In Methanol dissolved in liquid hydrocarbons 90 wt % methanol to still

The outlet water concentration is determined using the water content of natural gas at low temperatures (Fig. 8). Therefore, the amount of water condensed is:

2.25

lb MMscf

x 1.800

MMscf day

x --!-

I dav

168.8-

Ib hr

24 hrs

Qet the outlet concentration of the aqueous methasolution at 90 wt% methanol. Do a mass balance a-avund the separator. From data on the solubility of methanol in hydrocarbons (Fig. 9), there are 0.105 moles methanol dissolved in every 100 moles of hydrocarbon using extrapolated plant data or approximately 0.2 moles methanol/} 00 moles hydrocarbon using
2.000 1.500
Gas analysis

M Methanol in hydrocarbon "apor (standard conditions 60F, 14.696 psia) , .

Methanol in 0.835(0.83) 172,580(379.3) 106 Methanol in liquid hydrocarbon
1.2(0.20)25,160(32)

= 0.98

95 mole 0,0C,
5mo1e%~ Standard conditions 6O"F. 1 atm. 0-2% C02 in off gas

_ 4" lb MeOH - ~ hr phase:

100

1 932 lb MeOH

'hr

i c:
100 . 0.015 0.025 0.004 0.007 0.0150.025 0.005 0.1 0.15 ( \ Mole fraction MeOH in aQueous phase).1b MeOHIoss/MMsc.f

Methanol in aqueous methanol (0.9)(168.8)

0.10

phase:

1 ~20 lb MeOH
,~

Input

= Output:

Fig. 12-Methanol

content of natural gas trum

- 125 to - 1 75F.

0.98 M

= 45+

1,932+ 1,520

76

Hydrocarbon Processing, April1983

,/'1'-; ..,,{~;~~ '~:~;~~;~A;~:~:.:"t~i~%;J'i?q~~~1:.W\~j..j;:~,fb'~l1~~"t?~~\i,;,;".9iftf~;f.b,;~.yit:~~r;.:,~t1~~.. t~~;:;'~~:',;;~.kf~t~~.;.;#~~.&:.: ;;;~~\;~A;~;~.~~;\;>Jj):;~;..:i}S..' ..~? ,>,c0. . ~J6'::~'''."'';' :~~, ":'''';';<:~.t"~,. '2~;;K,.;,;fI~; "..'i-.~' ,;w.",; ,~,,,,:, '.' ;.. ~ ~ - -:\~..~{t:i{<.~,~. '.~, ".y- "":~ 'J. . ..~&t".i~i~f~':.,.<.;':~~~r ~.1$~.. ~",""..'...":t~: ,..". ~.,. ; ~..~:: '...'m .+.fr; :.~. ,.:;,f~~,.,;7'.7:~1!:," .'- ~):r:'~'..J ,~i<';";; .~~.<~:';.'; .",",'Xf.:: .. ~,,,;.!~~.:':!~~, .~z;;Wl~~:,..;, Tj:&Ji'@-:';.~;' ,~~\-:Ji_I,,...,.,,..~r,;V),";},.~~.~~t;~y;~-'~~,r , .~~U:<\~'''?f~:~ _ ..:'.!::{'.':~I':::"':~~:;&i,f~:{';\~;:r:.$; ~
~,~

---

30:

!!!!

3,570 ~: of 98 wt% ~(eOH

..
\

.
..

.. ..

(. ( a .

Therefore, the methanol injection rate is 3,570 Iblhr of 98 wt% methanol. Using Fig. 13, this equates to 9.2 gal. Ions per minute at 100F. Mode of injection. Methanol has a much higher vapor pressure than the glycols. Therefore, methanol should be injected upstream of the front end exchangers where it will be distributed and vaporized by the gas. 12 The superior distribution tendencies of methanol are important in both plant economics and performance. Spray nozzles should also be provided to spray meth. anol directlv onto the tubesheetS. These nozzles can be used during normal operation to add methanol beyond that required to saturate the gas phase, as a backup system, and to flood the exchanger with methanol if hydrates form. :Methanol injection points should also be located at the inlet of a turboexpander and at any refrigerated condensers in downstream fractionation. Removal points. Normally an aqueous phase will not be present in the liquid to a fractionator reboiler. However, deethanizers have experienced periodic upsets where the column discontinues good fractionation. 1 This phenomena is due to the accumulation of a separate methanol liquid phase in t.he fluid feeding the bottOm reboiler. Provisions to remove this phase eliminate this problem. Under certain conditions it may be possible to concentrate an aqueous methanol phase at various points in downstream fractionation. Provisions to remove the aqueous phase should be made at all locations with this potential. Part of the methanol injected into the gas stream will
1.00 0.98
Freezing point locus

Dataof NOOA.t

aI.J. ofa.n

Eng.of Japan:8, no 6. 492-3,1975

Calculated from data of NOOA

o ~

10

se

!
'I
J

es ria

t i 1 ; t

,
1

i , LJS

dissolve in the liquid hydrocarbon phase. To recover the dissolved methanol, it is necessary to wash the raw liquid or propane product with water. The water wash tower operates as a liquid extraction. tower. Water from the methanol still bottoms is used to extract the methanol. Water washing typically recovers over 90 percent of the dissolved methanol. Although partition coefficient data published by Herrin and Armstrongl are of the right order of magnitude, other data indicate the possibility of significant .. experimental error. Fig. 14, based on the work of Noda.13 contains partition coefficient data recommended for design.
5% 10

..................

--,

os

................................ .....................

...............

"
.

'""'.........

:Ii-

'""",

........
..............--.........

0.84 0.82
0.80 0.78

lange's handout 01chemlslry. 111h edition. 1973 Calculated pI. based on excess votume data. Thermodynamics Research lab. Washington University. 1973 . Calculated freezing pI. at various temp. and wi "'0 based on lange's graph and pure methanol and water density _ _Extended curve . Pure melhanol o Given freezing pI. by lange's graph -60 -40 -20

. .

Density vs temperature at various wt "10 methanol

0.76

20 Temperature.OF

40

60

80

100

Fig. 14-Plot

of density versus temperature for various aqueous methanol solutions.

j
q

~. tL!!

Hydrocarbon ProcessIng, April 1983

77

" ,
,,_, ,.
~,

-. .

I' ~

~
gas with'a

TABLE2-Comparatlve equipment list, methanol Injectionversus solid bed dehydration

De8crlpt1on
Y8ss8I8
Stilt Renux Drum

H"mbtr Meth8no8 Sotld Bed Required Requfr8d Dehydr8tlon

Inside Diameter )( X.T.T.

pounds is saturated feed gas at 55F. Each system"'Was designed to dehydrate 2.0 billion scfd of feed gas to 150F water dew point. Size sensitivity for the four pound gaswascheckedat 1.2 billion sefd of feed gas. Conclusions of the study are:

MeIIanoIStII MdIanoI Flash Drum W8I8r Watt Tower [)epropanizerFeed Drum Feed Ga Dehydrator Regenet8tionGas K.O. Drum Primaryliquid Separator Meth8noI torIge Tank S
Propane Dehydrators

1 1 1 1 1 6 1 1

30")( IV 42")(38'cr 3O"x IV 6I1'xscrcr 12fr_4OV

1scr 10'0" x
J'O" x 10'0"

Bur8neDeh)ocIraun EJId\8ngII8 DeeChanIz8r BonomaCooler M8thMoIStiI RefluxCondenser

MeCh8noI SIll R8tIOIIr

2 2 1 1

'68")( 48'cr 200 bbI 42")(14'cr 3trx ,4'cr

120' )(30'0"

,
1 1 1 1 1 1 1 1 1 1 0.1 0.8 0.4 0.4 0.1 0.3 0.3 0.2 0.2

MUBtuIhr 9.8 7.2

8.3

Wash Wat.- Trim Cooler

Watt TowerBoaoma Exchanger ColdMeth8noIHeater MeIh8noI ooler C MeII8naIStiI TrimCooler. VentVapor Regetl8latiol.Gas Heatef. Propane Dehydrator Regetl8f8tionGa Cooler. Propane Defir8tOr Rege8l8r8tio1t Hea1er.Butane Dehydrator Gas Reg8nerationGa Cooler, Butane Dehydrator
...

GasDehydrator ('jegetl8f8tion Gas. 1 Gas Heater. Gas Dehydrator <..:. Gas mCooler, Dehydrator T Gas
Reg8nerationGa Booster CoqIres$or, Gas D8hydndor Ethane RefrigerantCompressoriTurbine Prop8neRefrigeranICompressoriTurbine TUIboexpander Pun.- 8nd drivers MethanolSIll Reflux Wash WIler Cin:ufating
MeIh8noIInjec:tion

13.0 11.7

3.7

bt1>
1.340 15,750 10.100 2CVIO 4513 10r5 242 2,120 17,040 9.240

1
1 1 2 3 2 2

low water content (4 pounds H20/MMscf) ..equires lower capital and operating costs than an activated alumina dehydration unit. The conclusion remtins the same for processing 2 billion or 1.2 billion scfd of gas. . Processing gas with a high water content (23 pounds H20/MMscf) results in a lower Gipital cost for a methanol system than a molecular sieve dehydration unit, while the operating costs for the units are about the same. Table 2 shows the items affected and their relative sizes and requirement. The capital cost equivalents are for major equipment items which are either different, or required in one system but not the other. Cost equivalents are related to the 2.0 bscfd methanol system costs at 100 percent. The potential advantages inherent with proper use of methanol for hydrate control have not been fully appreciated by the gas processing industry. Experience indicates that plant overall performance will be better when hydrate control is managed by n1ethanol rather than by solid bed dehydration. This overall performance advantage can be realized along with lower capital and operating costs in many instances.
LITEJlA.TURE CITED I Herrin. J. I'.. ,md ArmstntnK. R. A.. MMethallullnp;iulI a'HI Rn:>".CT}'it! ;aTumnnl);!ndel" l'blll.- prnmtcd ..t (~s Cunditioninl( CCH,rc:n:na:. Sum Okla_ 1!'72. ::!Herrin.]. p..4'Gm Rec:u\-er5 85 Pcn:cm or "rnpane'- Oil.. (.. j..."",,-Junc 2f1. HI66. IJP. 181-ltI6. 3 ~Iilla- ",HI ("';''lJentcr.jOll,-mt1 II{(;4,.ir,,1 EHKi",.nlft /J",.. '."L 9. So. ,. P. :\71. mew. I Hammcnc:hmidt. E. (i.. MG;as Hydr.lte Funl1atium.- C;.4.'i.~I;a. 19:t9. p. 30. :. Re-"IIIn'. H. II.. Selleck. .'. and SaKe. B. H.. "Sullie I'rnpcnic-o "'- :\Iixc:d hr..llinic iI'KI Olefinic I.hdrolln." Petroleum Transactions. Vol. 195 p, 197. I~~. Adarn. N. K.. I'''.t.,irnl CA'.i."ry. Oxfurd l.:lIi..~nit~ Press. HI;;6. p. 21401. 7 Itr..usniu. J. ~I.. ,\1'''""0'. Th,n ".Tlln""r..lit FluiJ PM." "",1"-",... I'I~ lIilli. 1~169. pp. 31U'-j~1\. ~ I rrish. w. R.. I'rausniu. J :\1.. "J)issul"iiltiull I'~surn fIr (~ 1I"lr"l~ Funllc..d b\ (;ilS ~ixlurn.- 1...1"",-",1,..,,, ",m",.j"IC ehI'HI,."" p"",,-, 0,,,,:" I>r."I"p_III \\,1. II. p. :!fl. 1972. . 9 Tl'rh"'rnl1>tt'tt B,,,J.-P,,,,,II'''''' R"millf{. Ameri&...n l'1:trulC'ulII In!olillUe. ~"' YurL. Hl6Ci. IIIC;PSA 11,,,,",j,,/: Da'tt B,,,". r,OI' I'rtlcnson As"uc.i.uilln. Tul"" Ok I!r.'~. II I~n,.;. D. Y.,md Rnhinson. D. B.. -A :'IOe'"T,,~...c::ulI!tlillllfAflulinll nf ~"IC:.- 10Hi.11', (;I"... F.w"ttHlI'II'ttl...Vol. 15. p. 59. 1976. I: Nelson. K.. "Melhanollnjcaion CUtSCosts:' IlTd",r"rbr", p"" "',,~. Seplc:TI1hn"1~li:\. I' ~.Kb." ,,1. -rern;a~ Liquid-Liquid Equilibri.. ru,. S~SIellls..1 .-\quc:ulh :\Inhalllli S"lulions and l'rop;Ane or n-Bulane.- JUlln/ul 0( (;J".ir#ll E"f{'H"".~ .r{In,... \Col. II. ~u. 6. H175. p. ..~...? II Dc''K. E.. rt nl. -U:llnCllnic E...luatiun uf MClhal1"llnja1iulI 'C1"\USSo 1k'C1J)eh~"(lr..tN", S"'IClI\S'- itn unpublishM September. 19i7 .'IM,r in-h"u'C.' SlIICh. \.\ :\1iiia-' alld C;''lJC:lller, C:.II{C1r,.. E"K. Dalil. ",,1. 9. :'IOu. . p. 'i I. J!16-I. 3 Iii Koltz." ul. I-Iandhouk or X..lur..1 G;as En..rjll~rinx. 193C1.p. 196. .

A methanol

injection

system

processing

TABLE 3-Cost equivalent summary

Methanol Alumina
Capital cost Equivalent 2.0 bscfd 4 Ib HIMMscf 23 Ib H20IMMscf 1.2 bscfd

Molecular sieve

100 123

134

146

4 Ib HIMMscf
cost equivalent

71

93
193 208 124

\ ).18rating
C)2.0

bscfd 4IbHIMMscf 23 Ib HIMMscf 1.2 bscfd 4 Ib HIMMscf

100 193 67

The authors
RICHARD NIELSEN a principal process engiB. is neer with Fluor Engineers and Constructors. He holds fj as degree from MIT, a MS from USC and an MBA from UC. Irvine. His experience with Fluor includes LNG receiving and liquefaction terminals,gas processing, refinery design and synfuels. Presently. he is in South Africa working on the Sasol Two and Three coal gasification plants in Secunda.

Water flow rates through these towers are usually much lower than hydrocarbon flow rates. This results in a high methanoi concentration, typicaIly up to 30 wt%, in the tower effluent and reduces the load on the methanol still reboiler. In general, the hydrocarbonwater volumetric ratio should not be greater than 40: 1 as the methanol recovery decreases with higher ratios. COMPARISON WITH SOLID BED DEHYDRATION A capital and operating cost comparison of methanol versus solid bed dehydration was made for the 600 psig sample calculation gas. 14 Two inlet feed gas water levels were examined. 4 and 23 pounds per million standard cubic feet. Four pounds is the pipeline design water content as opposed to the 2.25 pounds usually experienced. Twenty-three
78 Hydrocarbon Processing. April1983

ence in gas processing with Fluor.He

played a key role

ROBERT.v. BUCIWNhas over 30 years' experihas

in conceptual process developments in NGL recovery by means of both cold-oil absorption and turboexpanders. Hy.. drate control with either ethylene glycol and
concur-

methanol injection were pioneered rently with these developments.

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