··- ___. .

1U G<u Production Engineering

~ W. R. and Prausnitz, J. M., 1972. "Disspciation Pressures of Gas

· ·. Hydrates Formed by Gas Mixtures," Ind. & Eng. Chern ., Proc= Di.sign
. IT D'eQ•• 11(1), 28-35. · . .
Nr.lleWn Extension Servict., 1972. field Handling of Natural Gas. 3rd.ed., •
~ Ualv. o£ Thus ·Press; Austin, Texas; 143pp.
1\0bm:son, D. B. md Ng, H. J., 1975. "Iniprove Hydrate Predictions," Hy-
. dloc. Proc;, 54(12, Dec.), 95-96.
Bobfnson,J. N., .Wichert, E ., Moore, R. G., and Heidemann, R. A., 1978.
· . ..Charts Help Estiinate H 20 Content of Sour Gases," 0. & Gas]., 76(6,
Desulfurization ·Processes
Eeb. 6), 76-78. '
~ S. and Campbell, J. M., 1984. Unpublished. Cited reference on p.
:143 in: .Gas Conditioning· and Processing, Vol. 1, by J. M. Campbell.
... Campbell Petroleum Series, Norman, Oklahoma, 326pp .
·Simpson, E: A. and Cummings, W. P., 19()1. "A Practical Way to Predict Introduction
~i!ica Gel Performance," Chern. Engr. l'rog., 60 (4., Apr.), 57-60.
Slvalls. C. R., 1976. "Glycol·Dehydrator Design Manual," Proc. Gas Con-
ditionmg-Com:;·uruv. of Oklahoma, 39pp. With increasing demands for natural gas, natural gases·containing hydro-
~ R. E . and Campbell, J. M., 1966. "Prediction of the B.ehavior of .gen ·su!fld.e (ti,S) are also being tapped for utilization after purification.
H)dtocarbon Clathrate Solutions," Proc. 15lst Meet. of Am. Chern. Soc., Natural ;;ases containing H 2S are classified as "sour;" ~d those th,at are
Petr. Chern. Div., Pittsburg, Penn., March 23-26, p . 61. are called "sw·eet" in processing practice. ·Produced gases £tom res"
Vander Waals, J. H~ and Platteeuw, J. C., 1959. "Clathrate Solutions," Ad- moil's u ;uali y contain HaS in· c:oncentrations ranging from barely detect-
oailref in Chemical. Physics, Vol. 2, edited· by I. Prigogine. Interscience ·. able quantities to more than 0.30% (3,000 ppm). Other sulfur derivatives',
Publ., a division of John Wiley & Sons, New York, 1 -57. besides l12S, are usually completely insignificant or present only in traqe
)?T(lporti•Jns. 'Most contracts for the sale·of natUral gas ·reqtiire ~ ·than 4
(parts per miEion) in the gas. Thus, a sulfur reinoval'process must'be
predse since t..'r)e initial product contains only a small fractional quan-
of stJfur that must be reduced several hundred tinie$.
:';·A cha;·acteristlc feature of all H 2S -bearing no.tural g&Se$ is -the pPe.tenoO cl
carbon d10xide (C02), the ccr.centr&tions of which ·are generally in the
range of 1 to 4.% . In gases devoid of H 11S, however, :;uch concentrations are
· rare. H2·) and C0 2 are commorly referred to as_.wacid.iases" because they
...
. form
~- ,_
acids or aciciic solutions in the presence of. water.
,.
~·. .. ..

.Reasons for Removal of H 2S and C0 2

. Besides Emitting a foul odor at low concentrations, HIS is deadly poison-

'~ us :and at <:·.mcentrations abcve 600 ppm it can be fatal in just t:hreE: to five
·,minutes. Its toxicity is comparabl.; to cyanide. Thus'\ it cannot be tol~ated
· i11,_gas :t.a~ would be used as domestic fuel . Further, H 1S is corrosive. to all
·. fr:etals r:ormally associated with gas transporting, processllig; . ~)andling
systems (although it is less corrosive to. ~tainless steel), and. may lead to pre-
.in~·t ure I ailure.of most such syste;ns. On ..:-ombustion,
' . .
it forms sulfur
. -..-.
ciioxide,

255

·:-:: , ... J . .- · ·-· · "-'~~

 e=::::r.:: -. r=---- ,.,..........r;=
-.. --
-~ . ......_,. .

__JL II !l _ \ \ ---~---· -.. .. -.·-· . ·• "'!r--t'"- -·--,.., ~-··: ·~"'"'"'f' "''"~..._,.... ..,- .. .
~-. . ........----~-· --.....---......-J..·~- _______ J _
_____-~ _
.. .
_LI J

b
,,
,
k..l

256 Gas Prod4jction Engineering Desuljurizatlon Pro~~ 257

which is also highly toxic and corrosive. H 2S and other ·sulfur corq:ounds So many sweetening processes are in use today that it would be impoSsible to
I~ can also cause catalyst poisoning in refinery processes.
C0 2 has no heating value and its removill may be required in some .in-
stances merely to inqrease the energy conte:J.t ,of the gas per unit vel ~me.
describe them allln·detail here. S<;~me widely used processes will be·briefly
mentioned, and some important ones among these will bepresentecBn·a lit-
tle more detail.
~ C01 remqval may also be required because it forms a complex, C02 · C0 2, 'I ~ '

I which is quite corrosive in the presence of water. For gas being sent to
ogenic plants, removal of C0 2 may qe necessary to prevent solidification of
the COt. Both· the acid gases, H 2S and· C0 2, promote hydrate formation,
cry- Criteria for Proeess Selection··

There are many variables .in·gas tr~ting, which makes the .precise defini-

I and t.~e presence of C0 2 may not be desired for this reason also. However, if
none of these situations are encountered, there is no need to remove C0 2."

Removal Pro,;sses
tion of the area of application of a given proCess very difficult. Among sev-
eral factors, the following are· the most significant that" need be oonsidered:
1. The types and concentrations of impurities in the gas, and the degree
of removal desired. . ·.. . , · .. , . ·
---------------- 2. Selectivity of acid gas· rerr.oval requhed, if any.
3. Temperature and pressure at which the sour gas is available, and at
The processes 'that have b~n developed to accomplish gas )?llrification which the sweet ga.ds to .be delivered.
vary hom a simple once-through wash operati.:::; ~o complex multiple step 4. Volume of the. gas to be processed, and itS hydrocarbOn composition.
recycle systems.:J11 many c<tSes, the procesti com~·luities arise from the need 5. C0 2 to H 2S ratio in·the gas. · · ·
for recovery. in one fol'IIl· or another, of the impu~ity {H 2S) being remo.ved or 6. Economics of the process.
recovery of the -materials (process chemicals) employed to remcve it. 7. The desirability ofstilfur reeove'ry due to environmental problems, or
Llke dehydration-p,Oces.ses, desulfurization processeS are primarily of twq economics.
' types: adsorption on a solid (dry process), and absorption into a liquid (wet.
Process). There are a ~ew processes -t hat use other method<, such as the.cellu-
Besides C0 2 and H;>, some gases may contain other ~ derivatives
such as mercapta:ns and carbonyl sulfide. The presence.of such ~pUrities
10$e acetate membranes. that rely upon the different diffusion rates "for hy-
drQ;Carbon and H2S, and liquid fractionation techPiqu~ that exploit th:: rel-
of
rna y eliminate some the sweetening processes~. The con~tration5 of. acid
components are importa11t to consider. Some. processes effectively remqve
ative volatility difference.-.Application of these !at ter types of processes has
large amounts of acid gas, but not to low enough le¥~, Others remove to
been quite limited.
ultra-low values, but cannot handle large amounts of acid cOmponents in
Both.the adsorption and absorption processes may be of the physical (no
the incoming stream economically.
c;iliemical reactions'involved) or chemical· type. These processes may also be
Selectivity of a process implies thedegree .of removal of one acid gas com- ·
clilssified into the.following categqries: . ·
. . ponent relative to another. Some processes remove both Hz$ and CO,, while
1. Non-regenerative, such as Chemsweet process (Manning, 1979), NCA others are designed to sel.ectivcly remove only H 2S; Generally, it is important
process (Sun, 1980), and the Slurrisweet process (Oil & Gcs /., 1981). to consider the selectivity of a process for H 2S -versus C02 to ensure desired
The materials used in treating the gas are not recoyered in these ):rO- e.'<tent of removal of these comp<iiients. For this reason; C0 2 to Hz$ ratio in
cesses. the gas is also an important parameter.
2. Regenerative processes with recovery as H 2S. .The:>e include the physi- Operating conditions ~feet the performance of several sweetening pro-
cal absoqition processes (water wash, Selexol, F1uor solvent, etc.), the cesses. Also, different processes discharge·the sweetened gas stream at differ-
amine processes {MEA, DEA, DCA, etc.), ho~ carbonate processes ent pressure and temperature levels relative to the. conditions of the. miiom - ..._;
(Benfield, CatacAI:b), Alkazid processes, molecular sieves, etc. ing stream. Thus, the inlet and outlet conditio!)$ desired itre signi L.•n•· ·
· 3. Regenerative processes with J'e(.'OVe.r y as element.al sulfur. The Holmes- variables to consider. It may be·ecOiiomlc·in·some-cases to -alter Inn,'"·
Stretford process; a,nd the Giamma,rco-Vetrocoke process fall in this . ditions to suit the process, and·outx1ow conditions to meet ·pif'<'l in··
category. · 'Wif.h growing enVironmental concern:; regarcllng sulfur ments.

~
emission, e-,~:;~ prx':'sses have acqufred a prominent role in desulfur- Some processes are economic for large gas volumes, whit.· ,,, 1
lzation opern.t·ons. economiC advant::arr·.:t. ,,..J.. .....- ' - · , ~

\I
 U8 . Ccu ·Ptodumlon Engineering
• Desuljuri%0tion ProctlUQ · 2.59

~Jl:o.~l)uld also be .considered, .~nee some processe:; are adve~y a!- latter process gives an improved performanCe., ·generating a hig)ter remoVal
~,:by; tb.O presence of heavier fractions, while others.may strip the gas of efficiency. as well as better regeneration. , . ·
·.lome o£ itl h~bon constituents. · . This process offers .advantages of simplicity, and •bsolute ielectivity,
. .'lhs ~ilityp£ recovering ~r as elemental sulfur reduces the choice which impli~ less gas shrinkage bee.ause COil is retained in the gas. It ·IS rela-
· ~ly..Jrocesses with sulfur recovery l!ave becofne very important in . gvely inexpensive. There are several disadvantages, such as difficult and e:(.
.A:merlca. ai1,d will become so worl9wide in the. nea.r future.dqe to Cl!viron- pensive regeneration, excessive pressure. losses through the bed, inabiJity·to
. · ~· p!'Pblems caused by sulfur limissions. Sulfur is a useful by-product. remove large amounts of-sulfur, and sulfur disposal .problems, since it does·
... 1:··,; gener:&lly In _go(;d demand. by the fertilizer and chernicah industry. There- not produce sulfur in a saleable form. Detiils about this process are· avail-
(J..
fore.. in: sever.al.Jnst:ances, sulfur recoyery may be attractive: from an .epo- able from various sources suoh.as Taylor (1956), Kohl and Riesenfeld (19&5),
nomfc '$iindpoint also. ,- · · ·· · and:Dud.:worth and Geddes {1965). ·

Molecular Sieves
.Solid Bed Sweetening ProCesse.s
Synthetically manufactured forms of crystalline sodium-calciU:XU alumino
These pr~ are based upon ,PhysiC<!~ or <:h~cal aosorption of acid silicates, molecul~.r sieves are porous In structure and have a ve.ry.large sur-
ga.sc;S·.on a solid surface. Although not as .widely · us~ as the liquid absorp- face area. The pores, formed by the removal ot water of crystallization, are
,. . tion pi'CI<:eSSe.S,. they offer advantages such l!.S simplicity, high selectivity (only · uniform throughout the material. .Seveiai grades o£ molec.Ular sieveS are
H 2S is generally removed), and a process efficiency ,almost independent of · available,. with el1,ch grade corresponding to a very narrow· range.of pore
,. ·sizes. · · ·
p~. These·processes are best applied to_gases with moderate concentra-
tions of II1S, and where0 C0 2 is to be retained in the gas~ , ,.Molecular sieves remove components throu&h .a combination of ·~-~siev;
. .
. ,ing" and physical adsorption process. Beckulo o£ their pore siZes, narrow
The Iron Sponge ProcesS ...~ey discriminate among the adsorbates on the basis of their mo~ sizes.
<· ;rhe sieves possess highly localized palar charges on their ~ that 1101: as

~ur .gas is passed thr~ugh a bed of wood chips that have been impregna· · sites for polar materials. Therefo~ polar rit poladz:ab1e -oom~
ted. With ~ special hydrated form of ferric oxide that .has a l:igh affini'Y f0r even in low concentrations, m adsorbed on thoaeve
IIIIfaQe. They·
H 2S. Th•! che.mical 'react:lon is ·as follows: · Ue..higftly selective in the removal cfH1S ind othor bompouDds &om ll1l:fur
1fatural gas, and offer a continuously hi&h a'Diorption e£acleucy. Tbay :r. ·
:ffidve water also (a polar compound) .and thlj' oiler ·a mll&lll of dmWtaDeous
FezOJ + 3HzS ~ F~S 3 + .3H10 ·...lfe'hydration and desulfurization. High water content·,. . ., howewr,:·miy
tfeqilire upstream dehydration (Rushton and Ha)'l, 19!11) •.
The te.mpe+ature must be kept at less th.an 120~·F. According to Kohl and ., , Fails and Harris (1960) conducted ieveral.pllotStudies onllavas·and other
I\ieserueld .(1985), temperatures above.l20°'f and miut;ral or acid conclitiQns · a.dsorbents. They found that the adsorptive capacity of molecUlar dev.es:for ·
l~d· to th.e loss of .the water of crystallization of the ferric oxide. The b~d H2S decreases with increasing temp~ature, and increases with iDcreaSing
then becom;,s very diliicult to regenerate. Iron oxide is .reger,erated by pass- . H2S/C0 2 ratio . Increasing contact tlme·is favorable to H 1S removal up to il
ing 'o xygen/air over the bed: ppirit, beyond ;.vhich there is no effect An.optiinum pressure;of'about 450
psi.a was identified by Fails and Harris, though the effect of .. pressure w&S
1/'.' 2Fe-.z5a + 302 ~ 2F~03 + 6S ~Pund to be quite small.
_Jhe.. process flow scheme, shown in Figure 6-1, is similar .to the ·iron
The pr:o<= operates ii\ a b;~.tch-type. reaction-regeneration cycle. Regen- ~p,onge process. The bed Is regenerated by passing a portion of the sweetened'
er11-tion of the bed, however, is quite difficult and incurs ..exc-=ive mainte- · ·;;~: preheated to about 400-600°F or more, for about 1.5 hours to heat.the
nance and operating costs. Also, sulfur eventually covers most()[ the surf;lCe ,As the temperature of the bed Increases, it releas.es the adsorbe9 Hz$
of the ferric-oxide particles ·and further regeneration becomes impossible. A ·the regeneration gas stream. The sour effluent regeneration gas is flaied
continuous regeneration process has also be;en. developed; where small According to Rushton and Hays (1961), about 1-2% of the gas treated is
amounts of oxygen or air are added along with the sour gas at the inlet. This lost in this regeneration process.

II r...... r
..._ __......., __ .. ___
~- - ...._ ........ ... . . .......~~- ........... -~, : ~ ·~ ~----- ··-·---·-··· -
- ··· __......... ...~~ -~·-· ··- ··- ... .
~
·--"-:-1
; l
.... "m·~'
L II
~
 ....... )

'1 .. ~ ' .. ,_...Jjj

.4k ' I.U • l \. ,, ..,. · · ~ ~· --...,o••r_._.._,._~·-· -· -••-•
-- ·11• - -'f, i ,. __ ..,.,_, . -- ... -~ ...... . --._.,.M~~~--...,.. -··1·-·-"" ·-··~ .. -..,.~·, n-··- --~-. •
•·-• - -.....--. j...-- •••r-•···- "-,--

•
Dcitilfurizatlon ·Proeesse$ 261
··.200 t:;a• Production Engineering

iNLI:T iou .. GAS

•fL:~. I
corrosion and fouling problems are generally tninixnal; These proeessesoffer
fair to good selectivity. The.solventilsed iS generally recOvel'edby"flashing
the·acid component-rich solvent (called:'rich solvent) in flash tanb at suCces-
sively lower p~c;ssures: ·T hus, little or no heat is required.foJ' ~~~on or
other purposes. But a sulfur ret:iJvery unit is requ:inid silioe th~'pr~ do
not alter the 'lCid componen~ chemi~y in any IlWlD~ SoDfe proCesses in
this category offer simultaneOus dehydration. 'Most solvenu.eum!:ittly in use ·
have a relatively high solubility for heavier l;lydrocarboDs, particularly·un-
saturated and aromatic companents. These' Components are very detrimen-
tal to the performance of most sulfur recovery processes and 'may yield an
unsuitable, contaminated·sulfur as the,product. ·So, for sour glues contain-
ing heavy hydrocarbonS (heptanes plus}.or unsaturated and aromatic hydro-
carbons, particular care mt.JSt be tak'etf.during the regeneration~ to pre-
vent their entry into the acid·gas stream that is to be sent to a sulfur recovery
unit.

Water Wash (Aquasorption)·.Proci:ss

This process is effective for high pressure gas, with high acid gas content
Agure·,S-1.•· Flowsheet for a·molecular·sleve desulfurization process. (After Fails and high H 2S to C0 2 ratio. According to Miiddox (1982), a waterw.ash op-
and Hams, ~ 9.60;. courtesy <>f 011 & Gas Journal.) eration followed by an amine process is 12 to 15% lower in capital invest-
ment, and about 50% lower in operating expenses as cempared to a 5ingle
:B,esid~ :regeneration iasses, gas is..also lost by the adSorption of hydrocar- amine unit for an equivalent sweetening job. For gases with a high HtS to
bon components by the
sie~e .•Unsat:Urated hydrocarbon components such ~s . C0 2 ratio, the savings can be as much as .4 0% in in.vestment;. and 00 to 70%
olefuis.and aromatic$ tend to be str011gly adsorbed (Conviser, 1965). Molec- in operating costs.
ular:sieves 'are also prone .to poisoning by several chemicals such as glycols In the water wash sweetening'process, sour ga.S is sent upward through a
an<l requhe thoipugh gas cleanirig metb.ods prior to the adsorption step. The contactor, countercurrent to the water (see Figure 6-2). The partially sweet•
p~ re<i.~ a cyclic operation, since ~tis batch-type, \vith a cycle time ened gas from the top of the tower is sent to further treatment ~ts (typi-
~Jhe order.of ..2 hours . .Initial qapital_iiivestments are high, and regenera- cally, an amine unit)·. The rich watef'solution froin the
bottom of the tower
tion reqwres ·a lot of heat. For gR$ st::reams containing C0 2 , carbonyl sulfide is sent to an intermediate pressure flash tank for recovery of dissolved hydrc).
JD+Y form as shown in .the followiD.g nwersible reaction: carbons. A power recovery turbine is provid~ for rep~g the water
· HiS + COt .•;; COS +H 0 2
before sending it to a low pressure .f lash tank where all of the acid, gas is
removed, and the lean water.obtained is recycled. ·
Molecular si.eves tend to catalyze this reaction. The problem has been stud- · Froning et al. (1964) presented calculation procedures for estimating the
ied extensively, and new 'molecular sieves have be•m developed to ;etard the performance of a water wash and provide data required for such calC'Ila-
COSfoiiiPltion. ' tions. Their results show that H~ is about three times more soluble in water
than C0 2 , thereby showing that the selectivity of the process is quite good.

Physical Absorption Processes Selexol Process •

·..· ~
.. •. ,,,,.,'"'\,
These processes rely upon physical absorption of acid '''"'i'onents as the This process uses dimethyl ether of pol5"ethylene glycol (DMPEG)'.U a.
gU rw~tenirtg mechani~Irt . Because only physical absorp"c;:1. i.~ if\volved. vent. Solubilities in So;lexol solveJ;Jt of H 2S and C0 2 and other addtu
..... • ....
'
·' I ''f

- .
,.. .,.._ ~....__.........-.......-·· ·-- -
/
~ '
.. · C.U Productli:>n..Eng!neering Desuljurl:c<J«on ~ 183

·poQctll ~re·dlrccUy proportional to the .partial-·pressures of. these compo-

~./The IOlubillty of H2S is about 10 times greater than col. and
~~-~ubllity..is quite sm.a ll ..Heavier hydrocarbons, however, have
~-~l\J;bili~-II.Ilci. interm!Jd.i~tte fl~_es are generally required for hydro-
carbon removal.
· Dif:ferei;t Selt;7-o~~.based pr~ have been designed and used success-
fUlly. Hegwer 'and Harris (1970) describe three·plants insta:lled for a Wide
~~HsS to .C01 ratios: one ·p lant for a high H2S to CQ 2 ratio, another.
fo{&Jo~ HsS tO COs ratio; and the third ·for a gas containing large amounts
. of,'bothHsS and C01 . ·
. Figuie 6-3 mows
a flow scheme for a low H2S. to C02 ratio gas. Sour gas,
pn:t\~ .t o ~ov~ any solids and free liquids, .is dehydrated, cooled to
<(()•F,;-senfto the absorber for a cowitcrcurrent contacbwith Selexol sol-
vent. Bich selexol £tom the bottom of the absorber is sent, via a surge tank to
remove entrained gas that_is recycled back into the absorber, and a power
recovery turbine for pr~urizing the solvent, to a high pressure flash. Most
of the absorbed methane and some of the C0 2 is released in this flash, and i::
~to the absorber. 6·3. Selexol'" based plant for a low .HrS to Coa ratlo-;ia. (At~. Raney,
~~printed from HydrocvponPrqcoasfng.) .. . . . . . :. . . . ·. ;
· In the ~nd flash stage, most of the vapor relep.$¢d is C0 2 and it i.s
vented after power ,~:ecovery. Finally, the Sclcxol is> sent to the low pressure
flash, which is operated at 16 psia. Here, H2S and the rerr:.:J.inin~ C0 2 are
flashed.off as the vapor stream, which is ver:ted to the atmo~here. ~
·;ukanol-amine processes are the most . propline.ni: .and Widely -~
for Hz$ and C01 removal. They offer good reactlvit§at low Cost
flex'ibility in design' arid operation;·Soi:Ile o"f'the tionlinoi:uy used
Kan0l-amine5 for -absorption desuifth.izao~ri 'iire: fuo~oethanol~ille
PAAT)AUY S'tlf[ CT OAS
10 ANIH( UMtT

diei:hanolamine (DEA), . triethanoi~i~i ('i',EA)! ~P:~ 'hjlqroxi~.

J:iapo!amine, usually called diglyeolamine (D<;,;A), di-isoprop~~~aii"..in~.
arid methyldiethanolam:!ne (MDEA). _T.able· ~~ showssame'ofth~

COKTAGTOR Table 6-1

Some Char~cte~istics . of Ethanolamines•
SOUP! FEED
-----.:u--
Chern. Formula
HOC,H;NH1
Mol. WI.
61.08 1.05 100
'I
(HOC1H;)sNH 105.14 .· D.058 58 .
(HOC 1H,),N 148.19 0.0063 41"
H(OC,H;) 1NH, 105.14 0.160 .. 58 .
·~·· .. (HOC,H.),NH 133.i9 o:tno · 46
(HOC1H,),NCH, 119.17 ,,· 0.0061 . S'l
Flgurt! 6.'2. "WPieal water wash ·process. (After Froning et al., ~964 ; reprinied
from Hydroc8JboirProcessing.) · . · . · .

11r o M r _,_,,,. ,,,...,.~ ..... .l,..,U.. ... ,_. - •••• --.. - - · .-..1.1. •..-1-..L.~o!O"~.,j,.lj -. ··--- ~- ~ ~~,.,~~ .......... ~- ·· ~
...·... t.•.;..,..-,.. ... 1.- Lt~• Ul " •·,., •• ~ •• ....... ~ -
·-----~ \ . . \H
 - - -~ ' .,,- ""';"-,~ .... \ f*?' •. iUjl!fiZLfi !\~19'~~

\\\\
~,._J_,__. ____,___.L . ...-- •~
11; \I \I - - I I
-•
........... . .... - · - -··· - ...... --~-- .. -.. "11~ ---t · -----r-~~·· ··-··
__ .,.,.,•......,,..u.., ··'--- ..,.______,..._:!'__... _..... I

i
it
~
:264 ..Cas-Prodtu;tlon- Engineering

by weight MEA, 45 tc> 85% by·weight TEG (methylene gl.:Yco~

.- Desulfuri.xation Proc.

important properties for these _six alkanol-amines. Among these, MEA and·
DEA proceSses-are the mo::t widely used. _ 25% by weight of water is used;-This process removes both C<:
MEA has the -highe$t reactivity, and therefore the highest acid gas re- : _ ~des dehydrating, the gas. · At high ·temperatures,.·the· .o:rlXtW
moVal capacity, and the low«;rt molecular weight among the amines." There- . very volatile :tnd difficult to:·handle, Alsil;'-the .glycol-~ 00
fore, it offers_the highest removal capacity on a unit weight or unit volume . <foes not dehydrate as well aS an Uidepen~t glycol unit. ..
basiS, which implies_lowenolutiorr circulation rates in a sweetening plant. The reactions for the ethanolarnines, MEA; DEA, and TEA·m
MEA is chemi¢ally st11ble (minimal solution degradation). The reactimi. ~ate ·. {Batt et al.-,. 1980, Rahman, i982}:· · ·· · · ·
. ' '. !.. . . . . . . ..Q ~ · ..
'o£ H 2S with MEA is greatei than tl\at:o£ C0 2 • The process, however, is con- · l. Formation of a bisulfide of the ethanolamine on reactj.on "11
~dered to be alnui~tJlim-sei.ective in it:; .-emoval capacity for-HiS and C0 2,
beca~e ·ev~n¢eSlower ~cting C02 is rapidly and _almost completely re- RNH1 + H 1S ~ RNH.S + heat
movect. toi
MEA is' able 11!mo_ve acid gases to pipeline specifications, and
even beyond. . · ' ·_ . _ _
2. For MEA and DEA, with C0.2, the carbamate.salt of the eth1
MEA. however, suffers £rom relatively high solution losses primarily due · is formed. TEA does not have_ #Us
reac:tion witl:_l C0 2• . .
totWo reasons: it has ~a: relatjvely high vapor pressure that causes gr~ater
vaporlzation"losses, and it reads: irreversibly with carbonyl sulfide and car- 2RNH2 + COz ~ RNHCOt + ;RNHt + heat
bon disulfide. High: vaporlzati;,n losses put a lill1itation on the operating:
temperatUres, which inust be ~ept low,- whereas the reactions leading to 3. In aqueous solution, with C0 2 ~ th~ c~rbonate salt of the etha
bulldup·_of solids necessitate ett~c;ient filtration schemes. --' -·; is formed. This is a slower reaction ..- . ·
D~ is .quite similar to MEA; 'except it is not as reactive, so H 2S remov:U
to p_lpeline ~c.ations ~ay .cause problems in some. cases; its reacti'?~. RNH2 + H20 + C02, ~ RNiiJHC0 3 + heat
with ..carbonyLsul&.d.e,ai_iq ·~l>ox; disulfide are slower andle?d to different
products; so filttlltion probl~s are less; and its vapor pressure is lower, · General Process F1ow Scheme ·
therefore vaporizatiop.lo~ an: ~ess. Thus, DEA can be advant:tgeous to use .
in stime cases, , · _ · _ .. · · _ .
·. MEA is usually preferred over DEA because it enables a ,smalleJ
· TEA has,been ilhO.o~t'totally replaced by MEA and DEA, primarily-be-'' tion rl!-te of the solution, although it has a higher vapor piessure
cause it h~ Je:iSer,:,eactiVit)r and px:')blems are encountered in sweetening ~he.:, creased ·chances of greater chemical losses.
ga5 to pipeline_sPecifications. D.GA has found application in recent years. It ·_ ' · The plant is very much like an absorption dehydration system. 1
has the same reactivity as DEA, and a i-~asonably lo·w vapor pressure. DIPA·l · differences are (Curry, 1981}:
is alSo able ,to trea:t
gas to.pipem;e spedfications, and is used in the Sulfinc{ •.
process by Shell, im&the.ADIP proCess. MDEA ha~ received renewed atten~ 1. The .contactor contains.m~y mo~e tray sections, up to 20 0
· · tion because it has a fairly good selectivity for H 2S, so C0 2 can be retained in 2. A side-stream reclaimer is provided in· an MEA system.
the gas; and it offers ·sQmc energy ,s2.vfilg in the regeneration step. MDEA, 3: _More elaborate filtr~tion and heat exchange equip~ent is re
however, may not be cominercially competitive with other amine processes . 4. Operating temperatures arc different. ·
(Maddox, 1982} .. 5. The reflux requirements are
gieater.
The problems encountered are also. quite sirrl.ilar, though in a m
. Solution Concentrations and Re2ctipns
form . Some such problems are eor:rosion1 foaming, solution losses,
For MEA, an appx:oxirnately 15% ·concentration (by weight) solution iS~ solution filtering. There are·otherproblems relatiil,g to "the high v
genm-ally used. -DEA' f:$. llSed -i n 20-30% or more Cl)ncentration. DIPA and sti.re of MEA. Solution loading, that is, the amount or level of liqu
·MDEA are· typically .used in 30-50'% _concentration in aqueous solution, the contactor, Is critical. The exothenntc reactions in the contacto
while DCA Is-used in thc.40-70o/• by weight concentration range. with the low boiling point of MEA make s~hition loading a diffl
.. Some ·plants use a mi:dure of a glycol" and an amine for simultaneous de- !em. The presence of stilfur'intellsifi!lS the--corroSion problemS,by I n
hydration and desulfurlzation. Generally, · a solution containing 10 to 30% stress corrosion.
•'