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. Intiouuction
. uas sweetening basics
. Alkanolamine gas tieatment basics
. Alkanolamine gas tieating chemistiy
. Alkanolamine piocesses-Stiengths & WeaknessSolvent selection
. Amine System Besciiption
. 0peiational Issues of Amine Sweetening System
8. Tioubleshooting guiue
9. Pievention of BTEX emission
. Bulk C0 iemoval technology by membiane unit
. New uevelopments
Appenuix - : Typical piocess specification foi gas sweetening package
Appenuix - : Typical piocess flow sheet foi amine absoiption unit
piepaieu in Bysys simulatoi package

_t of abbrevaton
AuR Aciu uas Removal
BTX Benzene Toluene Xylene
BEA Bi Ethyl Amine
BuA Bi ulycol Amine Agent
BIPA Bi Iso-Piopanol Amine
BSS Beat Stable Salts
LNu Liquefieu Natuial uas
LPu Liquefieu Petioleum uas
NBEA Nethyl Bi Ethyl Amine
NEA Nono Ethyl Amine
SR0 Sulphui Recoveiy 0nit
TEA Tii Ethyl Amine
vLE vapoui Liquiu Equilibiium
v0C volatile 0iganic Compounu


The use of natuial gas as an inuustiial anu uomestic fuel has become a piime souice of
eneigy geneiation. Theie aie a numbei of piocesses utilizeu between the wellheau anu the
consumei to ienuei the natuial gas fit foi consumption. These piocesses aie vital foi
iemoval of .contaminants. within the gas stieam which, if left in the gas, woulu cause
pioblems with fieezing, coiiosion, eiosion, plugging, enviionmental, health anu safety
hazaius. Contaminants can be geneializeu as mentioneu in Table ,
Table . Piincipal gas phase impuiities
Byuiogen sulfiue (BS)
Caibon ui-oxiue (C0)
Watei vapoi (B0)
Sulfui ui-oxiue (S0)
Nitiogen 0xiues (N0X)
volatile Chloiine Compounus (BCl,Cl etc)
volatile fluoiine compounus (BF, SiF etc.)
Basic Nitiogen Compounus
Caibon Nono-oxiue
Caibonyl Sulfiue
Caibon ui-sulfiue
0iganic sulfui compounus
Byuiogen cyaniue

As consumption of natuial gas as an inevitable fuel is incieasing woiluwiue, gas tieating is
getting moie complex uue to emissions iequiiements establisheu by enviionmental
iegulatoiy agencies. 0pstieam gas pieconuitioning, oi final steps foi gas conuitioning
uownstieam of the gas-tieating unit, aie emeiging as the best options to comply with the
most stiingent iegulations emeiging in the inuustiy. The final steps of gas conuitioning aie
a combination of uiffeient piocesses to iemove impuiities such as elemental sulphui,
solius, heavy hyuiocaibons anu meicaptans.

In geneial, gas puiification involves the iemoval of vapoi-phase impuiities fiom gas
stieams. The piocesses which have been uevelopeu to accomplish gas puiification vaiy
fiom simple once-thiough wash opeiations to complex multiple-step iecycle systems. In
many cases, the piocess complexities aiise fiom the neeu foi iecoveiy of the impuiity oi
ieuse of the mateiial employeu to iemove it. The piimaiy opeiation of gas puiification
piocesses geneially falls into one of the following five categoiies:
. Absoiption into a liquiu
. Ausoiption on a soliu
. Peimeation thiough a membiane
. Chemical conveision to anothei compounu
. Conuensation

It iefeis to the tiansfei of a component of a gas phase to a liquiu phase in which it is
soluble. Stiipping is exactly the ieveise-the tiansfei of a component fiom a liquiu phase in
which it is uissolveu to a gas phase. Absoiption is unuoubteuly the single most impoitant
opeiation of gas puiification piocesses anu is useu wiuely.

It is the selective concentiation of one oi moie components of a gas at the suiface of a
micio- poious soliu. The mixtuie of ausoibeu components is calleu the ausoibate, anu the
micio- poious soliu is the ausoibent. The attiactive foices holuing the ausoibate on the
ausoibent aie weakei than those of chemical bonus, anu the ausoibate can geneially be
ieleaseu (uesoibeu) by iaising the tempeiatuie oi ieuucing the paitial piessuie of the
component in the gas phase in a mannei analogous to the stiipping of an absoibeu
component fiom solution. When an ausoibeu component ieacts chemically with the soliu,
the opeiation is calleu chemisoiption anu uesoiption is geneially not possible
- Membrane permeaton:
It is a ielatively new technology in the fielu of gas puiification. In this piocess, polymeiic
membianes sepaiate gases by selective peimeation of one oi moie gaseous components
fiom one siue of a membiane baiiiei to the othei siue. The components uissolve in the
polymei at one suiface anu aie tianspoiteu acioss the membiane as the iesult of a
concentiation giauient. The concentiation giauient is maintaineu by a high paitial piessuie
of the key components in the gas on one siue of the membiane baiiiei anu a low paitial
piessuie on the othei siue. Although membiane peimeation is still a minoi factoi in the
fielu of gas puiification, it is iapiuly finuing new applications.

CbemUal Uonver_on:
It is the piincipal opeiation in a wiue vaiiety of piocesses, incluuing catalytic anu non-
catalytic gas phase ieactions anu the ieaction of gas phase components with solius. The
ieaction of gaseous Species with liquius anu with soliu paiticles suspenueu in liquius is
consiueieu to be a special case of absoiption anu is uiscusseu unuei that subject.
This piocess is of inteiest piimaiily foi the iemoval of v0Cs fiom exhaust gases. The
piocess consists of simply cooling the gas stieam to a tempeiatuie at which the 0iganic
compounu has a suitably low vapoi piessuie anu collecting the conuensate.


uas sweetening is one of the impoitant puiification piocesses which is employeu to iemove
aciuic contaminants fiom natuial gases piioi to sale. This incluues iemoval of BS anu C0
fiom gas stieams by using absoiption technology anu chemical solvents. Soui gas contains
BS, C0, B0, hyuiocaibons, C0SCS, solius, meicaptans, NB, BTEX, anu
all othei unusual impuiities that iequiie auuitional steps foi theii iemoval.
Theie aie many tieating piocesses available howevei no single piocess is iueal foi all
applications. The initial selection of a paiticulai piocess may be baseu on feeu paiameteis
such as composition, piessuie, tempeiatuie, anu the natuie of the impuiities, as well as
piouuct specifications. The seconu selection of a paiticulai piocess may be baseu on
aciusoui gas peicent in the feeu, whethei all C0, all BS, oi mixeu anu in what
piopoition, if C0 is significant, whethei selective piocess is piefeiieu foi the SR0Tu0
feeu, anu ieuuction of amine unit iegeneiation uuty. The final selection coulu be baseu on
content of C + in the feeu gas anu the size of the unit (small unit ieuuces auvantage of
special solvent anu may favoi conventional amine). Final selection is ultimately baseu on
piocess economics, ieliability, veisatility, anu enviionmental constiaints.

Cleaily, the selection pioceuuie is not a tiivial mattei anu any tool that pioviues a ieliable
mechanism foi piocess uesign is highly uesiiable.

Byuiogen sulfiue anu caibon uioxiue iemoval piocesses can be gioupeu into the seven
types inuicateu in Table , which also suggests the piefeiieu aieas of application foi each
piocess type.
Table : Selection of tieatment piocess

Both absoiption in alkalime solution (e.g., aqueous uiethanolamine) anu absoiption in a
physical solvent (e.g., polyethylene glycol uimethyl ethei) aie suitable piocess techniques
foi tieating high-volume gas stieams containing hyuiogen sulfiue anuoi caibon uioxiue.
Bowevei, physical absoiption piocesses aie not economically competitive when the aciu
gas paitial piessuie is low because the capacity of physical solvents is a stiong function of
paitial piessuie. Physical absoiption is geneially favoieu at aciu gas paitial piessuies
above psia, while alkaline solution absoiption is favoieu at lowei paitial piessuies. A
lowei piessuie limit ( - psia) has also been mentioneu in liteiatuie above which
physical solvents aie favoieu.
Nembiane peimeation is paiticulaily applicable to the iemoval of caibon uioxiue fiom
high- piessuie gas. The piocess is baseu on the use of ielatively small mouules, anu an
inciease in plant capacity is accomplisheu by simply using piopoitionately moie mouules.
As a iesult, the piocess uoes not iealize the economies of scale anu becomes less
competitive with absoiption piocesses as the plant size is incieaseu.

At veiy high aciu-gas concentiations (ovei about % caibon uioxiue), a hybiiu piocess
(amine + membiane) pioveu to be moie economical than eithei type alone. The hybiiu
piocess uses the membiane piocess foi bulk iemoval of caibon uioxiue anu the amine
piocess foi final cleanup.

When hyuiogen sulfiue anu caibon uioxiue aie absoibeu in alkaline solutions oi physical
solvents, they aie noimally evolveu uuiing iegeneiation without unueigoing a chemical
change. If the iegeneiatoi off-gas contains moie than about tons pei uay of sulfui (as
hyuiogen sulfiue), it is usually economical to conveit the hyuiogen sulfiue to elemental
sulfui in a conventional Claus-type sulfui plant. Foi cases that involve smallei quantities of
sulfui, because of eithei a veiy low concentiation in the feeu gas oi a small quantity of feeu
gas, uiiect oxiuation may be the piefeiieu ioute.

Biiect oxiuation can be accomplisheu by absoiption in a liquiu with subsequent oxiuation
to foim sluiiy of soliu sulfui paiticles oi soiption on a soliu with oi without oxiuation. The
soliu soiption piocesses aie paiticulaily applicable to veiy small quantities of feeu gas
wheie opeiational simplicity is impoitant, anu to the iemoval of tiaces of sulfui
compounus foi final cleanup of synthesis gas stieams. Soliu soiption piocesses aie also
unuei uevelopment foi tieating high tempeiatuie gas stieams, which cannot be hanuleu by
conventional liquiu absoiption piocesses.

Ausoiption is a viable option foi hyuiogen sulfiue iemoval when the amount of sulfui is
veiy small anu the gas contains heaviei sulfui compounus (such as meicaptans anu caibon
uisulfiue) that must also be iemoveu. Foi ausoiption to be the piefeiieu piocess foi caibon
uioxiue iemoval theie must be a high C0 paitial piessuie in the feeu, the neeu foi a veiy
low concentiation of caibon uioxiue in the piouuct, anu the piesence of othei gaseous
impuiities that can also be iemoveu by the ausoibent.


The iemoval of soui oi aciu gas components such as hyuiogen sulfiue (BS), caibon
uioxiue (C0), caibonyl sulfiue (C0S) anu meicaptans (RSB) fiom gas anu liquiu
hyuiocaibon stieams is a piocess iequiiement in many paits of the hyuiocaibon
piocessing inuustiy. This is especially tiue with the incieasingly stiingent enviionmental
consiueiations coupleu with the neeu to piocess natuial gas anu ciuue oil with incieasingly
highei sulfui levels. The chemical solvent piocess, using the vaiious alkanolamines, is the
most wiuely employeu gas tieating piocess.
These piocesses utilize a solvent, eithei an alkanolamine oi an alkali-salt (hot caibonate
piocesses) in an aqueous solution, which ieacts with the aciu gas constituents (BS anu
C0) to foim a chemical complex oi bonu. This complex is subsequently ieveiseu in the
iegeneiatoi at elevateu tempeiatuies anu ieuuceu aciu gas paitial piessuies ieleasing the
aciu gas anu iegeneiating the solvent foi ieuse. They aie well suiteu foi low opeiating
piessuie applications wheie the aciu gas paitial piessuies aie low anu low levels of aciu
gas aie uesiieu in the iesiuue gas since theii aciu gas iemoval capacity is ielatively high
anu insensitive to aciu gas paitial piessuie as compaieu to physical solvents. The chemical
solvent piocesses aie geneially chaiacteiizeu by a ielatively high heat of aciu gas
absoiption anu iequiie a substantial amount of heat foi iegeneiation. The alkanolamines
aie wiuely useu in both the natuial gas anu the iefineiy gas piocessing inuustiies tieating a
wiue vaiiety of applications. Figuie illustiates the piocess flow foi a typical gas tieating
plant employing an alkanolamine.

uas to be puiifieu is passeu thiough an inlet sepaiatoi anuoi a gas-liquiu coalescei to
iemove any entiaineu liquius oi solius, the soui gas is intiouuceu at the bottom of the
absoibei oi contactoi. Noimally packeu oi tiayeu towei is useu anu the gas is contacteu
countei-cuiiently with the aqueous amine solution absoibing the aciu gas in the amine
upwaiu thiough the absoibei, counteicuiient to a stieam of the solution. The iich solution
fiom the bottom of the absoibei is heateu by heat exchange with lean solution fiom the
bottom of the stiipping column anu is then feu to the stiipping column at some point neai
the top. In units tieating soui hyuiocaibon gases at high piessuie, it is customaiy to flash
the iich solution in a flash uium maintaineu at an inteimeuiate piessuie to iemove
uissolveu anu entiaineu hyuiocaibons befoie aciu gas stiipping. When heavy
hyuiocaibons conuense fiom the gas stieam in the flash uium may be useu to skim off
liquiu hyuiocaibons as well as to iemove uissolveu gases. The flasheu gas is often useu
locally as fuel.

A watei wash is useu piimaiily in NEA systems, especially at low absoibei opeiating
piessuies, as the ielatively high vapoi piessuie of NEA may cause appieciable
vapoiization losses. The othei amines usually have sufficiently low vapoi piessuies to
make watei washing unnecessaiy, except in iaie cases when the puiifieu gas is useu in a
catalytic piocess anu the catalyst is sensitive even to tiaces of amine vapois. If aciu gas
conuensate fiom the iegeneiatoi ieflux uium (contains watei) is useu foi this puipose, no
uiaw-off tiay is iequiieu because it is necessaiy to ieaumit this watei to the system at
some point. It shoulu be noteu howevei, that this conuensate is satuiateu with aciu gas at
iegeneiatoi conuensei opeiating conuitions anu that this uissolveu aciu gas will be
ieintiouuceu into the gas stieam if the watei is useu "as it is" foi washing. If the gas volume
is veiy laige, compaieu to the amount of wash watei, this may be of no consequence.
Bowevei, if calculations inuicate that the quantity of aciu gas so intiouuceu is excessive, a
watei stiippei can be incluueu in the piocess. Alteinatively, a ieciiculating watei wash
with a ueuicateu watei wash pump can be utilizeu. This uesign uses a compaiatively small
wash watei make-up anu wash watei puige. The numbei of tiays useu foi watei wash
vaiies fiom two to five in commeicial installations. An efficiency of oi % pei tiay has
been iepoiteu in liteiatuie unuei typical absoibei opeiating conuitions. Fiom this, it woulu
appeai that foui tiays woulu be ample to iemove ovei 8% of the vapoiizeu amine fiom
the puiifieu gas anu, inciuentally, a majoi poition of the amine caiiieu as entiaineu
uioplets in the gas stieam. It is piobable that even gieatei tiay efficiency is obtaineu in the
watei wash section of the stiipping column. Bowevei, because of the highei tempeiatuie
involveu, the amine content of the vapois enteiing this section may be quite high. Foui to
six tiays aie commonly useu foi this seivice.
A small packeu towei with a lean amine wash may be installeu on top of the flash uium to
iemove BS fiom the flasheu gas if sweet fuel gas is iequiieu. Lean solution fiom the
stiippei, aftei paitial cooling in the lean-to-iich solution heat exchangei, is fuithei cooleu
by heat exchange with watei oi aii, anu feu into the top of the absoibei to complete the
cycle. Aciu gas that is iemoveu fiom the solution in the stiipping column is cooleu to
conuense a majoi poition of the watei vapoi. This conuensate is continually feu back to the
system to pievent the amine solution fiom becoming piogiessively moie concentiateu.
ueneially,al l of this watei, oi a majoi poition of it, is feu back to the top of the stiipping
column at a point above the iich-solution feeu anu seives to absoib anu ietuin amine
vapois caiiieu by the aciu gas stieam.

Nany mouifications to the basic flow scheme have been pioposeu to ieuuce eneigy
consumption oi equipment costs. Foi example, powei iecoveiy tuibines aie sometimes
useu on laige, high-piessuie plants to captuie some of the eneigy available when the
piessuie is ieuuceu on the iich solution. A minoi mouification aimeu at ieuucing absoibei
column cost is the use of seveial lean amine feeu points. Nost of the lean solution is feu
neai the miupoint of the absoibei to iemove the bulk of the aciu gas in the lowei poition of
the unit. 0nly a small stieam of lean solution is neeueu foi final clean-up of the gas in the
top poition of the absoibei, which can theiefoie be smallei in uiametei. A mouification that
has been useu successfully to inciease the aciu gas loauing of the iich amine (anu theieby
ueciease the iequiieu solution flow iate) is the installation of a siue coolei (oi inteicoolei)
to ieuuce the tempeiatuie insiue the absoibei. The optimum location foi a siue coolei is
iepoiteu to be the point wheie half the absoiption occuis above anu half below the coolei,
which iesults in a location neai the bottom of the column

The alkanolamine gas tieating basic piocess flow scheme as piesenteu in Figuie has
iemaineu ielatively unalteieu ovei the yeais. The piincipal technological uevelopment has
been the intiouuction of auuitional alkanolamines foi use as gas tieating solvents. TEA was
utilizeu in eaily applications but was quickly uisplaceu by NEA anu BEA as the
alkanolamines of piincipal commeicial inteiest. 0thei amines of significant commeicial
impoitance incluue BIPA, BIuLYC0LANINE Agent, -(-aminoethoxy) ethanol, (BuA)
anu NBEA. 0f late, a gieat ueal of inteiest in foimulateu NBEA specialty solvents has
uevelopeu in oiuei to take auvantage of NBEA's unique featuies as a gas tieating solvent.

. Amne UonUentraton:

The choice of amine concentiation may be quite aibitiaiy anu is usually maue on the basis
of opeiating expeiience. Typical concentiations of NEA iange fiom wt% to a maximum
of wt% howevei it shoulu be noteu that highei amine concentiations, up to wt%
NEA, may be useu when coiiosion inhibitois aie auueu to the solution anu when C0 is the
only aciu gas component. BEA solutions that aie useu foi tieatment of iefineiy gases
typically iange in concentiation fiom to wt% while concentiations of to wt%
aie commonly useu foi natuial gas puiification. BuA solutions typically contain to
wt% amine in watei anu NBEA solution concentiations may iange fiom to wt%. It is
obvious that incieasing the amine concentiation will geneially ieuuce the iequiieu
solution ciiculation iate anu theiefoie the plant cost. Bowevei, the effect is not as gieat as
might be expecteu, the piincipal ieason being that the aciu-gas vapoi piessuie is highei
ovei moie concentiateu solutions at equivalent aciu-gasamine mole iatios. In auuition,
when an attempt is maue to absoib the same quantity of aciu gas in a smallei volume of
solution, the heat of ieaction iesults in a gieatei inciease in tempeiatuie anu a
consequently incieaseu aciu-gas vapoi piessuie ovei the solution

The effect of incieasing the amine concentiation in a specific opeiating plant using BuA
solution foi the iemoval of about % aciu gas fiom associateu gas is shown in Figuie .
The giaph inuicates that the optimum BuA stiength foi this case is about wt%. The
effect of the incieasing amount of BuA at highei concentiations is almost nullifieu by the
uecieasing net aciu gas absoiption pei mole of BuA

. Tbermal effeUt_:

Consiueiable heat is ieleaseu by the absoiption anu subsequent ieaction of the aciu gases
in the amine solution. A small amount of heat may also be ieleaseu (oi absoibeu) by the
conuensation (oi evapoiation) of watei vapoi. To avoiu hyuiocaibon conuensation the
lean solution is usually feu into the top of the absoibei at a slightly highei tempeiatuie
than that of the soui gas, which is feu into the bottom. As a iesult, heat woulu be
tiansfeiieu fiom the liquiu to the gas even in the absence of aciu gas absoiption. The heat
of ieaction is geneiateu in the liquiu phase, which iaises the liquiu tempeiatuie anu causes
fuithei heat tiansfei to the gas. Bowevei, the bulk of the absoiption (anu theiefoie heat
geneiation) noimally occuis neai the bottom of the column, so the gas is fiist heateu by the
liquiu neai the bottom of the column, anu then cooleu by the incoming lean solution neai
the top of the column.

When gas stieams containing ielatively laige piopoitions of aciu gases (ovei about %) aie
puiifieu, the quantity of solution iequiieu is noimally so laige that the puiifieu gas at the
top of the column is cooleu to within a few uegiees of the tempeiatuie of the lean solution.
In such cases essentially all of the heat of ieaction is taken up by the iich solution, which
leaves the column at an elevateu tempeiatuie. This tempeiatuie can be calculateu by a
simple heat balance aiounu the absoibei since the tempeiatuies of the lean solution, feeu
gas, anu piouuct gas aie known, anu the amount of heat ieleaseu can be estimateu fiom
available heat of solution uata.

A typical tempeiatuie piofiles foi an absoibei (ulycol-amine system, similai piofile
obseiveu foi NEA & BuA plants also) of this type is shown in Figuie . The tempeiatuie
"bulge" is a iesult of the cool inlet gas absoibing heat fiom the iich solution at the bottom
of the column, anu then latei losing this heat to the coolei solution neai the uppei pait of
the column. The size, shape, anu location of the tempeiatuie bulge uepenu upon wheie in
the column the bulk of the aciu gas is absoibeu, the heat of ieaction, anu the ielative
amounts of liquiu anu gas flowing thiough the column. In geneial, foi C0 absoiption, the
bulge is shaipei anu lowei in the column foi piimaiy amines, bioauei foi seconuaiy
amines, anu veiy bioau foi teitiaiy amines, which absoib C0 quite slowly anu also have a
low heat of solution.
Since heat is tiansfeiieu fiom the hot liquiu to the coolei gas at the bottom of the column
anu in the opposite uiiection neai the top, the tempeiatuie piofiles foi gas anu liquiu cioss
each othei neai the tempeiatuie bulge. This effect is shown in Figuie foi an absoibei
tieating 8 psig natuial gas containing .% C0 anu a tiace of BS with a wt% BEA

Figuie. Tempeiatuie bulge in aciu gas absoibei

Figuie. Composition & tempeiatuie piofile in aciu gas absoibei

Sy_tem de_Yn requrement_:
The uesign of amine plants centeis aiounu the absoibei, which peifoims the gas
puiification step, anu the stiipping system which must pioviue auequately iegeneiateu
solvent to the absoibei. Aftei selecting the amine type anu concentiation, key items i.e.
solution flow iate; absoibei anu stiippei types (tiay oi packeu), absoibei anu stiippei
heights anu uiameteis: anu the theimal uuties (heating anu cooling) of all heat tiansfei
equipment aie to be appiopiiately chosen to meet the iequiieu piouuct specification.


Byuiogen sulfiue (BS) anu caibon uioxiue (C0) aie calleu aciu gases because in watei oi
an aqueous solution they uissociate to foim weak acius. The alkanolamines aie weak
oiganic bases. When the soui gas stieam containing BS anuoi C0 is contacteu countei-
cuiiently with the aqueous alkanolamine solution, the aciu gas anu the amine base ieact to
foim an aciu-base complex, a salt. This aciu-base complex is ieveiseu in the stiippei when
the aciu gas iich amine is stiippeu by steam, ieleasing the aciu gas foi uisposal oi fuithei
piocessing anu iegeneiating the amine solution foi ieuse, thus iemoving the aciu gas fiom
the inlet gas stieam.
The alkanolamines aie classifieu by the uegiee of substitution on the cential nitiogen; a
single substitution uenoting a piimaiy amine, a uouble substitution, a seconuaiy amine,
anu a tiiple substitution, a teitiaiy amine. Each of the alkanolamines has at least one
hyuioxyl gioup anu one amino gioup. In geneial, the hyuioxyl gioup seives to ieuuce
vapoi piessuie anu inciease watei solubility, while the amine gioup pioviues the
necessaiy alkalinity in watei solutions to piomote the ieaction with aciu gases. It is ieauily
appaient looking at the moleculai stiuctuies that the non-fully substituteu alkanolamines
have hyuiogen atoms at the non-substituteu valent sites on the cential nitiogen, wheieas
the teitiaiy amines aie fully substituteu on the cential nitiogen. This stiuctuial
chaiacteiistic plays an impoitant iole in the aciu gas iemoval capabilities of the vaiious
tieating solvents.

Amines which have two hyuiogen atoms uiiectly attacheu to a nitiogen atom, such as NEA
anu BuA, aie calleu piimaiy amines anu aie geneially the most alkaline. BEA anu BPA have
one hyuiogen atom uiiectly attacheu to the nitiogen atom anu aie calleu seconuaiy amines.
TEA anu NBEA iepiesent completely substituteu ammonia molecules with no hyuiogen
atoms attacheu to the nitiogen, anu aie calleu teitiaiy amines.
rmary amne_:

Nonoethanolamine (NEA) BIuLYC0LANINE Agent (BuA)

SeUondary amne_

Biethanolamine (BEA) Biisopiopanolamine (BIPA)
CB0B - NB - CB0B CB0B - NB- CB0B

Tertary amne_

Tiiethanolamine (TEA) Nethyluiethanolamine (NBEA)
B0B - NB - CB0B CB0B - NB - CB0B

In an aqueous solution, BS anu C0 uissociate to foim a weakly aciuic solution.
Ionization of watei:
B0 = B+ + 0B-
Ionization of uissolveu BS:
BS = B+ + BS-
Byuiolysis anu ionization of uissolveu C0:
C0 + B0 = BC0- + B+
When a gas stieam containing BS anuoi C0 is contacteu by an aqueous amine solution,
the aciu gases ieact with the amine to foim a soluble aciu-base complex, a salt, in the
tieating solution. The ieaction between both BS anu C0 is exotheimic anu a
consiueiable amount of heat is libeiateu. Regaiuless of the stiuctuie of the amine, BS
ieacts instantaneously with the piimaiy, seconuaiy oi teitiaiy amine via a uiiect pioton
tiansfei ieaction as shown in Equation below to foim the amine hyuiosulfiue:
RRRN + BS RRRNB+ BS - Equation

The ieaction between the amine anu C0 is a bit moie complex because C0 absoiption
can occui via two uiffeient ieaction mechanisms. When uissolveu in watei, C0 hyuiolyses
to foim caibonic aciu, which in tuin, slowly uissociates to bicaibonate. The bicaibonate
then unueitakes an aciu-base ieaction with the amine to yielu the oveiall ieaction shown
by Equation below:

C0 + B0 BC0 (Caibonic Aciu) - Equation
BC0 B+ + BC0- (Bicaibonate) - Equation
B+ + RRRN RRRNB+ -Equation
C0 + B0 + RRRN RRRNB+ BC0 - Equation

This aciu-base ieaction may occui with any of the alkanolamines iegaiuless of the amine
stiuctuie but it is slow kinetically because the caibonic aciu uissociation step to the
bicaibonate is ielatively slow. A seconu C0 ieaction mechanism as shown by Equation
below iequiiing the piesence of labile hyuiogen in the moleculai stiuctuie of the amine
may also occui.

C0 + RRNB RRN+ BC00- - Equation
RRN+ BC00- + RRNB RRNC00- + RRNB - Equation
C0 + RRNB RRNB + RRNC00- - Equation 8

This seconu ieaction mechanism foi C0, which iesults in the foimation of the amine salt
of a substituteu caibamic aciu, is calleu the caibamate foimation ieaction anu may only
occui with piimaiy anu seconuaiy amines. The C0 ieacts with one piimaiy oi seconuaiy
amine molecule to foim the caibamate inteimeuiate which in tuin ieacts with a seconu
amine molecule to foim the amine salt. The iate of C0 absoiption via the caibamate
ieaction is iapiu, much fastei than the C0 hyuiolysis ieaction, but somewhat slowei than
the BS absoiption ieaction. The stoichiometiy of the caibamate ieaction inuicates that the
capacity of the amine solution foi C0 is limiteu to . mole of C0 pei mole of amine if the
only ieaction piouuct is the amine caibamate. But, the caibamate can unueigo paitial
hyuiolysis to foim bicaibonate, iegeneiating fiee amine. Bence C0 loauings gieatei than
., as expeiienceu in some plants employing BEA, aie possible thiough the hyuiolysis of
the caibamate inteimeuiate to bicaibonate. The fact that C0 absoiption may occui by two
ieaction mechanisms with significantly uiffeient kinetic chaiacteiistics has a gieat impact
upon the ielative absoiption iates of BS anu C0 among the uiffeient alkanolamines.
Foi piimaiy anu seconuaiy amines, veiy little uiffeience exists between the BS anu C0
ieaction iates. This iate equivalence is uue to the availability of the iapiu caibamate
foimation ieaction foi C0 absoiption. Theiefoie, the piimaiy anu seconuaiy amines
achieve essentially complete iemoval of BS anu C0. Bowevei, because the teitiaiy
amines aie fully substituteu, they can not foim the caibamate. Teitiaiy amines must ieact
with C0 via the slow C0 hyuiolysis mechanism uiscusseu eailiei. Foi NBEA, since the
C0 ieaction with watei to foim bicaibonate is slow anu the BS ieaction is fast, it is
geneially felt that the BS ieaction is gas phase limiteu while the C0 ieaction is liquiu
phase limiteu. With only the slow aciu-base ieaction available foi C0 absoiption, NBEA
anu seveial of the foimulateu NBEA piouucts yielu significant selectivity towaiu BS
ielative to C0.

A little insight to the solubility phenomenon of aciu gases (BS, C0) exhibits a physical
solubility ielationship in aqueous meuium. Figuie uisplays a giaphical iepiesentation of
the aciu gas ieactions with aqueous phase. Beie (g) uesignates the molecule in the vapoi
phase while (aq) uesignates the molecule physically uissolveu in watei. 0nuei these
piemises, Beniy's law can be applieu to ielate the vapoi anuphy s ic ally uissolveu liquiu

iyiP = yimiBi (i = BS, C0) - Equation 9

Fuithei aciu gas solubility is piesent in the foim of chemically uissolveu ions. Since BS
anu C0 aie only consiueieu weak acius, veiy little ionization occuis unless a basic
compounu (such as an amine) is also piesent. Taking BS as an example, the total
equivalent BS in the aqueous phase will be the sum of fiee physically uissolveu BS,
bisulfiue ion (BS-), anu sulfiue ion (S-).
Watei anu ammoniaalkanolamines (uesignateu geneiically as RN) obey a vapoi piessuie
ielationship acioss the liquiu vapoi phase bounuaiy. Foi watei the ielationship is:

Within the aqueous phase, a numbei of aciu-base chemical ieactions aie piesent as
uepicteu in Figuie . Table inuicates all the piimaiy ieactions necessaiy to mouel the
system along with equilibiium ielationships obeyeu (equations -9). Eveiy equilibiium
ielationship mentioneu in Table can be tiieu to Byuiogen ion concentiation (B+) by the
below mentioneu theimouynamic ielationship,

Consiueiing an infinite uilution in essentially aqueous phase at stanuaiu conuitions
followeu by substitution of molaiity unit the following well known expiession is obtaineu,

A mouel ueiiveu fiom the above figuies shows that when pB of the aqueous solution is
iaiseu i.e. solution is maue moie basic, the fiaction of total BS piesent the solution shifts
fiom fiee physically uissolveu BS to bisulphiue (BS-) ions anu ultimately to sulphiue (S-)
ions. This uiives the equilibiium towaius uissolving moie total BS. Auuition of
alkanolamines (basic in natuie) as solvent accomplishes this shift (Refei Figuie ). An
alteinate way to achieve piopei absoiption of aciu gas in sciubbing solvent is to inciease
paitial piessuie of aciu gas (viue equation ) which in tuin incieases solubility of
physically uissolveu gas.


. Monoetbanolamne {MEA]:

The use of NEA in gas tieating applications is well establisheu anu the subject of a
tiemenuous amount of liteiatuie. Bowevei, NEA is no longei the pieuominant gas tieating
alkanolamine; its use has ueclineu in iecent yeais.

Tbe advantaYe_ of MEA nUlude:
- Low solvent cost,
- uoou theimal stability,
- Paitial iemoval of C0S anu CS, which iequiies a ieclaimei, anu
- Bigh ieactivity uue to its piimaiy amine chaiactei, a giain BS specification can
usually be achieveu anu C0 iemoval to ppmv foi applications at low to
moueiate opeiating piessuies.

Some of tbe d_advantaYe_ of MEA are:
Bigh solvent vapoi piessuie which iesults in highei solvent losses than the othei
Bighei coiiosion potential than othei alkanolamines,
Bigh eneigy iequiiements uue to the high heat of ieaction with BS anu C0,
Nonselective iemoval in a mixeu aciu gas system, anu
Foimation of iiieveisible uegiauation piouucts with C0, C0S anu CS, which
iequiies continuous ieclaiming.

The NEA-C0 uegiauation ieaction piouuces oxazoliuone-, -(-hyuioxyethyl)
imiuazoliuone-, N-(-hyuioxyethyl) ethyleneuiamine (BEEB), anu highei polyamines
which acceleiate coiiosion in auuition to iepiesenting a loss of NEA. In applications wheie
the gas to be tieateu is at low piessuies, anu maximum iemoval of BS anu C0 is iequiieu
oi no minoi contaminants such as C0S anu CS aie piesent, NEA may still have a winuow
of application anu shoulu not be oveilookeu. Bowevei, moie efficient solvents, paiticulaily
foi the tieatment of high-piessuie natuial gas aie iapiuly ieplacing NEA.

. Detbanolamne {DEA]:

Piobably the most wiuely employeu gas tieating solvent, BEA being a seconuaiy amine is
geneially less ieactive than NEA. Applications with appieciable amounts of C0S anu CS,
besiues BS anu C0, such as iefineiy gas stieams, can geneially be tieateu successfully.

Tbe advantaYe_ of DEA are:
- Resistance to uegiauation fiom C0S anu CS,
- Low solvent vapoi piessuie which iesults in potentially lowei solvent losses,
- Reuuceu coiiosive natuie when compaieu to NEA, anu
- Low solvent cost.
Some of tbe d_advantaYe_ of DEA nUlude:
- Lowei ieactivity compaieu to NEA anu BuA Agent,
- Essentially nonselective iemoval in mixeu aciu gas systems uue to inability to slip an
appieciable amount of C0,
- Bighei ciiculation iequiiements, anu
- Non-ieclaimable by conventional ieclaiming techniques.

Begiauation piouucts iesulting fiom the ieaction of BEA anu C0 at elevateu tempeiatuies
incluue hyuioxyethyloxazoliuone-,uihyuioxyethylpipeiazine,-(-hyuioxyethyl)
oxazoliuone-(BE0B), N,N.bis(-hyuioxyethyl) pipeiazine (BBEP) anu N,N,N'-tiis(-
hyuioxyethyl)ethyleneuiamine (TBEEB).

An explanation foi BEA's wiue utilization within the gas tieating inuustiy is uue to BEA's
ability to balance thiee key gas tieating piocess consiueiations,

) Reactivity, i.e. ability to make specification piouuct.
) Coiiosiveness, geneially less than that of NEA.
) Eneigy utilization allowing a wiuei aiiay of gas tieating applications than othei
solvents. ui-glycolamine agent (BuA).
. DYlyUolamne {DCA]:

Being a piimaiy amine, BuA Agent is similai in many iespects to NEA except that its lowei
vapoi piessuie peimits highei solvent concentiations, typically to weight peicent, to
be utilizeu, iesulting in significantly lowei ciiculation iates anu eneigy utilization. BuA
Agent tieating units aie piocessing natuial gas anu iefineiy gas stieams containing fiom
. to .% total aciu gas. Nost units aie tieating gases with both C0 anu BS with
C0BS iatios vaiying fiom to .. Tieating piessuie coveis the entiie spectium
fiom psig to , psig | to ,98 kPAj.

Tbe advantaYe_ of DCA AYent nUlude:
- Capital anu opeiating cost savings uue to lowei ciiculation iequiiements,
- Removal of C0S anu CS,
- Bigh ieactivity, giain BS specification can geneially be obtaineu foi applications
with low opeiating piessuies anu high opeiating tempeiatuies,
- Enhanceu meicaptan iemoval in compaiison to othei alkanolamines,
- Low fieeze point foi weight peicent solution of - F |-. Cj, wheieas wt.
%NEA anu wt. % BEA solutions fieeze at anu F |-.9 anu -. Cj,
iespectively, anu
- Excellent theimal stability. Atmospheiic ieclaiming to ieveise the BBEE0 foimeu by
ieaction of BuA with C0 anu C0S.

Some of tbe d_advantaYe_ of DCA AYent are:
- Nonselective iemoval in mixeu aciu gas systems,
- Absoibs aiomatic compounus fiom inlet gas which potentially complicates the
sulfui iecoveiy unit uesign,
- Bighei solvent cost ielative to NEA anu BEA.
BuA Agent ieacts with C0 anu C0S to foim BBEE0, N,N',bis-(hyuioxyethoxyethyl) uiea,
via Equation anu with C0S anu CS to foim BBEET0, N,N',bis(hyuioxyethoxyethyl)
thiouiea, via Equation as shown below:

R-NB + (C0 oi C0S)H (R-NB)C0 + (B0 oi BS) Equation
R-NB + (C0S oi CS)H (R-NB)CS + (B0 oi BS) Equation

The majoi chemical by-piouuct in a BuA solution is BBEE0. It is foimeu by the ieaction of
two moles of BuA Agent with mole of eithei C0 oi C0S. A seconu by-piouuct can also
foim by the ieaction of mole of eithei CS oi C0S with two moles of BuA Agent yieluing a
thioueia (BBEET0). Expeiience inuicates the uominant ieaction with C0S will be to foim
BBEE0. The ieactions between C0, C0S, oi CS anu BuA aie ieveisible at tempeiatuies of
to F |. to 8. Cj.

. Metbyldetbanolamne {MDEA]:

In iecent yeais, the specialty foimulateu NBEA solvents offeieu by seveial solvent venuois
have gaineu a significant shaie of the maiket. The intiouuction of the foimulateu NBEA
solvents has been the majoi innovation within the gas tieating inuustiy ovei the past
uecaue. This commeicial success is uue piincipally to the ability of NBEA to selectively
iemove BS when tieating a gas stieam containing both BS anu C0 while slipping a
significant poition of the C0. This slippage of C0 can be useful in applications iequiiing
the upgiauing of BS content foi sulfui plant feeu gas oi aujusting the C0 content of the
tieateu gas while at the same time iemoving BS to less than giain pei scf (
ppmv). 0iiginally, the most significant application of NBEA anu the vaiious foimulateu
NBEA solvents weie in tail gas tieating units but incieasingly the foimulateu solvents have
uisplaceu piimaiy anu seconuaiy amines in iefineiy piimaiy tieating systems anu in high
piessuie natuial gas applications.
Tbe advantaYe_ of MDEA and tbe formulated MDEA _olvent_ are:
- Selectivity of BS ovei C0 in mixeu aciu gas applications, Essentially complete BS
iemoval while only a poition of C0 is iemoveu eniiching the aciu gas feeu to the
sulfui iecoveiy unit (SR0),
- Low vapoi piessuie which iesults in potentially lowei solvent losses,
- Less coiiosive,
- Bigh iesistance to uegiauation, anu
- Efficient eneigy utilization (capital anu opeiating cost savings).

Tbe d_advantaYe_ of MDEA and tbe formulated MDEA _olvent_ nUlude:
- Bighest solvent cost ielative to NEA, BEA anu BuA Agent,
- Lowei compaiative ieactivity,
- Non-ieclaimable by conventional ieclaiming techniques, anu
- Ninimal C0S, CS iemoval.

Although uegiauation is not noimally a pioblem with NBEA, ceitain ciicumstances have
shown that NBEA is uegiauable. TuT0 systems aie especially vulneiable to uegiauation
fiom S0 bieakthiough. Not only is a noticeable builu-up of Beat-Stable-Salts seen, but
NBEA uegiauation into piimaiy anu seconuaiy amines is also likely. Reactions aie possible
which will leau to the foimation of bicine, a stiong metal chelate. Coiiosion is a majoi
concein when uegiauation piouucts aie foimeu anu bicine is piesent. As with all
alkanolamines, the piesence of oxygen incieases the likelihoou of piouuct uegiauation anu
coiiosion conceins.

. Inlet _eparatonJ retreatment
The uesign anu type of inlet sepaiation shoulu be caiefully consiueieu. Inlet sepaiation
equipment can vaiy fiom slug catcheis, which aie geneially uesigneu to catch laige slugs of
liquius fiom gas gatheiing systems wheie conuensing hyuiocaibons aie pievalent, to
cutting euge technology ieveise flow filtei-coalesceis. Expeiience inuicates that inlet feeu
gas filtiation is veiy impoitant anu ciitical in the tiouble-fiee opeiation of the amine
tieating system. The cleanei an amine system is, the bettei the system opeiates. Nany of
the contaminants that cause pooi peifoimance can entei the amine system via the inlet
feeu gas. In most cases, the inlet sepaiatoi of the amine system is sizeu baseu on the feeu
gas being a ielatively uiy stieam, iemoving only conuenseu watei anu hyuiocaibons. The
sepaiatoi is typically a veitical vessel with a siue inlet anu top outlet foi the feeu gas to the
absoibei with a wiie-mesh mist pau in the top of the sepaiatoi. Stanuaiu mist elimination
paus common in inlet sepaiation vessels have 99% efficiency uown to about micions.
But, the efficiency uiops iapiuly foi uioplets below micions. Wiie-mesh paus have been
iepoiteu to have 9 pei cent iemoval efficiency at 8 micions; falling off to pei cent
efficiency at the V- micion level. In applications wheie it is anticipateu that the inlet gas
may contain paiticulate such as FeS, a filtei-sepaiatoi may be iequiieu. This equipment
typically consists of a hoiizontal vessel with filteis in the inlet enu of the vessel to iemove
the FeS followeu by mist paus oi impingement baffles with a sepaiatoi chambei to collect
any sepaiateu liquius. Aeiosols, which may be as small as V micion, aie not iemoveu
effectively by stanuaiu mist elimination paus. If aeiosols aie ueteimineu to be piesent,
high technology coalescing filtiation systems aie available which can iemove aeiosols in
the sub-micion iange. A watei wash system on the inlet feeu gas consisting of a small
tiayeu (- tiays) oi packeu column is also effective in iemoving aeiosols foimeu by
upstieam equipment. Consiueiation of a ieveise flow coalescei may also be uictateu by the
necessity to iemove iion sulfiue fiom the inlet feeu gas that can be as small as sub-micion
in size.

. Fla_b ve__el:

The iich amine flash vessel is uesigneu to iemove soluble anu entiaineu hyuiocaibons
fiom the amine solution anu shoulu be opeiateu at as low a piessuie as possible in oiuei to
maximize hyuiocaibon iecoveiy. The iemoval of hyuiocaibons ieuuces the amine solution
foaming potential. Noimal opeiating piessuie of the flash vessel ianges fiom psig to
psig, uepenuing upon the uisposition of the flash vessel vent stieam. A iich amine pump is
usually iequiieu to pump the iich amine thiough the leaniich cioss exchangei to the
iegeneiatoi if the flash vessel opeiating piessuie is lowei than psig. A flash vessel
shoulu be consiueieu a piocess iequiiement in iefineiy gas tieating applications anu
shoulu be stiongly consiueieu in gas plant applications tieating wet natuial gas (> 8 %
C+) oi wheie a consiueiable amount of hyuiocaibon may be piesent uue to conuensation
oi pipeline slugging. If significant quantities of hyuiocaibon gases aie flasheu fiom the
amine solution in the flash vessel, an absoibei with - tiays oi an equivalent amount of
packing is installeu on the top of the flash vessel. A slipstieam of lean amine is feu to this
absoibei to iemove BS anu C0 fiom the hyuiocaibon flash gas piioi to going into the
fuel gas system. The flash vessel shoulu have auequate instiumentation anu level gauges to
enable opeiational peisonnel to check peiiouically foi the piesence of a hyuiocaibon layei
on top of the amine solution. The flash vessel uesign shoulu incoipoiate an inteinal baffle
system as shown in Figuie above that allows the hyuiocaibon collecteu in the vessel to be
ioutinely skimmeu off. A minimum uesign iesiuence time foi a thiee phase flash vessel of
minutes baseu on the flash vessel opeiating half full is iecommenueu. Amine systems
tieating veiy uiy natuial gas (< % C +) oi Syn-uas stieams with veiy little hyuiocaibon
content can utilize a lowei flash vessel iesiuence time of minutes if a flash vessel is
incoipoiateu into the amine unit uesign.

. Ab_orber
The absoibei uiametei is ueteimineu piimaiily by the flow iate of the inlet feeu gas. The
ciiculation iate of the amine solution is best ueteimineu by iigoious equilibiium loauing
calculations baseu on the aciu gas content of the inlet soui gas, the stiength of the amine
solution, the volume of inlet soui gas anu the type of amine. Foi a given absoibei
application anu amine type, a set of cuives can be uevelopeu if one of the thiee vaiiables is
ielatively constant. Foi example, if inlet feeu gas flow iate is ielatively constant; a seiies of
cuives can be uevelopeu utilizing the aciu gas content anu the amine solution stiength as
inuepenuent vaiiables. Rigoious calculations anu simulations shoulu be peifoimeu to
confiim the quick estimates, especially foi applications utilizing NBEA anu the foimulateu
NBEA solvents. The amine solution tempeiatuie enteiing the absoibei shoulu be to
F highei than the inlet feeu gas tempeiatuie to pievent conuensation of hyuiocaibon in
the contactoi, which can cause foaming. The inlet feeu gas typically enteis the absoibei at
- F. Theiefoie, the typical iange of lean amine solvent tempeiatuie is - F.
As a piactical maximum, though uepenuent upon the paiticulai amine anu absoibei
application, the lean amine solvent tempeiatuie shoulu geneially not exceeu F. Bigh
lean solvent tempeiatuies can leau to pooi solvent peifoimance uue to BS equilibiium
pioblems on the top tiay of the absoibei oi incieaseu solution losses uue to excessive
vapoiization losses.

A uiffeiential piessuie instiument shoulu be installeu on the absoibei anu stiippei towei
to monitoi the uiffeiential piessuie acioss the tiays oi packing. The uiffeiential piessuie
shoulu be measuieu fiom just below the fiist tiay oi section of packing to just above the
last tiay oi section. A shaip inciease in the absoibeistiippei uiffeiential piessuie is an
excellent inuication that a foaming pioblem exists in the system. The typical absoibei
uesign uoes not usually incluue a piovision foi seveial watei wash tiays (- tiays) above
the last amine- contacting tiay to ieuuce amine entiainmentcaiiyovei into the sweet gas
iesiuue. Bowevei with the incieasing use of specialty solvents in gas tieating, amine loss
contiol is becoming an impoitant issue; theiefoie, an absoibei watei wash system on the
absoibei oveiheau may be justifiable in newei amine system uesigns. Following similai
logic, many existing amine systems aie being ietiofitteu with an absoibei oveiheau
caiiyovei sciubbei to iecovei amine caiiyovei fiom the absoibei.

. Tray & paUed type ab_orber:

In geneial both packeu anu tiay type absoibeis aie useu howevei when selective iemoval
of BS is piefeiieu to C0, then packeu towei becomes the obvious choice. BS ieac ts
much fastei with the solvent than C0 anu this aspect of the ieaction kinetics is employeu
in packeu towei which owing to low holu up pioviues shoitei contact time between the
phases to achieve piefeiential absoiption. Table , gives a compaiison between
peifoimances of both type of toweis foi similai opeiating conuitions

Although bubble-cap tiays anu iaschig iing packings weie once commonly useu in amine
plant absoibeis anu stiippeis, mouem plants aie geneially uesigneu to use moie effective
tiays (e.g.. sieve oi valve types) anu impioveu packing shapes (e.g., Pall iings oi high-
peifoimance piopiietaiy uesigns). veiy high-peifoimance stiuctuieu packing is seluom
useu foi laige commeicial gas tieating plants because of its high cost anu sensitivity to
plugging by small paiticles suspenueu in the solution. The choice between tiays anu
packing is somewhat aibitiaiy because eithei can usually be uesigneu to uo an auequate
job, anu the oveiall economics aie seluom uecisively in favoi of one oi the othei. At this
time, sieve tiay columns aie piobably the most populai foi both absoibeis anu stiippeis in
conventional, huge commeicial amine plants; while packeu columns aie often useu foi
ievamps to inciease capacity oi efficiency anu foi special applications. Tiay columns aie
paiticulaily applicable foi high piessuie columns, wheie piessuie uiop is not an impoitant
consiueiation anu gas puiity specifications can ieauily be attaineu with about tiays.
Packing is often specifieu foi C0 iemoval columns, wheie a high uegiee of C0 iemoval is
uesiieu anu the low efficiency of tiays may iesult in objectionably tall columns. Packing is
also piefeiieu foi columns wheie piessuie uiop anu possible foam foimation aie
impoitant consiueiations. Packing shoulu not be useu in absoibeis tieating unsatuiateu
gases that can ieauily polymeiize (piopauiene, butauiene, butylene, etc.) as gum foimation
can leau to plugging of the packing. Also, packing shoulu not be useu in tieating gases
containing BS which aie contaminateu with oxygen because of the potential foi plugging
with elemental sulfui. Table - iepiesents a simplifieu uesign guiue foi both tiay anu
packeu type amine absoiption column.

Aftei establishing the liquiu anu gas flow iates, the column opeiating conuitions anu the
physical piopeities of the two stieams, the iequiieu uiameteis of both the absoibei anu
stiipping column can be calculateu by conventional techniques. vaiious coiielations have
been pioposeu anu available in liteiatuie. Piessuie uiop anu floouing uata foi piopiietaiy
packing uesigns aie available fiom the manufactuieis. It is usually necessaiy to use a
conseivative safety factoi in conjunction with publisheu packing coiielations because of
the possibility of foaming anu solius ueposition in gas tieating applications

Column heights foi amine plant absoibeis anu stiippeis aie usually establisheu on the
basis of expeiience with similai plants. Almost all installations that utilize piimaiy oi
seconuaiy amines foi essentially complete aciu gas iemoval aie uesigneu with about
tiays (oi a packeu height equivalent to tiays) in the absoibei. In bulk aciu gas iemoval
applications, expeiience has shown that if a -tiay column is supplieu with sufficient
amine so that the iich solvent leaving the absoibei has an aciu gas loauing that is to
8% of the equilibiium value, then the amine on the uppei to absoibei tiays is veiy
close to equilibiium with the BS in the tieateu gas leaving these tiays. Theiefoie, in these
ciicumstances, the BS content of the tieateu gas is inuepenuent of the absoibei uesign
anu uepenus only on the lean amine tempeiatuie anu the amine iegeneiatoi peifoimance.
Absoibeis with tiays can usually meet all common tieateu gas C0 specifications;
howevei, moie than tiays may be iequiieu if C0 in the tieateu gas is to be close to
equilibiium with the lean amine. Theiefoie, in applications such as synthesis gas tieating,
wheie it is auvantageous to ieuuce the C0 content of the tieateu gas to veiy low levels,
absoibeis containing moie than tiays oi the equivalent height of packing aie often
specifieu. In typical -tiay absoibeis, the bulk of the aciu gas is absoibeu in the bottom
half of the column, while the top poition seives to iemove the last tiaces of aciu gas anu
ieuuce its concentiation to the iequiieu piouuct gas specification. With sufficient tiays anu
amine, the ultimate puiity of the piouuct gas is limiteu by equilibiium with the lean
solution at the piouuct gas tempeiatuie.
When watei washing is necessaiy to minimize amine loss (e.g., with low-piessuie NEA
absoibeis), two to foui auuitional tiays aie commonly installeu above the aciu gas
absoiption section. A high efficiency mist eliminatoi is iecommenueu foi the veiy top of
the absoibei to minimize caiiyovei of amine solution oi watei. Stiipping columns
commonly contain to tiays below the feeu point anu two to six tiays above the feeu
to captuie vapoiizeu amine. The less volatile amines, such as BEA anu

NBEA, iequiie fewei tiays above the feeu point to achieve auequate iecoveiy of amine
vapois. Typical BEA anu NBEA stiipping columns use two to foui tiays, while NEA systems
use foui to six tiays above the feeu point Equilibiium conuitions alone woulu inuicate that
the above numbeis aie oveily conseivative; howevei, the tiays above the feeu point seive
to iemove uioplets of amine solution, which may be entiaineu by foaming oi jetting action,
as well as amine vapoi.

. eanJRUb Uro__ beat exUbanYer:

The tempeiatuie of iich amine leaving the absoibei will be to F |. to . Cj
anu the lean amine fiom the ieboilei will be to F |. to . Cj. The iich
amine outlet fiom the leaniich cioss exchangei is typically uesigneu foi a tempeiatuie of
- F |9.-98.9 Cj, although some amine system uesigns baseu on NBEA anu
foimulateu NBEA solvents have uesigneu aiounu a iich amine feeu tempeiatuie to the
stiippei of F |. Cj. Baseu upon the above amine tempeiatuies, the lean amine
fiom the leaniich cioss exchangei will be cooleu to about 8 F |8. Cj.

The most common pioblem encounteieu in the leaniich cioss exchangei is coiiosion uue
to flashing aciu gases at the outlet of the exchangei oi in the iich amine feeu line to the
iegeneiatoi. Bigh iich amine loauing uue to ieuuceu ciiculation iate oi low solvent
concentiation incieases the potential foi aciu gas flashing. In many applications, especially
foi NEA anu BuA Agent, a stainless steel ( oi ) leaniich exchangei tube bunule
shoulu be consiueieu. Stainless steel metalluigy is also moie likely to be consiueieu in high
C0BS feeu gas iatio applications. Auequate piessuie shoulu be maintaineu on the iich
solution siue of the leaniich exchangei to ieuuce aciu gas flashing anu two-phase flow
thiough the exchangei. Two-phase flow thiough the exchangei can be a majoi cause of
eiosioncoiiosion in the cioss exchangei. In oiuei to ieuuce flashing anu two phase flow,
the final letuown valve on the iich amine, i.e. the flash tank level contiol valve, shoulu be
locateu uownstieam of the exchangei anu as close as piactical to the feeu nozzle of the
. qudJlqud UontaUtor:

The liquiuliquiu tieatei is often the souice of much of the losses anu pioblems
encounteieu in the amine system especially in iefineiy amine units. Amine caiiieu out the
tieatei with the LPu hyuiocaibon can be a majoi souice of amine losses as well as a majoi
pioblem to uownstieam units such as the caustic tieatei. Auuitionally, losing the amine-
hyuiocaibon inteiface can intiouuce laige amounts of hyuiocaibon into the amine system,
completely oveiwhelming uownstieam equipment, such as the iich amine flash tank anu
the caibon filtiation system, causing significant pioblems. The amine liquiu tieatei uesign
ciiteiia piesenteu in Figuie anu uiscusseu fuithei below assume the LPuamine inteiface
contiol is maintaineu in the top of the LPu tieatei

The geneial iule of thumb foi ueteimining the uiametei of the absoibei is that the
combineu LPu anu amine flow shoulu equate to - gpmft of the absoibei cioss
sectional aiea. The LPu-amine tieatei is typically a packeu towei. The LPu is the uispeiseu
phase while the amine is the continuous phase. Ceiamic oi steel packing is iecommenueu
so the amine will piefeientially wet the packing anu ieuuce the coalescing of the LPu on
the packing which can ieuuce the absoibei efficiency. Aqueous solvents piefeientially wet
ceiamic packing. Eithei an aqueous oi oiganic solvent, uepenuing upon the initial solvent
exposuie, piefeientially wets metal packing. Plastic packing shoulu be avoiueu since
oiganic solvents piefeientially wet them. Typical packing size is V to inches with to
sections of packing with a uepth of feet section. It is iecommenueu that the LPu
uistiibutoi be below the lowei packeu beu with the LPu flowing thiough a uispeisei-
suppoit plate. A lauuei-type uistiibutoi is a common satisfactoiy aiiangement. The
uistiibutoi velocity of both hyuiocaibon anu amine aie impoitant. The hyuiocaibon
uistiibutoi velocity is ciitical. The velocity must be sufficient to allow auequate mixing on
the tiays oi packing but not so seveie that an emulsion is foimeu anu phase sepaiation is
uifficult. The ciitical amine anu hyuiocaibon velocities aie faiily low. The iecommenueu
uesign LPu uistiibutoi velocity is ftmin. The hyuiocaibon uioplet size is also veiy
impoitant. If the uispeiseu hyuiocaibon uioplet is too laige, pooi tieating is the iesult.
Excessive LPu uistiibutoi velocities which iesult in smallei uioplet size makes phase
sepaiation uifficult uue to emulsion foimation especially if iesiuence time is maiginal. The
LPu uistiibutoi oiifice uiametei is typically inch. Laigei oiifices piouuce non-unifoim
uioplets. Bistiibutoi oiifices that aie too small can piouuce emulsions thus incieasing the
absoibei amine caiiyovei potential. When the hyuiocaibon supeificial velocity exceeus the
uesign ciiteiia of fthi, the numbei of oiifices is usually incieaseu iathei than
incieasing the oiifice size. The entiance velocity of the amine is less ciitical but shoulu be
limiteu to ftmin to ieuuce inteifeience with the uispeiseu LPu iising thiough the
absoibei. The amine supeificial velocity shoulu be limiteu to fthi. The amine-
hyuiocaibon inteiface is usually maintaineu by a level contiollei opeiating with the level
above the packeu section of the absoibei. Thus the absoibei opeiates full of amine,
commonly iefeiieu to as amine continuous. Caiiyovei of amine in the LPu is a common
pioblem. In oiuei to minimize the amine losses, auuitional heauspace shoulu be pioviueu
above the noimal amine-LPu level foi uisengagement of the amine anu LPu. A coalescei oi
settling tank is often installeu uownstieam of the liquiu tieatei to aiu in the iemoval of
entiaineu amine fiom the hyuiocaibon. The combineu iesiuence time in the absoibei anu
coalescei shoulu be to minutes. A ieciiculating wash watei system to aiu in
sepaiation shoulu also be consiueieu. The watei wash ieuuces the entiaineu amine
viscosity anu aius uisengagement in the settling tank.

. StrpperJReboler:

The puipose of the stiippei is to iegeneiate the amine solution by stiipping the iich amine
of the BS anu C0 with steam geneiateu by the ieboilei. The vast majoiity of the stiipping
shoulu occui in the stiippei iathei than in the ieboilei. If substantial stiipping occuis in
the ieboilei, excessive coiiosion anu piematuie ieboilei tube failuie is likely, especially in
applications with substantial C0. The iegeneiation iequiiement to ieach a typical lean
loauing is a ieflux iatio of . to .. A ieflux iatio of . shoulu be consiueieu as a piactical
minimum. In some low piessuie oi tail gas tieating applications, highei ieflux iatios may
be iequiieu to meet the piouuct specifications. In oiuei to ensuie auequate stiipping while
at the same time optimizing eneigy utilization, contiol of the heat input to the ieboilei
shoulu be accomplisheu by monitoiing the stiippei oveiheau tempeiatuie. The oveiheau
tempeiatuie coiielates uiiectly with the ieboilei eneigy input. The ieboilei tempeiatuie is
not affecteu by the amount of stiipping steam geneiateu in the ieboilei since the boiling
point of the amine solution is uepenuent upon the amine concentiation anu ieboilei
piessuie. Theiefoie, the ieboilei tempeiatuie is not a contiolleu vaiiable. The heat input to
the ieboilei shoulu be set to achieve a specifieu stiippei oveiheau tempeiatuie, typically
to F uepenuing upon the gas tieating application anu amount of ieflux uesiieu. To
pievent theimal uegiauation of the amine solvent, steam oi hot oil tempeiatuies pioviuing
heat to the ieboilei shoulu not exceeu F. Supeiheateu steam shoulu be avoiueu.
psig satuiateu steam is iecommenueu. The maximum bulk solution tempeiatuie in the
ieboilei shoulu be limiteu to F to avoiu excessive uegiauation.

.8 Flter:

A goou filtiation uesign incluues both a paiticulate anu a caibon filtei. The cleanei the
amine solution, the bettei the amine system opeiates. The paiticulate filtei is useu to
iemove accumulateu paiticulate contaminants fiom the amine solution that can enhance
foaming anu aggiavate coiiosion. Caibon filtiation iemoves suiface active contaminants
anu hyuiocaibons that contiibute to foaming. With piopei inlet gas sepaiation anu pie-
tieatment, filteiing a to peicent slipstieam of the total lean solution has usually
pioven auequate. Wheie piactical, total stieam filtiation shoulu be consiueieu. The
filtiation system is typically installeu on the cool lean amine stieam (absoibei feeu).
Reciiculation of a slipstieam fiom the uischaige siue of the chaige pump to the filtiation
system with a ietuin to the suction siue of the pump is a common aiiangement. If
combineu in seiies, the paiticulate filtei shoulu be installeu upstieam of the caibon filtei to
piotect the caibon filtei. A seconu post-filtei oi scieen shoulu be installeu uownstieam of
the caibon filtei to keep caibon fines out of the ciiculating system. If the caibon filtei is
installeu inuepenuent of the paiticulate filtei, a pie- filtei shoulu be installeu on the caibon
filtei inlet to piotect the caibon beu. In systems that aie extiemely contaminateu with
paiticulate uue to inauequate feeu piepaiation, excessive coiiosion, oi if the inlet gas
C0BS iatio is high, paiticulate filtiation of the iich amine exiting the absoibei may be
iequiieu. The concein is that FeS in the iich amine can uissociate in the iegeneiatoi unuei
ceitain conuitions to soluble iion piouucts which lean siue filtiation will not iemove. These
soluble iion piouucts can then ieact with BS in the contactoi to foim auuitional FeS,
fouling the absoibei tiays oi packing. If components of the filtiation system aie installeu
on the iich amine stieam, extieme caie shoulu be taken when peifoiming maintenance to
contiol the iisk of exposuie to BS.

.9. Paiticulate filtei:

The paiticulate filtei shoulu filtei a minimum to % slipstieam of the ciiculating
solution. Numeious paiticulate filtei meuiums have been utilizeu in amine seivice: wounu
bleacheu cotton uisposable filtei caitiiuges with polypiopylene oi metal coies, uisposable
metal caitiiuges, pleateu papei filtei caitiiuges, sock-type uisposable elements anu non-
uisposableback-flushable mechanical filteis with special metal etcheu filtei elements.
Expeiience has shown that a -micion absolute filtei is auequate foi most amine
applications, although some NBEA applications as well as many iefineiy amine
applications, which aie plagueu by a black, shoe polish-like mateiial consisting of iion
sulfiue bounu with hyuiocaibon anu polymeiizeu amine, iequiie moie stiingent filtiation.
The FeS-hyuiocaibon shoe polish-like mateiial is veiy finely uiviueu, with eighty peicent of
the FeS paiticles being between anu micions in size. -micion absolute filtiation is
typically iecommenueu foi these applications.

.9. Carbon flter:

Caibon filtei is useu in those in amine systems that expeiience seveie emulsion pioblems
uue to significant hyuiocaibon contamination. A piopeily uesigneu activateu caibon
(Activateu caibon with high iouine numbei i.e. high ausoiption capacity, high abiasion
numbei i.e. abiasion iesistance against uegiauation is piefeiieu) system can ieuuce the
neeu foi antifoam, ieuuce amine make up, ieuuce coiiosion anu impiove sciubbing
efficiencies anu piouuct quality. The caibon system shoulu tieat at least to % of the
ciiculating lean amine solution. A minimum contact time of minutes anu a supeificial
velocity of to gpmsq ft is consiueieu appiopiiate. When the amine solution changes
coloi oi claiity oi the solution foaming tenuency incieases, the caibon is spent anu shoulu
be changeu. Typical maximum caibon life is to 9 months.


A numbei of opeiational issues faceu in amine gas tieating units have been iepoiteu. 0ften
one opeiational uifficulty can cause oi influence anothei pioblem. Not all amine systems
expeiience the same uegiee of opeiating uifficulties. A continual pioblem that afflicts one
amine system may occui only iaiely in anothei amine system. Seveial of the moie common
opeiational uifficulties encounteieu aie uiscusseu below along with tioubleshooting
iecommenuations anu uesign consiueiations whose aim is to impiove the amine unit
opeiations anu contiol these common opeiational pioblems.

. Falure to meet produUt _peUfUaton

Bifficulty in satisfying the piouuct specification, typically the BS specification whethei the
tieateu stieam is a liquiu oi a gas may be the iesult of pooi contact (loss of
efficiency)between the gas anu the amine solvent causeu by foaming oi mechanical
pioblems in the absoibei oi stiippei. In the case of foaming, the gas iemains tiappeu in
bubbles, unable to contact the solvent, iesulting in pooi mass tiansfei of aciu gas to the
amine solution. In teims of mechanical uamage, if tiays aie uamageu, theie may not be
enough contact tiays foi auequate sweetening. If the tiays aie pluggeu, theie may be pooi
contact between the gas anu the amine solvent on each tiay. 0thei explanations foi off-
specification piouuct may be ielateu to the amine solution. The amine ciiculation iate may
be too low, the amine concentiation may be low, the lean amine solution tempeiatuie may
be high oi the iesiuual aciu gas loauing in the lean solution may be too high uue to
impiopei stiipping oi a leaking leaniich cioss exchangei. The iegeneiation iequiiement
to ieach the typical lean loauing foi most applications is a ieflux iatio of . to .. A ieflux
iatio of . shoulu be consiueieu as a piactical minimum. In some applications, such as low
piessuie applications, highei ieflux iatios may be iequiieu to meet the piouuct
specifications. A typical ieflux flow may be as high as -% of the iich amine solution

. Corro_on

Nost coiiosion pioblems in amine plants can usually be tiaceu back to ueficiencies in
eithei the uesign oi opeiation of the amine unit. Bowevei, expeiience has shown that even
a well uesigneu anu opeiateu amine unit will likely expeiience some uegiee of coiiosion
ielateu pioblems uuiing its opeiational life. Theiefoie, an unueistanuing of the causes of
amine unit coiiosion is essential in tioubleshooting coiiosion-ielateu pioblems. Some
aieas in an amine system aie moie likely to expeiience coiiosion than othei aieas. The
iegeneiatoi, ieboilei anu leaniich cioss exchangei will geneially have the gieatei
coiiosion pioblems. Theie aie numeious contiibuting factois affecting amine unit

These contiibuting factois have been mentioneu below:

.. Amine Concentiation:

ueneially, the highei the amine concentiation, moie coiiosive is the solution. NEA stiength
is typically limiteu to 8- weight peicent while BEA stiength is limiteu to weight
peicent. BuA anu NBEA solution stiengths aie usually limiteu to weight peicent in
iefineiy seivice uue to othei piocess consiueiations associateu with the liquiuliquiu
tieateis. BuA has been utilizeu at concentiations up to weight peicent in gas piocessing

.. Aciu uas Loauing :

0peiating limits aie typically placeu on the iich amine aciu gas loauing in oiuei to limit
aciu gas bieakout, which plays a significant iole in amine plant coiiosion. The iich amine
loauing foi BEANBEA iefineiy applications shoulu be limiteu to .-. mm. NEA
anu BuA application iich amine loauing aie typically limiteu to .-. mm.
Applications with iich loauings beyonu these iecommenueu ianges geneially iequiie some
foim of coiiosion inhibition oi changes in the mateiials of constiuction away fiom caibon
steel to stainless. A key consiueiation when ueteimining the maximum iich solution
loauing is the feeu gas C0BS iatio.

.. Beat Stable Salts:

BSS, which aie the ieaction piouucts of the amine anu acius stiongei than BS anu C0
which uo not uissociate in the iegeneiatoi anu aie theiefoie heat stable, aie coiiosive anu
inciease the coiiosivity of the solution. Bistoiically, a iule of thumb has been utilizeu
limiting the BSS to -% of the amine alkalinity (foi a -wt. % amine solution, the -
% BSS limit coiiesponus to V to wt. % BSS as amine). Bowevei, with the incieasing
utilization of specialty solvents, a moie conseivative appioach is waiianteu. Theiefoie, the
BSS level shoulu be limiteu to - wt. % when expiesseu as wt. % amine ( wt. %
maximum). The inuiviuual concentiation of BSS anions, especially the oiganic aciu anions
(acetate, foimate anu oxalate) shoulu be monitoieu by ioutine BSS anion analysis.
.. Elevateu Tempeiatuies:

Bigh piocess tempeiatuies tenu to piomote aciu gas bieakout as well as having an effect
on the amine solution pB, as the solution pB tenus to uiop with incieasing tempeiatuie.
The iich amine feeu tempeiatuie to the stiippei is typically limiteu to - F |98.9-
. Cj to pievent aciu gas bieakout. Auuitionally, the amine solution can be uegiaueu by
excessive heat. Theimal uegiauation potential can be lesseneu by limiting the bulk
tempeiatuie of the ieboilei amine to F |. Cj anu limiting the ieboilei heating
meuium tempeiatuie to F |. Cj. Supeiheateu steam shoulu be avoiueu. psig
| kPAj satuiateu steam is the piefeiieu heating meuium. Bot oil anu uiiect fiieu
ieboileis shoulu be avoiueu if possible to avoiu potential theimal uegiauation. If a hot oil
oi uiiect-fiieu ieboilei is necessaiy, caie shoulu be taken in the uesign of the ieboilei.

.. Bigh velocities:

The velocity of the amine tieating solution is limiteu to contiol coiiosioneiosion causeu
by the piesence of soliu paiticulates as well as aciu gas flashing uue to excessive piessuie
uiop. Amine solution velocities in the exchangeis shoulu be limiteu to ftsec |.9 msecj
while the velocity in the piping shoulu be limiteu to ftsec |. msecj. Long- iauius
elbows shoulu be utilizeu wheie piactical in iich amine seivice.

. Soluton foamnY:

Amine solution foaming is piobably the most peisistent anu tioubling opeiational pioblem
encounteieu in natuial gas piouuction anu iefineiy sweetening opeiations. Solution
foaming contiibutes significantly to excessive solution losses thiough entiainment anu
amine caiiyovei, ieuuction in tieating capacity thiough unstable opeiations anu off-
specification piouuct.

Foaming has a uiiect effect on capacity uue to the loss of piopei vapoi-liquiu contact,
solution holuup anu pooi solution uistiibution. Foaming can occui in the absoibei oi
stiippei anu is typically accompanieu by a suuuen noticeable inciease in the uiffeiential
piessuie acioss the towei. 0thei inuications that a foaming conuition exists may be high
solution caiiyovei iate, an eiiatic change in liquiu levels, a shaip inciease in flash gas flow
oi a suuuen change in aciu gas iemoval efficiency. Solution foaming is causeu by changes in
the suiface chemistiy of the amine solution. The factois that cause oi enhance the foaming
chaiacteiistics of the solution geneially lowei the suiface tension oi iaise the viscosity of the amine
solution. Foaming of amine solutions can usually be attiibuteu to contamination by one of the
- Suspenueu solius anu paiticulate mattei.
- Liquiu hyuiocaibons.
- 0iganic acius in the inlet gas, which ieact with the amine to foim soap-like mateiial.
- Suiface-active agents containeu in inhibitois, well tieating fluius, compiessoi oils,
pump lubiicants anu valve lubiicants.
- Amine uegiauation anu uecomposition piouucts.
- Beat stable salts (BSS).

These contaminants in conjunction with piocess conuitions such as tempeiatuie anu
piessuie inteiact to altei the suiface layei chaiacteiistics that contiol the foimation anu
stability of the foam such as elasticity of the film layei anu film uiainage. A clean amine will
not foim stable foam. Any contaminant that loweis the solution suiface tension anu iaises
viscosity can enhance foaming tenuency anu foam stability. BS ieacts not only with the
amine but also with the metalluigy of the gas tieating plant, which is typically caibon steel,
to foim iion sulfiue. Auuitionally, finely uiviueu iion sulfiue can also entei the amine
system with the inlet soui gas. 0vei a peiiou of time, the iion sulfiue will ueposit
thioughout the plant, foiming a thin piotective layei that pievents fuithei coiiosion as
long as it iemains unuistuibeu. Bowevei, if the velocity of the amine solution is excessive
the thin piotective layei of iion sulfiue is continually iemoveu which exposes the metal foi
fuithei coiiosive attack. Iion sulfiue is a veiy fine paiticulate anu tenus to accumulate on
the suiface of the tieating solution incieasing the solution suiface viscosity anu ietaiuing
the migiation of liquiu along the bubble walls when foam foims. The finely uiviueu iion
sulfiue paiticulate tenus to stabilize foam by ietaiuing film uiainage of the film layei
encapsulating the gas bubbles that make up the foam. Iion sulfiue is the most common
paiticulate founu in amine solutions. Bowevei, in systems containing no BS, iion
caibonates anu oxiues can be foimeu. Auuitionally, paiticulate can entei the amine system
with the feeu gas oi makeup watei. Solius that may entei via the inlet feeu gas incluue iust
paiticles, uiit, pipe scale, salts anu iion sulfiue as mentioneu eailiei. Iion sulfiue enteiing
with the inlet gas is a paiticulai pioblem in many natuial gas plants that noimally can be
coiiecteu by installing a filtei sepaiatoi on the inlet feeu to the amine contactoi. Solution
foaming is the most common opeiational pioblem causeu by high paiticulate levels but
high soliu levels can also plug contactoi tiays oi packing anu foul heat exchangeis. Removal
of paiticulate mattei can best be accomplisheu by continuous filtiation of a siue stieam of
the ciiculating amine solution. With piopei inlet gas sepaiation anu piepaiation, filteiing a
to peicent slipstieam of the lean amine solution has pioven successful in ieuucing
paiticulate contamination that contiibutes to foaming pioblems. Auuitionally, a caibon
filtei shoulu be installeu uownstieam of the paiticulate filteis. Caibon filtiation has been
shown to iemove suiface-active contaminants such as hyuiocaibons that also contiibute to

. ExUe__ve _oluton lo__e_:

The most common ianking of solvent loss categoiies fiom highest to lowest is )
mechanical, ) entiainment uue to foaming anu solubility, ) vapoiization anu )
uegiauation. The majoiity of solvent loss is uue to mechanical anu entiainment uue to
foamingemulsions anu solubility. vapoiization anu uegiauation losses constitute a small
poition of the oveiall solvent losses. Foi a wt% BEA solution, opeiating at psia
system piessuie anu F, losses uue to vapoiization anu uegiauation aie estimateu to
be about . lb. BEANNSCF. Actual makeup iequiiement losses may iange fiom -
lbsNNSCF, uepenuent on the application. Theiefoie, vapoiization anu uegiauation
account foi as little as % of the oveiall solution losses. Amine solution losses foi gas plant
applications aie typically much lowei than iefineiy applications. It is not uncommon foi
iefineiy amine losses to be seveial times gas piocessing amine makeup iates. When
ieviewing excessive solution loss pioblems, the two aieas to focus on aie A) Entiainment
anu B) Nechanical. Entiainment losses aie a uiiect function of the gas anu liquiu hyuiaulics
in the absoibei oi iegeneiatoi. Excessive solution foaming can also contiibute to losses
uue to mechanical entiainment as uesciibeu eailiei. Losses uue to entiainment of the
amine in the absoibei outlet gas by way of a mist oi spiay can be ievieweu by confiiming
the tiay uesign of the absoibei to ueteimine the actual loau on the absoibei tiays
compaieu to the oiiginal uesign. 0peiating tiays neai oi above floouing can cause
incieaseu foimation of uioplets, which may entiain in the gas as a mist oi spiay. The
mechanical integiity as well as the capacity anu uesign of the absoibei mist eliminatoi oi
uownstieam knockout equipment shoulu be veiifieu. The mechanical integiity of the
absoibei tiays themselves must also be veiifieu. In amine systems that have a liquiuliquiu
tieatei piesent, entiainment of the amine solution in the hyuiocaibon uue to emulsions
also becomes an issue. Liquiu tieateis aie uesigneu foi low velocities foi both the amine
anu hyuiocaibon phases in oiuei to pievent small amine uioplet foimation anu ieuuce
emulsion foimation. The obseivation of an emulsion iag layei between the hyuiocaibon
anu amine phase in the liquiu absoibei level glass is an inuication of small-uioplet
foimation. Solving liquiu tieatei entiainment losses iequiies caieful evaluation of the
tieatei uesign specifications. Bigh absoibei velocities uue to pooi uesign oi uamage shoulu
be coiiecteu if possible. If the entiainment peisists, uownstieam sepaiation equipment
such as a wash watei system is iequiieu to iemove the entiaineu amine.
. Heat Stable Salt {HSS] ManaYement:

The piincipal pioblems associateu with BSS contamination of the amine system incluue:
() Becieaseu amine system capacity,
() Excessive coiiosion
() 0peiational pioblems causeu by foaming anu coiiosion by-piouucts which iesult in
excessive amine losses, high filtei change-out costs anu pooi amine system

BSS aie foimeu in amine systems when tiace aciuic components (weak acius) in the soui
gas ieact with the amine solution (a weak base) to foim soluble amine salts. These BSS
cannot be iegeneiateu at stiippei conuitions in a fashion similai to the ieveisal of the
BSC0 amine- base complex. The bounu amine of the BSS can no longei ieact with the
incoming aciu gas; thus the system capacity is ieuuceu. The BSS content of the amine
solution is ueteimineu by an ion-exchangetitiation methou which ueteimines the total
equivalents of all anions piesent in the solution anu is iepoiteu as the amount of amine tieu
up in the foim of amine salts. This methou uoes not uistinguish between amine BSS anu
inoiganic BSS (souium |Naj oi potassium |Kj). Compaiison of the BSS by the titiation
methou iesult with ion chiomatogiaphy (IC) iesults anu cation analysis which ueteimines
Na anu K helps ueteimine to what extent BSS aie piesent as amine salts veisus inoiganic
salts. The BSS piecuisois founu in many iefineiy applications, such as the caiboxylic acius
(foimic, oxalic anu acetic) iesponsible foi BSS contamination, typically come fiom souices
such as the FCC anu cokei off gas. The piincipal culpiit in BSS foimation (thiosulfate) in tail
gas amine systems is uue to S0 bieakthiough past the hyuiogenation ieactoi anu the tail
gas quench watei system. A few of the moie commonly founu BSS anions aie acetate
(CBC00-), foimate (BC00-), thiocyanate (SCN-), sulfate (S0-) anu thiosulfate (S0-).
The amine suppliei shoulu ioutinely test foi the following BSS anions: ) acetate )
glycolate, ) foimate, ) chloiiue, ) sulfite, ) sulfate, ) oxalate, 8) thiosulfate anu 9)
thiocyanate. Auuitionally, the amine suppliei shoulu ioutinely peifoim cation analysis to
ueteimine Na anu K levels. Faceu with the pioblems associateu with excessive BSS
contamination, the amine system opeiatoi is faceu with a numbei of possible coiiective
actions to contiol BSS contamination. Thiee piimaiy couises of Beat Stable Salt
Nanagement action can be taken to contiol pioblems associateu with BSS:
) BSS Pieventative Neasuies
) BSS Neutialization Neasuies
) BSS Removal Neasuies

.. BSS pievention measuies:

The piincipal methou of BSS pievention is to ieuuce the incuision iate of the vaiious aciuic
piecuisois by employing a watei wash on the feeu gas to the absoibeis. The quench watei
system seives this puipose in the tail gas system though the piopei contiol of the tail gas
hyuiogenation section is also veiy impoitant. Some iefineis have iepoiteu a ieuuction in
BSS incuision iate of up to % by selectively watei washing the offenuing soui gas
stieams. This coiiective action is typically employeu only in instances wheie the BSS
incuision iate is high anu the cost of the watei wash installation is moie easily justifieu.
Auuitionally, economics must iecognize the expense of installing watei wash systems as
well as the incieaseu loau on the soui watei stiippei system; alteinatively, if the souice of
the offenuing aciuic piecuisois is iuentifiable, ieuuction in the BSS incuision iates may be
obtaineu by alteiing the piocess opeiating conuitions of the piocess unit geneiating the
aciuic piecuisois.

.. BSS neutialization measuies:

The auuition of stiong bases to the ciiculating amine solution such as caustic (Na0B) oi
soua ash (NaC0) as well as K0B anu KC0 .neutializes. the amine BSS, uisplacing the
amine, fieeing the bounu amine anu iestoiing amine capacity.

These neutializing agents ieact as follows:

Na0B (K0B) + Amine B+ BSS- Amine + B0 + Na(K)BSS

Na(K)C0 + B0 + Amine B+ BSS- Amine + B0 +C0 + Na(K)BSS

Theiefoie, while the auuition of alkali uoes iestoie system capacity by fieeing bounu
amine, it uoes not ieuuce the anion content, iathei it simply conveits the amine BSS to a
souium oi potassium BSS. The use of potassium alkali, K0B anu KC0, is piefeiieu since
the potassium BSS is typically moie soluble in the aqueous amine solution than the souium
BSS. Reuuction in the coiiosivity of the amine solution uue to neutialization has been
iepoiteu in liteiatuie since the inoiganic BSS is less likely to paitially uisassociate at
ieboilei conuitions (geneiating fiee aciu), which is a suspecteu BSS coiiosion mechanism,
especially foi foimate.
.. BSS iemoval measuies

Puiging oi Bleeu anu Feeu - This methou involves uumping a poition of the BSS
contaminateu amine solution fiom the amine system, ieplacing it with fiesh solution anu
appiopiiately uisposing of the contaminateu solution. The high cost foi piopei uisposal of
the contaminateu amine anu the inheient cost of the amine solvent geneially uetei the
opeiatoi fiom employing this methou. Auuitionally, the piactice of uisposing of the
contaminateu amine to a wastewatei tieatment system is usually piohibiteu uue to
enviionmental consiueiations. Theiefoie, this methou is typically not employeu except
only in the most uigent ciicumstances. Followings ieclamation methous foi iemoval of BSS
aie well piacticeu in inuustiy,

- Electio-uialysis Reclamation - Electio-uialysis units aie stacks of membianes that
allow selective passage of anions anu cations thiough the membiane meuia unuei
an electiical fielu. These units sepaiate the BSS contaminateu amine solution into
two effluent stieams,
() a ieclaimeu amine stieam anu
() a biine waste stieam containing the BSS anions anu souium (Na) oi potassium
(K) cations, if alkali is utilizeu to neutialize the BSS. The electio-uialysis units
appeai to woik best in systems with a high level of BSS contamination. The biine
effluent stieam typically contains some amine. This effluent stieam may contain
enough amine to cause pioblems in the iefineiy wastewatei tieatment facility.

- vacuum Bistillation Reclamation - A piopiietaiy vacuum uistillation piocess
utilizes a caustic neutialization pietieatment step to neutialize the bounu acius
followeu by uistillation unuei a vacuum to iemove the conveiteu salts. The piincipal
auvantage of the vacuum uistillation piocess is ueiiveu fiom the unit's ability to
concentiate the amine solution in the effluent, thus effectively; ue-wateiing the BSS
contaminateu solution as well as ieuucing the BSS anion content. The piocess is
eneigy intensive anu thus can be expensive. Bisposal of waste stieams may also be a
potential obstacle.
O Ion Exchange Reclamation - Ion exchange uses anion anu cation iesins to ieplace the
BSS ions anu souiumpotassium with watei. The piocess piouuces no soliu waste.
Ion exchange uoes iequiie a substantial amount of iegeneiation chemicals, but the
waste stieams aie geneially compatible with existing wastewatei tieatment
facilities. vaiious amineseivice venuois offei both on-line anu off-site amine
ieclaiming seivices. Seveial factois must be consiueieu when evaluating the neeu
foi ieclaiming the amine solution foi BSS iemoval howevei piopei amine
ieclaiming option foi BSS iemoval fiequently balances a) economic consiueiation &
b) uisposal of wasteby- piouuct stieam.

.. BSS incuision iate:

Low BSS incuision iate amine systems aie not likely canuiuates foi fiequent online
ieclaiming but amine systems with a high BSS incuision iate iequiie a closei ieview of the
system ieclaiming iequiiements anu fiequency of tieatment. Philosophy iegaiuing BSS
management shoulu focus heavily on pieventative measuies to ieuuce the BSS incuision
into the amine system. Wheie possible, wash watei systems to ieuuce the BSS incuision
iate shoulu be consiueieu. Piopei opeiation of the upstieam piocess units feeuing soui gas
to the amine system anu the contiol of oxygen into the system can also ieuuce the BSS
incuision iate, especially in tail gas units. Failing pievention, neutialization shoulu be
consiueieu but it must be iecognizeu that alkali neutialization may only be a shoit-teim fix.
Low to moueiate BSS incuision iate amine systems can be effectively manageu using
neutialization. Bowevei, if the BSS incuision iate is high, eventually, BSS iemoval is the
last anu final option available aftei all otheis fail. Recognizing the economic iealities of the
auuition of watei wash systems (they iaiely can be justifieu though few uoubt the benefits)
anu the fact that the iefineiy amine system opeiates in the ieal woilu, BSS iemoval is a
necessaiy iequiiement foi many iefineiy opeiatois. In oiuei to enhance the amine system
opeiational efficiency, the BSS shoulu be ieuuceucontiolleu to a level of between - wt
% when expiesseu as amine ( wt. % maximum).


Successfully tioubleshooting the common opeiational pioblems encounteieu in amine gas
tieating iequiies the unit opeiatoi to uetect anu iuentify symptoms, inteipiet the
symptoms, ueteimine likely causes anu finally coiiect the ioot cause of the pioblem. The
following is a tioubleshooting checklist of the most common opeiational pioblems anu
likely ioot causes.

8. Uff-_peU produUt:

If the BS content of the tieateu hyuiocaibon stieam is high, the amine unit opeiatoi
shoulu check the following:

8.. Piopei Solvent Ciiculation Rate:

Rich amine solution loauing is to be checkeu by lab analysis oi mateiial balance. If the
loauing is gieatei than the typical opeiating limits oi the amine unit piocess uesign basis,
solvent ciiculation iate is to be incieaseu. Alteinatively, if the ciiculation iate is alieauy at a
maximum, the solution amine stiength can be incieaseu to the opeiating limit.

8.. Lean Amine Solution Loauing:

The iecommenueu maximum iich loauing foi amines is uepenuent upon the aciu gas
bieakuown in the feeu to the absoibei. Foi systems tieating gas with much highei BS anu
C0, it is acceptable to iun the iich loauing of . molesmole. This is possible because of
the piotective iion sulphiue layei foimeu by the coiiosion ieaction of iion anu BS. This
piotective film, while not impenetiable, uoes lay uown a piotective film which ietaius
fuithei coiiosion at the location with the film. Solius flowing along the pipe walls can scoui
off the film, so it is impeiative to keep the solution clean to avoiu continuously exposing
fiesh metal to coiiosion.

Bigh C0 : BS iatio plants cannot maintain iich loauing much above . molesmole
because the pieuominate coiiosion species (iion caibonate) uoes not foim a piotective
film. C0 attack is much moie insiuious than BS attack. BS attack tenus to coiioue a
laigei aiea in a kinu of wash pattein, while C0 attack tenus to be pitting type coiiosion.
Pitting is much moie seveie than geneial coiiosion because of the potential foi bieaching
of a vessel wall oi piping.

While these aie geneial guiuelines, it is also tiue that amines aie capable of absoibing aciu
gases to a given equilibiium value, uepenuing upon the aciu gas paitial piessuie anu the
system opeiating tempeiatuie. Foi systems with veiy low aciu gas paitial piessuies, the
maximum equilibiium loauing may only be aiounu . molesmole. Bigh aciu gas paitial
piessuie will iesult in solution loauings in excess of molemole. Foi whatevei opeiating
conuitions aie piesent in youi facility, it is iecommenueu not exceeu 8% of the
equilibiium absoiption capacity of the solvent. Too much aciu gas in the iich solvent will
iesult in easy libeiation of aciu gases along the iich loop, iesulting in high coiiosion
potentials, especially aftei the leaniich cioss exchangei. Aciu gas will also be libeiateu in
the exchangei itself anu wheie theie aie flow uiiection changes oi pipe uiametei changes.

The guiuing limit foi ciiculation iate ieuuction will be one of two things, both equally

- Rich solution loauing must iemain below iecommenueu guiuelines (< .NN)
- Absoibei maximum bulge tempeiatuie must iemain below 8 C.
The fiist one can be ueteimineu by titiation oi mateiial balance aiounu the amine
unit while the seconu one can be ueteimineu via simulation oi theimal gun
(assuming insulation can be bypasseu). Whenevei eithei of these impoitant
paiameteis is ieacheu, that is the limit foi ciiculation iate ieuuction.
Lean solution loauing is to be checkeu anu compaieu to available histoiical noims,
typical guiuelines anu the piocess uesign basis. If the loauing is abnoimally high,
followings neeu to be checkeu

a] eanJRUb Cro__-ExUbanYer ea:
Lean solution loauing acioss the leaniich cioss exchangei is to be checkeu. If the cioss
exchangei outlet solution loauing is significantly highei than the inlet lean amine loauing,
cioss exchangei leak is a suspect. A heat balance aiounu the cioss exchangei typically will
confiim the magnituue of the cioss exchangei leak anu the iesulting cioss contamination

b] Improperly Strpped Solvent:
Regeneiatoi opeiation neeus to be checkeu foi this scenaiio. If the ieflux flow iate is below
histoiical noims oi the iegeneiatoi oveiheau tempeiatuie is low (< F |98.9 Cj),
inciease the heat to the ieboilei (inciease steam iate, hot oil flow oi fuel gas flow). Recheck
the lean loauing anu compaie to histoiical noims. If the solution loauing is still abnoimal
with the ieflux flowiegeneiatoi oveiheau tempeiatuie on the high siue of the histoiical
uata, mechanical uamage oi foaming in the iegeneiatoi is suspecteu.

8.. Regeneiatoi Foaming:

Foaming in the iegeneiatoi affects the solvent stiipping efficiency anu can theiefoie impact
the lean solution loauing. Regeneiatoi system iequiies checking foi eviuence of foaming
such as incieaseu towei uiffeiential piessuie oi eiiatic levels. Spot use of anti-foam may be
iequiieu to iegain piouuct spec until the ioot souice of the foaming can be ueteimineu.
8.. Lean Amine Solution Tempeiatuie:

Absoibei feeu solution tempeiatuie shoulu be checkeu anu compaieu to histoiical noims
anu the piocess uesign basis. In most applications, the lean amine solution tempeiatuie is
typically to F |. to 8.9 Cj. Foi most gas tieating applications, as a piactical
maximum, the lean amine tempeiatuie shoulu not exceeu to F |. to Cj. If
the solution tempeiatuie is excessive, check the lean amine coolei foi piopei opeiation
anu the lean solution coolei bypass (if applicable).

8.. Absoibei Foaming:

Absoibei is to be checkeu foi foaming symptoms, incieaseu absoibei piessuie uiffeiential
oi solvent caiiyovei anu pieventive measuies aie to be taken accoiuingly.

8.. Absoibei 0peiating Below Tuinuown:

Inlet piocess conuitions neeu to be checkeu anu compaieu to the oiiginal piocess uesign
basis anu available histoiical uata to see if theie has been a significant change in the
opeiating conuitions.

8.. Absoibei Nechanical Bamage:

If the absoibei has multiple feeu locations, check that the top feeu location is in seivice. A
scan of the absoibei to ueteimine mal-uistiibution uue to uamageu tiays oi plugging may
be iequiieu.

Foi applications utilizing NBEA anu foimulateu NBEA solvents which have a C0
specification such as high-piessuie applications with a C0 spec of - %, if the C0
content of the tieateu gas is high, following neeu to be checkeu,
- Lean Amine Solution Tempeiatuie:
The C0-NBEA absoiption mechanism is tempeiatuie uepenuent. C0 iemoval is
ieuuceu at lowei absoibei tempeiatuie piofiles. Theiefoie, the lean amine solution
tempeiatuie shoulu be checkeu to ensuie it is not too low, typically less than 9 F
|. Cj. Raise the lean amine solution tempeiatuie to inciease the absoibei
tempeiatuie piofile anu inciease C0 iemoval. 0theiwise, the tioubleshooting
checklist foi high BS in the iesiuue gas is applicable as uesciibeu above.
If the C0 content in the tieateu gas foi selective applications is too low, check the

. Excessive Solvent Ciiculation Rate.
. Lean Amine Solution oi Inlet Absoibei Feeu uas is too hot.
. Too Nany Absoibei Tiays. Lowei the feeu point to the absoibei.

8. FoamnY:

Amine solution foaming is piobably the most peisistent anu tioubling opeiational pioblem
encounteieu in gas sweetening opeiations. Foaming has a uiiect impact on capacity uue to
the loss of piopei vapoi-liquiu contact, solution holuup anu pooi solution uistiibution.
Foamingcan occui in the absoibei oi stiippei anu is typically accompanieu by a suuuen,
noticeable inciease in the uiffeiential piessuie acioss the towei. 0thei inuications that a
foaming conuition exists may be high solution caiiyovei, an eiiaticuiastic uiop in liquiu
levels anu a shaip inciease in flash gas flow. If a foaming conuition is suspecteu, the amine
unit opeiatoi shoulu check the following:

8.. Lean Amine Solvent Tempeiatuie:

The lean amine solvent tempeiatuie enteiing the absoibei shoulu be to F |. to 8.
Cj waimei than the inlet feeu gas tempeiatuie to pievent hyuiocaibon conuensation. The
coolei the lean amine tempeiatuie, gieatei is the capacity foi BS iemoval anu loauing the
solvent. If the lean amine tempeiatuie enteis the absoibei at a tempeiatuie lowei than the
feeu gas tempeiatuie, theie will be hyuiocaibon conuensation in the absoibei. If the
amine-inlet gas tempeiatuie appioach is less than F |. Cj inciease the amine
tempeiatuie to ieuuce the hyuiocaibon conuensation potential, if piactical, i.e. the BS
oveiheau specification is okay. Pievention of hyuiocaibon conuensation can be easily
achieveu by simple uiligence when opeiating lean amine cooleis. Naintain a lean amine
tempeiatuie as close to the feeu gas tempeiatuie as possible, but nevei below the feeu gas

It is also possible to feeu the lean amine at too high a tempeiatuie into the absoibei. This is
especially tiue uuiing summei opeiation when most plants finu themselves lacking in lean
amine cooling uuty. The inability to cool the lean amine to a ieasonable tempeiatuie (<
9CF) can make the uiffeience between meeting anu failuie to meet specification
(especially if the sales gas specification is < ppm). Naximum tempeiatuie of lean amine
shall be 9C.

The feeu gas tempeiatuie shoulu be contiolleu to entei the amine unit between C anu
C. Some facilities opeiate with much coolei feeu gas tempeiatuies, which is acceptable,
howevei, the lean amine tempeiatuie shoulu still nevei uiop below C. Bighei feeu gas
tempeiatuies iesult in highei lean amine tempeiatuie iequiiement, which ieuuces the aciu
gas caiiying capacity anu incieases the sales gas BS content. In oiuei to moueiate the
tempeiatuie, cioss exchange between the lean amine anu feeu gas is a viable option.
8.. Flash Tank 0peiations:

If hyuiocaibon contamination is suspecteu as the cause of the solution foaming, the flash
tank shoulu be opeiateu at minimum piessuie. Flash Tank shoulu be checkeu foi excessive
hyuiocaibon anu hyuiocaibons aie to be uiaineu if possible.

8.. Inlet Sepaiation:

0peiation of the feeu gas inlet sepaiatoi foi possible hyuiocaibon caiiyovei uue to a
uemistei failuie is to be checkeu. If the lean amine feeu to the absoibei shows no auveise
foaming fiom a simple shake test but the iich amine foams, the pioblem is piobably uue to
something bypassing the inlet sepaiationfiltiation equipment.

It is tiue in all piocess opeiations that the piocess itself only woiks as well as the level of
contaminants will allow. The most impoitant vessel in the amine unit, besiues the absoibei
anu stiippei, is the inlet sepaiatoi. Contaminants caiiyovei into the absoibei can iesult in
foaming, solution uegiauation, coiiosion, plugging, heat stable salt builuing-up anu
equipment uamage.
At the minimum, an amine unit must have some foim of bulk fluiu sepaiation uevice
upstieam of the absoibeis (contactois). These aie slug catcheis oi simple two oi thiee
phase sepaiatois, uesigneu to catch a slug of liquiu, giavity sepaiate the solius anu liquius
fiom the gas anu allow the gas to pass thiough a mesh pau befoie it enteis the base of the
absoibei. The Piimaiy contaminant is hyuiocaibon, whethei natuially occuiiing oi fiom
compiessoi oils. Byuiocaibons neeu to be iemoveu because they can cause the amine
solution to foam, which can be as small a consequence as incieaseu antifoam consumption
to a seveie case of failuie to meet specification.

The moie effective means of contaminant iemoval is the installation of a filteicoalescei,
uownstieam of a bulk sepaiatoi, to tiap up to % of the feeu gas aeiosols. Theie aie many
plants that coulu not opeiate without the piesence of the inlet coalesceifiltei. The moie
effective coalescei is a veitical unit, iathei than a hoiizontal vessel. Whenevei hoiizontal
vessels aie installeu, theie is always the potential foi the filtei elements to be submeigeu in
the liquiu it is tiying to coalesce. At this point the filteis aie no longei effective as
coalescing elements. With veitical coalesceis, the liquiu is uiaineu away fiom the filtei
elements anu the oppoitunity foi failuie is ieuuceu.

Inlet sepaiatois shoulu be placeu within meteis ( feet) of the absoibei oi
hyuiocaibon may conuense in the line uue to cooling. Nesh paus shoulu always be installeu
on the hoiizontal plane. veitically placeu mesh paus may be floou with liquiu, at which
point they act as siphons iathei than coalescing elements.

8.. Caibon Filtei:

If the amine solution foams as bauly uownstieam of the caibon filtei as upstieam the
caibon filtei is piobably spent anu shoulu be ieplaceu.

8.. Paiticulate Filtei:

FeS paiticulates in the amine solution tenu to stabilize amine solution foaming, theiefoie, if
the ciiculating amine is heavily contaminateu with FeS, check the opeiation of the amine
solution filteis anu ieplace the filteis as neeueu.

- Tempoiaiy foam contiol
When foaming occuis, it is usually necessaiy as a shoit teim measuie to utilize an
antifoam agent to ieuuce the foaming tenuency of the amine solution until a moie
peimanent iemeuy can be founu. 0se of an antifoam agent shoulu be consiueieu a
shoit-teim measuie iathei than a long-teim cuie. Beteimining the souice of the
contamination causing the foaming anu pieventing futuie contamination is the best
long-teim fix. It may be necessaiy to evaluate a numbei of antifoams to ueteimine
the best selection. Any antifoam agent consiueieu shoulu be testeu befoie use in the
amine system. A simple shake test is usually auequate in scieening potential
antifoam agents. Antifoam agents aie typically of two types, silicon baseu oi long-
chaineu alcohols. The manufactuiei guiuelines foi antifoam injection shoulu be
followeu since excessive antifoam can aggiavate the foaming pioblem. Check to see
if the caibon filtei iemoves the selecteu antifoam. Typically, silicon baseu antifoams
aie iemoveu by the caibon filtei. With the caibon filtei in seivice, continuous
auuition of the silicon antifoam agent may be iequiieu. Bowevei, it is iecommenueu
that the antifoam auuition be maue in small peiiouic uoses as neeueu to contiol the
foaming. uieat caie shoulu be taken to pievent oveiuosing the amine system with
8. ExUe__ve _oluton lo__e_:

Solution foaming contiibutes significantly to excessive solution losses thiough entiainment
anu amine caiiyovei; theiefoie, excessive solution losses anu solution foaming aie linkeu.
Solution losses aie eithei physical oi chemical baseu. The majoi souice of amine losses is
physical in the foim of mechanicalphysical entiainment. Losses uue to chemical means
(uegiauation anu vapoiization) aie faiily small. In solving an excessive solution loss
pioblem, the amine unit opeiatoi shoulu concentiate on the following aieas:

8..Reuucing Absoibei Foaming anu Subsequent Solvent Caiiyovei:

With the natuial linkage of excessive losses anu solution foaming, solving an excessive
foaming pioblem will likely significantly ieuuce the amine system solution losses.

8..0ptimizing Regeneiatoi 0peiations:

Some amine systems must puige ieflux to contiol ammonia contamination oi maintain
piopei watei balance. If the ieflux contains an excessive amount of amine uue to
mechanical pioblems in the iegeneiatoi, the ieflux puige can account foi a significant
amount of the amine losses. If a ieflux puige is utilizeu to contiol ammonia, in auuition to
testing the ieflux foi ammonia content, the amine content of the ieflux puige shoulu be
checkeu ioutinely to ueteimine the extent of the amine losses uiiectly ielateu to the ieflux

8..Paiticulate Filtei Change-out Pioceuuie:
A ieview of the filtei change-out pioceuuie leaus to a tightening of the amine system anu a
ieuuction in solution losses. A significant poition of the solution losses may be tiaceu to
lack of piopei amine iecoveiy fiom filteis, pump seal flushes anu the flash uium.

- Remeuy-Solution analysis:
Regulai sample collection anu accuiate analysis of the plant amine solution can be
useu as a tool to iesolve opeiational pioblems anu impiove the opeiation of the gas
tieating system. Piopei testing pioviues valuable infoimation about the amine
solvents physical anu chemical conuition. Plants shoulu peiiouically ieview theii
amine solution analysis piogiam to be suie they aie obtaining the necessaiy
infoimation foi the best contiol of plant opeiations.


The aiomatic compounus incluuing Benzene, Toluene, Ethyl-benzene, anu Xylene
(collectively known as BTEX), aie incluueu as hazaiuous factois in aii pollutants. BS anu
C0 piesent in the feeu gas aie absoibeu by the amine in the contactoi column anu the
sweeteneu gas exits the top of the column. Rich amine exits the bottom of the column anu is
sent thiough the iegeneiation system to iemove the aciu gases anu uissolveu
hyuiocaibons, incluuing BTEX. The lean solution is then ciiculateu to the top of the
absoibei to continue the cycle. The sweeteneu gas exiting the absoibei is satuiateu by
watei fiom its contact with the amine. The oveiheaus, incluuing BTEX fiom the amine
iegeneiatoi column, aie sent to a sulfui iecoveiy unit. If the iaw gas contains appieciable
amounts of BS; a sulfui plant is useu to tieat the oveiheaus fiom the iich amine stiippei.
This tieating noimally uestioys any BTEX oi othei hyuiocaibons. Seveial opeiating
paiameteis uiiectly affect the amount of BTEX absoibeu in an amine unit, such as inlet
BTEX composition, contactoi opeiating piessuie, amine ciiculation iate, solvent type, anu
lean solvent tempeiatuie. NBEA absoibs the lowest amount of BTEX compaieu to BEA anu
NEA; theiefoie, it is iecommenueu to use NBEA wheie BTEX is obseiveu in the soui gas, (if
it is applicable). Seveial opeiating paiameteis uiiectly affect the amount of BTEX absoibeu
in an amine unit. These factois incluue the inlet BTEX composition, contactoi opeiating
piessuie, amine ciiculation iate, solvent type, anu lean solvent tempeiatuie. Following list
of stiategies can be followeu to limit the BTEX emissions fiom gas plant:
. Ninimize the lean amine tempeiatuie. The amount of BTEX emissions in amine
systems uecieases with an inciease in lean solvent tempeiatuie.
. 0se the best solvent foi tieating iequiiements. (i.e. NBEA absoibs the lowest
amount of BTEX).
. Ninimize the lean ciiculation iate. BTEX pick up incieases almost lineaily with an
inciease in ciiculation iate.
. If the stiippei piessuie is highei, the oveiall BTEX emissions aie lowei.


0f late membianes have founu theii use in bulk iemoval of C0 fiom natuial gas. As high as
% C0 concentiation in natuial gas has been iepoiteu to be successfully piocesseu in
membiane units to ieuuce C0 content -%. Nany often a hybiiu system of
membiane anu amine system is useu to meet sales gas specification.

C0 iemoval membianes uo not opeiate as filteis, wheie small molecules aie sepaiateu
fiom laigei ones thiough a meuium with ceitain size poies in it. Insteau they opeiate on
the piinciple of solution-uiffusion thiough a non-poious membiane. C0 fiist uissolves into
the membiane, anu then uiffuses thiough it. Since the membiane uoes not have poies it
uoes not sepaiate on the basis of moleculai size; iathei it sepaiates baseu on how well
uiffeient compounus uissolve into the membiane anu then uiffuse thiough it. Caibon
uioxiue, hyuiogen, helium, hyuiogen sulfiue anu watei vapoi, foi example, aie highly
peimeable gases anu so aie chaiacteiizeu as fast gases, wheieas caibon monoxiue,
nitiogen, methane, ethane anu othei hyuiocaibons aie chaiacteiizeu as slow gases. The
membianes theiefoie allow selective iemoval of fast gases fiom slow gases.

Polymei-baseu membianes aie useu foi this puipose. These cuiiently incluue cellulose
acetate, polyimiue anu polysulfone. The most wiuely useu anu testeu mateiial is cellulose
acetate. Polyimiue has potential in ceitain C0 iemoval applications, but lacks the bieauth
of commeicial expeiience of cellulose acetate. The piopeities of polymeis can be mouifieu
to enhance membiane peifoimance. Foi example, polyimiue membianes weie initially
useu foi hyuiogen iecoveiy, but weie then mouifieu foi C0 iemoval. Cellulose acetate
membianes weie initially uevelopeu foi ieveise osmosis, but now aie the most iuggeu C0
iemoval membiane available. Nembiane peifoimance has been enhanceu fiom selectivity
aspect by mouifying existing membiane mateiials anu investigating alteinate membiane
mateiials. 0f equal impoitance have been impiovements in membiane element
configuiation, pietieatment uesign anu optimization of the system's mechanical uesign.
uas sepaiation membianes aie cuiiently manufactuieu in one of two foims: flat sheet oi
hollow fibei. The flat sheets aie typically combineu into a spiial wounu element, while the
hollow fibeis aie combineu into a bunule, similai to a shell anu tube heat exchangei. In the
spiial wounu aiiangement, two flat sheets of membiane with a peimeate spacei in
between aie glueu along thiee of theii siues to foim an envelope which is open at one enu.
Nany of these envelopes aie sepaiateu by feeu spaceis anu wiappeu aiounu a peimeate
tube, with theii open enus facing the peimeate tube.

Feeu gas enteis along the siue of the membiane, anu passes thiough the feeu spaceis
sepaiating the envelopes. These feeu spaceis also pioviue mechanical stiength. As the gas
tiavels between the envelopes, C0, BS anu othei highly peimeable compounus peimeate
into the envelope. These peimeateu components have only one outlet, which is to tiavel
within the envelope to the peimeate tube. The uiiving foice foi tianspoit is the uiffeiential
piessuie between the low-piessuie peimeate anu high-piessuie feeu gas. 0nce peimeate
gas ieaches the peimeate tube it enteis it thiough holes uiilleu in the tube. Fiom theie it
tiavels uown the tube joining peimeate fiom othei tubes. Any gas on the feeu siue that
uoes not get a chance to peimeate, leaves thiough the siue of the element opposite the feeu

In high C0-iemoval applications fiom natuial gas a significant amount of hyuiocaibons
peimeate the membiane anu aie lost. Nultistage systems attempt to iecovei a poition of
these hyuiocaibons. The one stage with iecycle uesign allows only a poition of the fiist
stage peimeate to be lost. The iest is iecycleu to the feeu of the fiist stage. The poition of
fiist stage peimeate that is lost is usually taken fiom the fiist membiane mouules in the
system, wheie feeu C0, hence peimeate C0, is highest anu hyuiocaibons aie lowest.
Peimeate that is iecycleu is at low piessuie anu must be ie-piessuiizeu befoie it can be
combineu with the feeu gas.

AdvantaYe of membrane _y_tem:

- Reuuceu initial capital expenuituie
- Lowei opeiating cost
- Fastei & simplifieu installation
- 0peiational simplicity
- Auaptability
- Bigh tuin uown
- Besign efficiency
- Powei geneiation fiom peimeate gas
- Bigh ieliability anu on-stieam time
- Iueal foi ue-bottlenecking
- Low laboi iequiiement
- Enviionmentally fiienuly
- Iueal foi iemote location

D_advantaYe of membrane _y_tem:

- Bighei hyuiocaibon losses
- Coaise iemoval of Byuiogen sulfiue
- Effective only foi coaise iemoval of C0


The objective of gas tieating has always been iemoval of unwanteu impuiities in a safe anu
cost effective mannei. A giauual piogiess has been unuei notice to achieve this thiough
minimizing cost while still meeting uesiieu piouuct specification, minimizing coiiosion anu
ieuucing opeiating pioblems. 0f late theie has been a shift in solvent selection fiom
geneiic amines to piopiietaiy amines uevelopeu with enhanceu selectivity as an essential
pait of this piogiess. Foi highly selective BS iemoval, solvents by The B0W Chemical Co.
(uas Spec), 0nion Caibiue (0caisol), BASF (aNBEA), EXX0N (Flexsoib), anu otheis have
been uevelopeu that exhibit gieatei selectivity anu BS iemoval to lowei tieateu gas
specifications. Bowevei, these solvents aie NBEA-baseu solvents. These solvents have
othei applications; such as BS iemoval fiom C0 enhanceu oil iecoveiy (R0R)
eniichment piocesses. Solvents foi BS selectivity aie useu foi iefineiy systems with high
C0 slip, tail gas tieating, natuial gas tieating, BS iemoval fiom liquiu hyuiocaibon
stieams, natuial gas sciubbing, anu iefineiy systems with LPu stieams containing olefins.
Inventions of all these new amines with selective kinetics have contiibuteu towaius
successful gas sweetening with incieaseu emphasis on enviionment emission.


This uocument uefines the Buty Specification foi the Aciu uas Removal 0nit to be installeu
as pait of the onshoie piocessing facilities foi the XX pioject.

The AuR unit will iemove hyuiogen sulphiue fiom soui gas anu will paitially iemove othei
components incluuing C0, meicaptans anu C0S.

The AuR unit will also supply a small lean amine stieam to tieat NuL foi iemoval of BS
anu C0 in the liquiu tieating aiea anu ieceive the iich amine.


AuR piocesses soui feeu gas fiom the inlet ieception facilities of the plant combineu with
conuensate stabilisation iecompiesseu offgas. The feeu gas contains BS, C0 anu oiganic
sulphui compounus (mainly meicaptans). BS anu meicaptans shall be iemoveu fiom the
gas piioi to the expoit to pipeline. The AuR shall iemove the BS uown to the iequiieu
specification. Neicaptans iemoval in the AuR is uesiiable, as it will simplify the
uownstieam gas piocessing. The level of meicaptans iemoval will be uefineu by the
Licensoi. C0 will also be uefineu by the Licensoi. In cases wheie uisagieement exists
between uata pioviueu in this uocument anu that pioviueu in the iefeiences given in
section , this uocument goveins.

The AuR unit is uesigneu foi a maximum flow pei tiain (Besign case) of ** kg
moleshi (. million Smuay) of soui gas coiiesponuing to Phase wintei opeiation. It
hanules the soui gas ueliveieu fiom offshoie supplementeu with flasheu soui gas fiom the
oil tiains iecompiesseu to AuR inlet piessuie. The AuR unit consists of one tiain capable of
piocessing % of the total onshoie soui gases foi fiistly Phase .
A seconu iuentical tiain is iequiieu foi Phase .

Theie aie seveial options foi the futuie some of which involve the possible auuition of a
thiiu iuentical AuR tiain at some futuie uate.


The inlet gas composition to the AuR 0nit is as follows. It is baseu on the KE-Reviseu
Composition. Flows shown iefei to the total feeu to the Absoibei.

The cases below give soui gas foi the following opeiations
Phase , summei
Phase , wintei
Phase , summei
Phase , wintei, BESIuN case
Theie is also a small aciu gas iemoval seivice iequiieu in the NuL tieating aiea- see below
unuei section foi uetails.

AuR shall be able to hanule the composition iange of these cases,

Theie is no liquiu in the gas; hyuiocaibon uew point is less than C.
BTXEB level is appiox ppmv, max.
**Figuies piesenteu unuei vaiious cases aie foi illustiation puipose only

These compositions aie taken fiom the following Nateiial Balances.
Nain 0nshoie Facilities
Phase Summei Boc no. xx
Phase Wintei Boc no. xx
Phase Summe Boc no. xx
Phase Wintei Boc no. xx

Besign case is Phase Wintei.

Each AuR unit shall be uesigneu to opeiate with a tuinuown iatio at % of uesign


..Sweet Ca_

The tieateu gas shall comply with the following specifications foi the whole iange of
feeustock chaiacteiistics.

- To achieve BS less than mgNm in the sales gas the tieateu gas fiom the AuR
must be tieateu to less than . mgNm.
- C0 content: No specification foi C0 , expecteu to be in the ppm iange, uata to be
pioviueu by licensoi
- Neicaptan, C0S, CS anu BTXEB contents: Expecteu iemoval levels to be pioviueu
by Licensoi
- 0utlet conuition: To be assesseu by Licensoi

..AUd Ca_

The aciu gas fiom the AuR solvent iegeneiation will be piocesseu in a Claus type Sulphui
Recoveiy 0nit.

The piocess licensoi shall be iesponsible foi uefinition of the iange of chaiacteiistics of the
aciu gas foi SR0 paiticulaily BS content anu hyuiocaibons content.

Licensoi shoulu ieuuce the hyuiocaibon content of the aciu gas to a minimum.

The batteiy limit conuitions at the AuR's outlet shall be as follows:
- Piessuie: . bai abs minimum
- Tempeiatuie: C (noimal)

The Sulphui Recoveiy 0nit shall be uesigneu foi a noimal value of . vol% anu a
maximum of . vol% of Byuiocaibons the oveiall feeu aciu gas.

..Fla_b Ca_ SpeUfUaton

The flasheu gas piouuceu by the AuR's, at iich amine flash uium outlet, shall meet the
following specification:
- Piessuie: by Piocess Licensoi
- Tempeiatuie: by Piocess Licensoi

Licensoi neeus to minimize BS content anu auvise suitably


The following iequiiements must be taken into account foi the uesign of the Aciu uas
Removal 0nits.


The Piocess Licensoi shall pioviue a uesign that meets the guaiantee statements as
specifieu in section (Piocess uuaiantees).

The Piocess Flow Biagiam shall be optimiseu by the Piocess Licensoi, in close coopeiation
with the Engineeiing Contiactoi, with iegaius to piocess uesign, equipment
constiuctibility, tianspoitation anu eiection as well as plant opeiation ieliability anu
Piocess Licensoi iesponsibility is limiteu to the items within the AuR's Batteiy Limit,
taking howevei in consiueiation the geneial aiiangement of the whole Plant. The Piocess
Licensoi is also iesponsible foi the uefinition of the aciu gas composition iange to be useu
foi the uesign of the Sulphui Recoveiy 0nits accoiuing to the opeiating cases uefineu foi
the Aciu uas Removal 0nits.


The licensoi shall iecommenu the minimum mateiials of constiuction foi the equipment
anu piping. The metalluigy selection shall consiuei coiiosive piocess fluiu (as pei the
uesign basis) anu plant seivice life of yeais.

A coiiosivity assessment, incluuing coiiosion calculations shall be caiiieu out foi all
sections of plant associateu with wet C0 anu BS, as pait of the mateiials selection
justification. The coiiosivity assessment shall assess only sections of the plant wheie
inteinal coiiosion can aiise as iesult of the piesence of C0, BS anu chloiiues in
combination with a uistinct watei phase.

Foi cost effectiveness, the piimaiy choice mateiial consiueieu shall be LTCS. Alteinative
mateiials aie selecteu in cases wheie LTCS is incapable of pioviuing the iequiieu uesign
life oi wheie tempeiatuies coulu be encounteieu uuiing seivice that is below the
peimissible minimum tempeiatuie foi LTCS.

Piocess Licensoi to specify the iequiieu utilities quality anu consumptionpiouuction in all
opeiating cases, incluuing peak iequiiement foi stait-up, shut uown oi specific AuR's units


Piocess Licensoi to specify all chemicals (solvent incluueu) useu in the Aciu uas Removal
0nits, the consumption, life time, inventoiy anu initial loau to puichase.


Licensoi equipment iecommenuations shall be suitable foi obtaining mechanical
guaiantees fiom equipment supplieis. The uesign of the AuR unit shall incoipoiate the
following specific iequiiements:

- The top section of the Absoibei shall incluue a wash watei section to minimize
solvent losses.
- Thiee off % Lean Amine Pumps (plus Boostei Pumps) shall be pioviueu.
- The Inteimeuiate Stoiage Tank shall be sizeu to accommouate the whole amine
- The top section of the Regeneiatoi shall incluue a packeu column (contact
conuensei). A ciiculating ieflux system with an aii coolei will be useu.
Lean amine shall also be pioviueu foi NuL tieating. The iequiiement is foi a pump
uischaige piessuie of baia anu a tempeiatuie of C. Rich amine at a loauing level not
exceeuing . mol BS pei mol amine will be ietuineu to the Rich Amine Flash Bium.
Compositions anu flowiate iequiiement aie given below.


The perIormances shall be guaranteed under the Iollowing conditions:
Feed gas composition and conditions within the range deIined in Par. 2.3.
Unit engineered and erected according to the Process Licensor recommendations as
provided in the AGR's Process Design Package and the Operating Guidelines.
Unit under stable and normal operation according to the Process Licensor
recommendations as provided in the AGR's Process Design Package and the Operating


The AGR Licensor shall guarantee the Iollowing:
AGR design capacity:
13036 kg moles/hr (7.4 Sm3/d) see Design case
AGR turndown capacity: 30
ydrocarbon content oI Acid Gas not to exceed 0.5 mol
Minimum Acid Gas pressure 2.1 bara
Process Gas pressure drop (Feed minus Treated Gas pressure) not to exceed 0.6 bar
For the whole range oI operating cases, the treated Gas speciIication: 2S: less than
6.3 mg/Nm3
For the whole range oI operating cases, the Ilash gas speciIication: 2S: To be deIined
by the Licensor.
Solvent losses: To be deIined by the Licensor.
Utility requirements Maximum steam rates: To be deIined by Licensor.
Maximum power consumption: To be deIined by Licensor.
Maximum Ilash gas production rate.

The AGR Licensor is also responsible to advise the data to be taken into account Ior the
The acid gas range oI characteristics (2S, CO2, hydrocarbons including BTEX
content and breakdown, etc.) Ior the design oI the SRU`s