Instructor:
Dr.
Istadi
(http://tekim.undip.ac.id/staf/istadi
)
Email:
istadi@undip.ac.id
Course
Syllabus:
(Part
1)
1. Definitions
of
Natural
Gas,
Gas
Reservoir,
Gas
Drilling
and
Gas
production
(Pengertian
gas
alam,
gas
reservoir,
gas
drilling,
dan
produksi
gas)
2. Overview
of
Gas
Plant
Processing
(Overview
Sistem
Pemrosesan
Gas)
and
Gas
Field
Operations
and
Inlet
Receiving
(Operasi
Lapangan
Gas
dan
Penerimaan
Inlet)
3. Gas
Treating:
Chemical
Treatments
(Pengolahan
Gas:
secara
kimia)
and
Sour
Gas
Treating
(Pengolahan
Gas
Asam)
4. Gas
Treating:
Physical
Treatments
(Pengolahan
Gas:
secara
fisika)
5. Gas
Dehydration
(Dehidrasi
Gas)
6. Gas
Dehydration
(Dehidrasi
Gas)
7. Hydrocarbons
Recovery
(Pengambilan
Hidrokarbon)
DEFINISI
! Acid
gas:
gas
alam
yang
mengandung
H2S,
dan
CO2
! Sour
gas:
gas
alam
yang
mengandung
H2S
dan
senyawa
sulfur
lainnya
(COS,
CS2,
dan
mercaptan)
! Sweet
gas:
gas
alam
yang
mengandung
CO2
! Gas
treating:
reduction
of
the
“acid
gases”
to
sufficiently
low
levels
to
meet
contractual
specifications
or
permit
additional
processing
in
the
plant
without
corrosion
and
plugging
problems.
! Questions:
! Why
are
the
acid
gases
a
problem?
! What
are
the
acid
gas
concentrations
in
natural
gas?
! How
much
purification
is
needed?
! What
is
done
with
the
acid
gases
after
separation
from
the
natural
gas?
! What
processes
are
available
for
acid
gas
removal?
Natural
Gas
Pipeline
Specifica>on
Acid
Gas
Defini>ons
! Hydrogen
Sulfida
(H2S):
! Hydrogen
sulfide
is
highly
toxic,
and
in
the
presence
of
water
it
forms
a
weak
corrosive
acid.
! threshold
limit
value
(TLV):
10
ppmv
! When
H2S
concentrations
are
well
above
the
ppmv
level,
other
sulfur
species
can
be
present:
carbon
disulfide
(CS2),
mercaptans
(RSH),
and
sulfides
(RSR),
in
addition
to
elemental
sulfur.
! If
CO2
is
present,
the
gas
may
contain
trace
amounts
of
carbonyl
sulfide
(COS).
! ASTM
D4084
Standard
test
method
for
analysis
of
hydrogen
sulfide
in
gaseous
fuels
H2S…
! At
0.13
ppm,
H2S
can
be
sensed
by
smell.
! At
4.6
ppm,
the
smell
is
quite
noticeable.
! As
the
concentration
increases
beyond
200
ppm,
the
sense
of
smell
fatigues,
and
the
gas
can
no
longer
be
detected
by
odor.
! At
500
ppm,
breathing
problems
are
observed
and
death
can
be
expected
in
minutes.
! At
1000
ppm,
death
occurs
immediately.
Acid
Gas
Defini>ons
! Carbon
dioxida
(CO2):
! Carbon
dioxide
is
nonflammable
and,
consequently,
large
quantities
are
undesirable
in
a
fuel.
! it
forms
a
weak,
corrosive
acid
in
the
presence
of
water.
! If
the
partial
pressure
of
CO2
exceeds
15
psia,
inhibitors
usually
can
only
be
used
to
prevent
corrosion.
! The
partial
pressure
of
CO2
depends
on
the
mole
fraction
of
CO2
in
the
gas
and
the
natural
gas
pressure.
! Corrosion
rates
will
also
depend
on
temperature.
! Threshold
Limit
Value
(TLV):
of
a
chemical
substance
is
a
level
to
which
it
is
believed
a
worker
can
be
exposed
day
after
day
for
a
working
lifetime
without
adverse
health
effects.
Gas
Purifica>on
Level
! The
inlet
conditions
at
a
gas
processing
plant
are
generally
temperatures
near
ambient
and
pressures
in
the
range
of
300
to
1,000
psi
(20
to
70
bar),
so
the
partial
pressures
of
the
entering
acid
gases
can
be
quite
high
! If
the
gas
is
to
be
purified
to
a
level
suitable
for
transportation
in
a
pipeline
and
used
as
a
residential
or
industrial
fuel,
then
the
H2S
concentration
must
be
reduced
to
0.25
g/100
SCF
(6
mg/m3)
! the
CO2
concentration
must
be
reduced
to
a
maximum
of
3
to
4
mol%
! However,
if
the
gas
is
to
be
processed
for
NGL
recovery
or
nitrogen
rejection
in
a
cryogenic
turboexpander
process,
CO2
may
have
to
be
removed
to
prevent
formation
of
solids.
! If
the
gas
is
being
fed
to
an
LNG
liquefaction
facility,
then
the
maximum
CO2
level
is
about
50
ppmv
Acid
Gas
Disposal
! What
becomes
of
the
CO2
and
H2S
after
their
separation
from
the
natural
gas?
!
The
answer
depends
to
a
large
extent
on
the
quantity
of
the
acid
gases.
!
Warning:
CO2
is
the
most
greenhouse
gas
contributor
! For
CO2,
if
the
quantities
are
large
!
sometimes
used
as
an
injection
fluid
in
EOR
(enhanced
oil
recovery)
projects.
In
the
case
of
H2S,
four
disposal
op>ons
are
available:
! Incineration
and
venting,
if
environmental
regulations
regarding
sulfur
dioxide
emissions
can
be
satisfied
! Reaction
with
H2S
scavengers,
such
as
iron
sponge
! Conversion
to
elemental
sulfur
by
use
of
the
Claus
or
similar
process
(2
H2S
+
O2
→
S2
+
2
H2O)
! Disposal
by
injection
into
a
suitable
underground
formation,
!
if
concentration
is
too
high
Acid
Gas
Removal
Processes
Natural
Gas
Sweetening
Processes
! 1.
Batch
solid
bed
adsorption:
For
complete
removal
of
H2S
at
low
concentrations,
the
following
materials
can
be
used:
iron
sponge,
molecular
sieve,
and
zinc
oxide.
! 2.
Reactive
solvents:
MEA
(monoethanol
amine),
DEA
(diethanol
amine),
DGA
(diglycol
amine),
DIPA
(di-‐isopropanol
amine),
hot
potassium
carbonate,
and
mixed
solvents.
These
solutions
are
used
to
remove
large
amounts
of
H2S
and
CO2
and
the
solvents
are
regenerated.
! 3.
Physical
solvents:
Selexol,
Recitisol,
Purisol,
and
Fluor
solvent.
They
are
mostly
used
to
remove
CO2
and
are
regenerated.
! 4.
Direct
oxidation
to
sulfur.
Stretford,
Sulferox
LOCAT,
and
Claus.
These
processes
eliminate
H2S
emissions.
! 5.
Membranes.
This
is
used
for
very
high
CO2
concentrations.
AVIR,
Air
Products,
Cynara
(Dow),
DuPont,
Grace,
International
Permeation,
and
Monsanto
are
some
of
these
processes
Process
Selec>on?
Please
consider:
! The
type
and
concentration
of
impurities
and
hydrocarbon
composition
of
the
sour
gas.
! The
temperature
and
pressure
at
which
the
sour
gas
is
available.
! The
specifications
of
the
outlet
gas
(low
outlet
specifications
favor
the
amines).
! The
volume
or
flow
rate
of
gas
to
be
processed.
! The
specifications
for
the
residue
gas,
the
acid
gas,
and
liquid
products.
! The
selectivity
required
for
the
acid
gas
removal.
! Feasibility
of
sulfur
recovery
! The
capital,
operating,
and
royalty
costs
for
the
process.
! Acid
gas
selectivity
required
! Presence
of
heavy
aromatic
in
the
gas
! Well
location
!
Relative
economics
! The
environmental
constraints,
including
air
pollution
regulations
and
disposal
of
byproducts
considered
hazardous
chemicals.
PURIFICATION
PROCESS
! Four
scenarios
are
possible
for
acid
gas
removal
from
natural
gas:
! CO2
removal
from
a
gas
that
contains
no
H2S
! H2S
removal
from
a
gas
that
contains
no
CO2
! Simultaneous
removal
of
both
CO2
and
H2S
! Selective
removal
of
H2S
from
a
gas
that
contains
both
CO2
and
H2S
Process
selec>on
chart
for
CO2
removal
with
no
H2S
present
Process
selec>on
chart
for
H2S
removal
with
no
CO2
present
Process
selec>on
chart
for
simultaneous
H2S
and
CO2
removal
Process
selec>on
chart
for
selec8ve
H2S
removal
with
CO2
present
CO2
and
H2S
Removal
Processes
for
Gas
Streams
SOLVENT
ABSORPTION
PROCESSES
! In
solvent
absorption,
the
two
major
cost
factors
are:
! the
solvent
circulation
rate,
which
affects
both
equipment
size
and
operating
costs,
! and
the
energy
requirement
for
regenerating
the
solvent
Comparison
of
Chemical
and
Physical
Solvents
Amine
Structure
! Primary
amine
! Secondary
amine
! Tertiary
amine
amines…
! The
amines
are
used
in
water
solutions
in
concentrations
ranging
from
approximately
10
to
65
wt%
amines
! All
commonly
used
amines
are
alkanolamines,
which
are
amines
with
OH
groups
attached
to
the
hydrocarbon
groups
to
reduce
their
volatility
Molecular
structures
of
commonly
used
amines
Amines
remove
H2S
and
CO2
in
a
two
step
process
! The
gas
dissolves
in
the
liquid
(physical
absorption).
! The
dissolved
gas,
which
is
a
weak
acid,
reacts
with
the
weakly
basic
amines.
! Absorption
from
the
gas
phase
is
governed
by
the
partial
pressure
of
the
H2S
and
CO2
in
the
gas,
whereas
the
reactions
in
the
liquid
phase
are
controlled
by
the
reactivity
of
the
dissolved
species
Basic
Amine
Chemistry
! Amines
are
bases,
and
the
important
reaction
in
gas
processing
is
the
ability
of
the
amine
to
form
salts
with
the
weak
acids
formed
by
H2S
and
CO2
in
an
aqueous
solution
! The
reaction
between
the
amine
and
both
H2S
and
CO2
is
highly
exothermic
! Direct
proton
transfer:
! R1R2R3N
+
H2S
↔
R1R2R3NH+HS−
! The
reaction
between
the
amine
and
the
CO2
is
more
complex
because
CO2
reacts
via
two
different
mechanisms.
! When
dissolved
in
water,
CO2
hydrolyzes
to
form
carbonic
acid,
which,
in
turn,
slowly
dissociates
to
bicarbonate.
!
The
bicarbonate
then
undertakes
an
acid−base
reaction
with
the
amine
to
yield
the
overall
reaction
! A
second
CO2
reaction
mechanism,
requires
the
presence
of
a
labile
(reactive)
hydrogen
in
the
molecular
structure
of
the
amine.
! The
CO2
reacts
with
one
primary
or
secondary
amine
molecule
to
form
the
carbamate
intermediate,
which
in
turn
reacts
with
a
second
amine
molecule
to
form
the
amine
salt
! The
rate
of
CO2
reaction
via
carbamate
formation
is
much
faster
than
the
CO2
hydrolysis
reaction,
but
slower
than
the
H2S
acid
−base
reaction.
! These
reactions
are
reversible
and
are
forward
in
the
absorber
(at
low
temperature)
and
backward
in
the
stripper
(at
high
temperature).
Monoethanolamine
! Monoethanolamine
(MEA)
is
the
most
basic
of
the
amines
used
in
acid
treating
and
thus
the
most
reactive
for
acid
gas
removal.
! It
has
the
advantage
of
a
high
solution
capacity
at
moderate
concentrations,
and
it
is
generally
used
for
gas
streams
with
moderate
levels
of
CO2
and
H2S
when
complete
removal
of
both
impurities
is
required.
! A
slow
production
of
“heat
stable
salts”
form
in
all
alkanol
amine
solutions,
primarily
from
reaction
with
CO2.
! Oxygen
enhances
the
formation
of
the
salts.
MEA
Reac>ons
! 2(RNH2)
+
H2S
↔
(RNH3)2S
! (RNH3)2S
+
H2S
↔
2(RNH3)HS
! 2(RNH2)
+
CO2
↔
RNHCOONH3R
Some
Representa>ve
Opera>ng
Parameters
for
Amine
Systems
! The
MEA
process
is
usually
using
a
solution
of
15–20%
MEA
(wt%)
in
water.
! Loading
is
about
0.3–0.4
mol
of
acid
removed
per
mole
of
MEA.
! The
circulation
rate
is
between
2
and
3
mol
of
MEA
per
mole
of
H2S
! However,
commercial
plants
use
a
ratio
of
3
to
avoid
excessive
corrosion.
Monoethanolamine
Disadvantages
! A
relatively
high
vapor
pressure
that
results
in
high
vaporization
losses
! The
formation
of
irreversible
reaction
products
with
COS
and
CS2
! A
high
heat
of
reaction
with
the
acid
gases
that
results
in
high
energy
requirements
for
regeneration
! The
inability
to
selectively
remove
H2S
in
the
presence
of
CO2
! Higher
corrosion
rates
than
most
other
amines
if
the
MEA
concentration
exceeds
20%
at
high
levels
of
acid
gas
loading
(Kohl
and
Nielsen,
1997)
! The
formation
of
corrosive
thiosulfates
when
reacted
with
oxygen
(McCartney,
2005)
Opera>ng
Features
! MEA
forms
foam
easily
due
to
the
presence
of
contaminants
in
the
liquid
phases;
this
foam
results
in
carryover
from
the
absorber.
These
contaminants
could
be
condensed
hydrocarbons,
degradation
products,
iron
sulfide,
as
well
as
corrosion
products
and
excess
inhibitors.
! Solids
can
be
removed
by
using
a
filter;
hydrocarbons
could
be
flashed;
degradation
products
are
removed
using
a
reclaimer.
! The
number
of
trays
used
in
absorbers
in
commercial
units
is
between
20
and
25
trays.
However,
the
theoretical
number
of
trays
calculated
from
published
equilibrium
data
is
about
three
to
four.
! If
we
assume
an
efficiency
of
35%
for
each
tray,
then
the
actual
number
of
trays
is
12.
It
has
been
reported
that
the
first
10
trays
pick
up
all
of
the
H2S
and
at
least
another
10
trays
are
of
not
much
value.
Thus,
it
is
suggested
to
use
15
trays.
! It
is
recommended
that
MEA
be
used
if
the
feed
does
not
contain
COS
or
CS2,
which
form
stable
products
and
deplete
the
amine.
If
the
feed
has
these
compounds,
a
reclaimer
must
be
used,
where
a
strong
base
like
NaOH
is
used
to
regenerate
and
liberate
the
amine.
This
base
has
to
be
neutralized
later.
Diglycolamine
! Compared
with
MEA,
low
vapor
pressure
allows
Diglycolamine
[
2-‐(2-‐aminoethoxy)
ethanol]
(DGA)
to
be
used
in
relatively
high
concentrations
(50
to
70%),
! Which
results
in
lower
circulation
rates.
! It
is
reclaimed
onsite
to
remove
heat
stable
salts
and
reaction
products
with
COS
and
CS2.
Diethanolamine
! Diethanolamine
(DEA),
a
secondary
amine,
is
less
basic
and
reactive
than
MEA.
! Compared
with
MEA,
it
has
a
lower
vapor
pressure
and
thus,
lower
evaporation
losses;
! it
can
operate
at
higher
acid
gas
loadings,
typically
0.35
to
0.8
mole
acid
gas/mole
of
amine
(DEA)
versus
0.3
to
0.4
mole
acid-‐gas/mole
(MEA);
! and
it
also
has
a
lower
energy
requirement
for
reactivation.
! Concentration
ranges
for
DEA
are
30
to
50
wt%
and
are
primarily
limited
by
corrosion.
DEA
Reac>ons
! 2R2NH
+
H2S
↔
(R2NH2)2S
! (R2NH2)2S
+
H2S
↔
2R2NH2SH
! 2R2NH
+
CO2
↔
R2NCOONH2R2
! DEA
forms
regenerable
compounds
with
COS
and
CS2
and,
thus,
can
be
used
for
their
partial
removal
without
significant
solution
loss.
! DEA
has
the
disadvantage
of
undergoing
irreversible
side
reactions
with
CO2
and
forming
corrosive
degradation
products;
thus,
it
may
not
be
the
best
choice
for
high
CO2
gases.
! Removal
of
these
degradation
products
along
with
the
heat
stable
salts
must
be
done
by
use
of
either
vacuum
distillation
or
ion
exchange.
Methyldiethanolamine
(MDEA)
! Methyldiethanolamine
(MDEA),
a
tertiary
amine,
selectively
removes
H2S
to
pipeline
specifications
while
“slipping”
some
of
the
CO2.
! MDEA
has
a
low
vapor
pressure
and
thus,
can
be
used
at
concentrations
up
to
60
wt%
without
appreciable
vaporization
losses.
! Even
with
its
relatively
slow
kinetics
with
CO2,
MDEA
is
used
for
bulk
removal
of
CO2
from
high-‐concentration
gases
because
energy
requirements
for
regeneration
are
lower
than
those
for
the
other
amines.
! It
is
not
reclaimable
by
conventional
methods
Comparison
of
Amine
Solvents
Principles
of
Amine
Trea>ng
Process
! The
acid
gas
is
fed
into
a
scrubber
to
remove
entrained
water
and
liquid
hydrocarbons.
! The
gas
then
enters
the
bottom
of
absorption
tower
which
is
either
a
tray
(for
high
flow
rates)
or
packed
(for
lower
flow
rate).
! The
sweet
gas
exits
at
the
top
of
tower.
! The
regenerated
amine
(lean
amine)
enters
at
the
top
of
this
tower
and
the
two
streams
are
contacted
countercurrently.
In
this
tower,
CO2
and
H2S
are
absorbed
with
the
chemical
reaction
into
the
amine
phase.
! The
exit
amine
solution,
loaded
with
CO2
and
H2S,
is
called
rich
amine.
! This
stream
is
flashed,
filtered,
and
then
fed
to
the
top
of
a
stripper
to
recover
the
amine,
and
acid
gases
(CO2
and
H2S)
are
stripped
and
exit
at
the
top
of
the
tower.
! The
refluxed
water
helps
in
steam
stripping
the
rich
amine
solution.
! The
regenerated
amine
(lean
amine)
is
recycled
back
to
the
top
of
the
absorption
tower.
Process
Flow
Diagram
for
Amine
Trea>ng
Average
Heats
of
Reac>on
of
the
Acid
Gases
in
Amine
Solu>ons
Amine
Reclaiming
! Amines
react
with
CO2
and
contaminants,
including
oxygen,
!
to
form
organic
acids.
! These
acids
then
react
with
the
basic
amine
to
form
heat
stable
salts
(HSS).
As
their
name
implies,
these
salts
are
heat
stable,
accumulate
in
the
amine
solution,
and
must
be
removed.
! For
MEA
and
DGA
solutions,
the
salts
are
removed
through
the
use
of
a
reclaimer
which
utilizes
a
semicontinuous
distillation
! The
reclaimer
is
filled
with
lean
amine,
and
a
strong
base,
such
as
sodium
carbonate
or
sodium
hydroxide,
is
added
to
the
solution
to
neutralize
the
heat
stable
salts.
Opera>ng
Issues
! Corrosion—Some
of
the
major
factors
that
affect
corrosion
are:
! Amine
concentration
(higher
concentrations
favor
corrosion)
! Rich
amine
acid
gas
loading
(higher
gas
loadings
in
the
amine
favor
corrosion)
! Oxygen
concentration
! Heat
stable
salts
(higher
concentrations
promote
corrosion
and
foaming)
! the
corrosion
products
can
cause
foaming
! Solution
Foaming—
! Foaming
of
the
liquid
amine
solution
is
a
major
problem
because
it
results
in:
" poor
vapor−liquid
contact,
" poor
solution
distribution,
" and
solution
holdup
with
resulting
carryover
and
off
spec
gas.
! Among
the
causes
of
foaming
are:
" suspended
solids,
" liquid
hydrocarbons,
" surface
active
agents,
such
as
those
contained
in
inhibitors
and
compressor
oils,
" and
amine
degradation
products,
including
heat
stable
salts.
! One
obvious
cure
is
to
remove
the
above
materials;
the
other
is
to
add
antifoaming
agents.
ALKALI
SALTS
! Hot
potassium
carbonate
(K2CO3)
is
used
to
remove
both
CO2
and
H2S.
! Best
for
the
CO2
partial
pressure
is
in
the
range
30–90
psi.
! The
process
is
very
similar
in
concept
to
the
amine
process,
in
that
after
physical
absorption
into
the
liquid,
the
CO2
and
H2S
react
chemically
with
the
solution
! In
a
typical
application,
the
contactor
will
operate
at
approximately
300
psig
(20
barg),
with
the
lean
carbonate
solution
entering
near
225°F
(110°C)
and
leaving
at
240°F
(115°C).
Process
flow
diagram
for
hot
potassium
carbonate
process
Batch
Processes
for
Sweetening
! Iron
Sponge
(Fe2O3)
! Zink
Oxide
(ZnO)
! Molecular
Sieve
(crystalline
sodium
alumino
silicates)
Iron
Sponge
Process
! This
process
is
applied
to
sour
gases
with
low
H2S
concentrations
(300
ppm)
operating
at
low
to
moderate
pressures
(50–500
psig).
! Carbon
dioxide
is
not
removed
by
this
treatment.
! The
inlet
gas
is
fed
at
the
top
of
the
fixed-‐bed
reactor
filled
with
hydrated
iron
oxide
and
wood
chips.
! 2Fe2O3
+
6H2S
↔
2Fe2S3
+
6H2O
! The
reaction
requires
an
alkalinity
pH
level
8–10
with
controlled
injection
of
water.
! The
bed
is
regenerated
by
controlled
oxidation
as
! 2Fe2S3
+
3O2
↔ 2Fe2O3
+
6S
! Some
of
the
sulfur
produced
might
cake
in
the
bed
and
oxygen
should
be
introduced
slowly
to
oxide
this
sulfur,
Arnold
and
Stewart
[2]:
! S2
+
2O2
↔
2SO2
Iron
sponge
….
Zinc
Oxide
! Zinc
oxide
can
be
used
instead
of
iron
oxide
for
the
removal
of
H2S,
COS,
CS2,
and
mercaptans.
! However,
this
material
is
a
better
sorbent
and
the
exit
H2S
concentration
can
be
as
low
as
1
ppm
at
a
temperature
of
about
300
oC.
! The
zinc
oxide
reacts
with
H2S
to
form
water
and
zinc
sulfide:
! ZnO
+
H2S
↔
ZnS
+
H2O
! A
major
drawback
of
zinc
oxide
is
that
it
is
not
possible
to
regenerate
it
to
zinc
oxide
on
site,
because
active
surface
diminishes
appreciably
by
sintering.
! Much
of
the
mechanical
strength
of
the
solid
bed
is
lost
due
to
fines
formation,
resulting
in
a
high-‐pressure-‐drop
operation.
Molecular
Sieve
! Molecular
sieves
(MSs)
are
crystalline
sodium
alumino
silicates
(Al/Si)
and
have
very
large
surface
areas
and
a
very
narrow
range
of
pore
sizes.
! They
possess
highly
localized
polar
charges
on
their
surface
that
act
as
adsorption
sites
for
polar
materials
at
even
very
low
concentrations.
! This
is
why
the
treated
natural
gas
could
have
very
low
H2S
concentrations
(4
ppm).
! In
order
for
a
molecule
to
be
adsorbed,
it
first
must
be
passed
through
a
pore
opening
and
then
it
is
adsorbed
on
an
active
site
inside
the
pore.
! There
are
four
major
zones
in
a
sieve
bed
Adsorp>on
zone
in
a
molecular
sieve
bed
Sweetening
of
natural
gas
by
molecular
sieves
! If
it
is
desired
to
remove
H2S,
a
MS
of
5
A*
is
selected
! If
it
is
also
desired
to
remove
mercaptans,
13
X*
is
selected.
! In
either
case,
selection
made
to
minimize
the
catalytic
reaction:
! H2S
+
CO2
↔
COS
+
H2O
! Olefins,
aromatics,
and
glycols
are
strongly
adsorbed,
which
may
poison
the
sieves.