Dr.
Istadi
(http://tekim.undip.ac.id/staf/istadi
)
Email:
istadi@undip.ac.id
Course
Syllabus:
(Part
1)
1. Denitions
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
sika)
5. Gas
Dehydration
(Dehidrasi
Gas)
6. Gas
Dehydration
(Dehidrasi
Gas)
7. Hydrocarbons
Recovery
(Pengambilan
Hidrokarbon)
PHYSICAL
ABSORPTION
! Absorption processes are generally most efficient when the partial pressures of the acid gases are relatively high, because partial pressure is the driving force for the absorption. ! Heavy hydrocarbons are strongly absorbed by the solvents used, and consequently acid gas removal is most efficient in natural gases with low concentrations of heavier hydrocarbons. ! Solvents can be chosen for selective removal of sulfur compounds, which allows CO2 to be slipped into the residue gas stream and reduce separation costs. ! Energy requirements for regeneration of the solvent are lower than in systems that involve chemical reactions. ! Separation can be carried out at near-ambient temperature. ! Partial processes produce a water saturated product stream that must be dried in most applications. ! Organic liquid (solvents) are used in these processes to absorb H2S (usually) preferentially over CO2 at high pressure and low temperatures. ! Regeneration is carried out by releasing the pressure to the atmosphere and sometimes in vacuum with no heat. Proper>es
of
Physical
Solvents
SELEXOL
PROCESS
! Selexol is a typical application of physical absorption that uses a mixture of dimethyl ether and propylene glycols as a solvent. ! A cool stream of natural gas is injected in the bottom of the absorption tower operated at 1000 psia. ! The rich solvent is flashed in a high flash drum at 200 psia, where methane is flashed and recycled back to the absorber and joins the sweet gas stream. ! The solvent is then flashed at atmospheric pressure and acid gases are flashed off. Selexol
! The
solvent
is
then
stripped
by
steam
to
completely
regenerate
the
solvent,
which
is
recycled
back
to
the
absorber;
any
hydrocarbons
will
be
condensed
and
any
remaining
acid
gases
will
be
ashed
from
the
condenser
drum.
! This
process
is
used
when
there
is
a
high
acid
gas
partial
pressure
and
no
heavy
hydrocarbons.
! DIPA
(di-isopropanol
amine)
can
be
added
to
this
solvent
to
remove
CO2
down
to
pipeline
specications
Selexol
Process
Schema>c
K-Value
! Rk Value = K-value methane / K-value component ! The K-value is the ratio of the mole fraction of the component in the vapor phase (y) to its mole fraction in the liquid phase (x), K = y/x. ! High K-values indicate the material is predominately in the vapor phase, whereas low K-values indicate a higher concentration in the liquid Ki
=
Pisat/P
phase (x). yi.P
=
xi.
Pisat
Rk
Value
-
Selexol
! An
Rk
value
greater
than
unity
indicates
the
solubility
of
the
component
in
Selexol
is
greater
than
that
of
methane,
whereas
a
value
less
than
unity
indicates
the
opposite
! Because
RK
for
CO2
and
H2S
are
15
and
134,
respectively,
these
gases
are
preferentially
absorbed
(relative
to
CH4),
and,
consequently,
physical
absorption
is
an
eective
technique
for
acid
gas
removal.
! The
process
can
reduce
H2S
to
4
ppmv,
reduce
CO2
to
levels
below
50
ppmv,
and
essentially
remove
all
mercaptans,
CS2,
and
COS.
! RK
values
for
hydrocarbons
heavier
than
CH4
are
fairly
high
(6.4
for
C2H6,
15.3
for
C3H8,
and
35
for
n-C4H10),
Selexol
will
remove
substantial
quantities
of
these
hydrocarbons,
a
feature
that
can
be
either
positive
or
negative,
depending
on
the
composition
of
the
gas
being
processed
and
the
desired
products.
! Finally,
the
RK
value
of
H2O
is
extremely
high
and
consequently,
Selexol
provides
some
dehydration
Solubility
of
various
gases
in
Selexol
solvent
at
70F
(21C)
as
a
func>on
of
par>al
pressure
! For
an
ideal
system,
Henrys
law
assumes
a
linear
relation
between
the
solubility
of
gas
component
i
and
its
partial
pressure,
! yi.P
=
Hi.xi
! where
Hi
is
the
Henrys
constant.
HENRYS
LAW
! Pi = H.Xi or Xi = (Yi / H).P ! This implies that acid gas absorbed in liquid phase (Xi) is proportional to its gas mole fraction (Yi) and inversely to Henrys constant (which is constant for a given temperature). ! Much more importantly, the solubility is proportional to the total gas pressure (P). ! This means that at high pressure, acid gases will dissolve in solvents, and as the pressure is released, the solvent can be regenerated. Example:
Composi>on
of
Inlet
and
Outlet
Gas
in
a
Selexol
Unit
FLUOR
PROCESS
! This
process
uses
propylene
carbonate
to
remove
CO2,
H2S,
C2+,
COS,
CS2,
and
H2O
from
natural
gas.
! Thus,
in
one
step,
the
natural
gas
can
be
sweetened
and
dehydrated.
Purisol
Process
! This process uses N-methyl-2-pyrrolidone also known as NMP as a solvent (licensed by Lurgi). ! The solvent removes H2S, CO2, H2O, RSH, and hydrocarbons and elastomers. ! The feature of this solvent is that it is highly selective for H2S. ! It has a boiling point of 396 oF, which is rather low to be used in amine mixed solvents. ! Regeneration is accomplished by two strippers, where dissolved hydrocarbons are stripped off as fuel gas nitrogen in the first drum ! and acid gases are stripped in the second stripper; ! regenerated NMP is recycled back to the absorber. Purisol
Process
Scheme
Sulnol/Claus
Process
! This process uses a solvent which is 40% sulfolane (tetrahydrothiophene 1-1 dioxide), 40% DIPA (di-isopropanolamine), and 20% water. ! Enhancing amine selectivity by adding a physical solvent such as sulfolane. Sulfolane is an excellent solvent of sulfur compounds such as H2S, COS, and CS2. Aromatics, heavy hydrocarbons, and CO2 are soluble to a lesser extent. ! Sulfinol is usually used for H2S/CO2 ratios greater than 1:1 or where CO2 removal is not required to the same extent as H2S. ! The sour gas components are removed from the feed gas by countercurrent contact with a lean solvent stream under pressure. ! The absorbed impurities are then removed from the rich solvent by stripping with steam in a heated regenerator column. ! The hot lean solvent is then cooled for reuse in the absorber absorber. Part of the cooling may be by heat exchange with the rich solvent for partial recovery of heat energy. Sulnol/Claus
Process
Comparison
of
Physical
Solvents
! Purisol has the highest capacity for absorption of acid gases and it is the most selective; however, it is the most volatile. ! Selexol is more selective than Fluor solvent, but it dissolves propane. ! All solvents exhibit significant affinity for heavy paraffins, aromatics, and water. ! Water absorption make them good dessicants. ! The loading capacity of physical solvent is much higher than amines. ! From Figure: At partial pressure of H2S 200 psia, the loading (mol H2S/gal solvent) of MEA (20% solution) is about 11.5, and at the same time, sulfolane (physical solvent) is about 18 and sulfinol (which is a mixed solvent) is about 19. Equilibrium
solvent
loadings
HYBRID
PROCESSES
! The
strengths
and
weaknesses
of
amine
and
physical
solvent
system
! To
take
advantage
of
the
strengths
of
each
type,
a
number
of
hybrid
processes
commercially
used,
and
under
development,
combine
physical
solvents
with
amines
! Depending
upon
the
solventamine
combination,
nearly
complete
removal
of
H2S,
CO2,
and
COS
is
possible
! Sulnol:
The
process
uses
a
combination
of
a
physical
solvent
(sulfolane)
with
DIPA
or
MDEA.
! Like
the
physical
solvent
processes,
the
hybrid
systems
may
absorb
more
hydrocarbons,
including
BTEX,
but
that
property
can
be
adjusted
by
varying
water
content.
ADSORPTION
! Acid gases, as well as water, can be effectively removed by physical adsorption on synthetic zeolites ! Applications are limited because water displaces acid gases on the adsorbent bed ! From typical isotherms for CO2 and H2S on molecular sieve, indicates that at ambient temperatures substantial quantities of both gases are adsorbed even at low partial pressures ! Molecular sieve can reduce H2S levels to the 0.25 gr/ 100 scf (6 mg/m3) specification. ! However, this reduction requires regeneration of the bed at 600F (315C) for extended time ????? Schema>c
of
integrated
natural
gas
desulfuriza>on
plant
! Dashed
line
denotes
regeneration
gas
stream.
CRYOGENIC
FRACTIONATION
! Distillation
!
the
most
widely
used
process
to
separate
liquid
mixtures
! It
seems
a
good
prospect
for
removing
CO2
and
H2S
from
natural
gas,
because
the
vapor
pressures
of
the
principal
components
are
dierent
! However,
problems
are
associated
with
the
separation
of
CO2
from
methane,
CO2
from
ethane,
and
CO2
from
H2S
Dierence
of
Vapor
Pressures
Dis>lla>on:
CO2
from
methane
! Relative
volatilities
(KC1/KCO2)
at
typical
distillation
conditions
are
about
5
to
1.
Therefore
one
would
expect
simple
fractionation
to
work.
! However,
because
the
liquid
CO2
phase
freezes
when
it
becomes
concentrated,
the
practical
maximum- vapor
concentration
of
methane
is
only
85
to
90
mol %.
Dis>lla>on:
CO2
from
ethane
! In
addition
to
solidication
problems,
CO2
and
ethane
form
an
azeotrope
(liquid
and
vapor
compositions
are
equal)
and
! consequently,
complete
separation
of
these
two
by
simple
distillation
is
impossible
Dis>lla>on:
CO2
from
H2S
! The
distillation
is
dicult
! The
mixture
forms
a
pinch
at
high
CO2
concentrations.
! This
separation
by
conventional
distillation
is
complicated
by
the
need
to
have
an
overhead
product
that
has
roughly
100
ppmv
H2S
if
the
stream
is
vented.
! The
bottoms
product
should
contain
less
than
two- thirds
CO2,
assuming
the
stream
is
feed
to
a
Claus
unit.
Membrane
Separa>on
! Membranes are used in natural gas processing for dehydration, fuel-gas conditioning, and bulk CO2 removal, but presently CO2 removal is by far the most important application ! Polymeric membranes separate gases by selective permeation of gas species in these membranes. ! The gas dissolves at the contact surface of the membrane and permeate across the membrane under the partial pressure gradient across the membrane wall. ! The basic idea of the process is to flow sour gas on one side of the membrane where only acid gases diffuse across the membrane to the permeate side and the rest of the gas exits as sweet gas Rate
of
Permea>on
! The
rate
of
permeation
of
gas
A(qA)
can
be
expressed
as:
! where
PM
is
the
gas
permeability
in
the
membrane,
Am
and
t
are
the
surface
area
and
thickness
of
the
membrane,
respectively,
and
PA
is
the
partial
pressure
of
gas
A
across
the
membrane.
CARBON
DIOXIDE
REMOVAL
FROM
NATURAL
GAS
! For
CO2
removal,
the
industry
standard
is
presently
cellulose
acetate.
! These
membranes
are
of
the
solution-diusion
type,
in
which
a
thin
layer
(0.1
to
0.5
m)
of
cellulose
acetate
is
on
top
of
a
thicker
layer
of
a
porous
support
material.
! Permeable
compounds
dissolve
into
the
membrane,
diuse
across
it,
and
then
travel
through
the
inactive
support
material.
! The
membranes
are
thin
to
maximize
mass
transfer
and,
thus,
minimize
surface
area
and
cost,
so
the
support
layer
is
necessary
to
provide
the
needed
mechanical
strength.
Hollow
Fiber
Membrane
Spiral
Wound
Membrane
Gas
ow
paths
for
spiral-wound
module
Single
Stage
CO2/CH4
Membrane
Separa>on
Two-stage
Membrane
process
Feed
Gas
Pretreatment
! Because
membranes
are
susceptible
to
degradation
from
impurities,
pretreatment
is
usually
required.
! The
impurities
possibly
present
in
natural
gas
that
may
cause
damage
to
the
membrane
ADVANTAGES
OF
MEMBRANE
SYSTEMS
! Low
capital
investment
when
compared
with
solvent
systems
! Ease
of
installation:
Units
are
normally
skid
mounted
! Simplicity:
No
moving
parts
for
single-stage
units
! High
turndown:
The
modular
nature
of
the
system
means
very
high
turndown
ratios
can
be
achieved
! High
reliability
and
on-stream
time
! No
chemicals
needed
! Good
weight
and
space
eciency
! Ease
of
operation:
process
can
run
unattended
DISADVANTAGES
OF
MEMBRANE
SYSTEMS
! Economy
of
scale:
Because
of
their
modular
nature,
they
oer
little
economy
of
scale
! Clean
feed:
Pretreatment
of
the
feed
to
the
membrane
to
remove
particulates
and
liquids
is
generally
required
! Gas
compression:
Because
pressure
dierence
is
the
driving
force
for
membrane
separation,
considerable
recompression
may
be
required
for
either
or
both
the
residue
and
permeate
streams
! For
natural
gas:
! Generally
higher
hydrocarbon
losses
than
solvent
systems
! H2S
removal:
H2S
and
CO2
permeation
rates
are
roughly
the
same,
so
H2S
specications
may
be
dicult
to
meet
! Bulk
removal:
Best
for
bulk
removal
of
acid
gases;
membranes
alone
cannot
be
used
to
meet
ppmv
specications