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PURIFICATION
ADVANCED PROCESS COMBINATION FOR RELIABLE
SYNGAS PRODUCTION
ABSTRACT
Lurgis Multi Purpose Gasification Process (MPG) is the reliable partial oxidation
process to convert hydrocarbon liquids, slurries and natural gas into valuable syngas.
The MPG burner has once again proven its capabilities in an ammonia plant based
on asphalt gasification. The advantages of a quick restart without inspection and the
inherent safety increase the availability and flexibility of the plant.
Lurgi is operating the HP-POX demonstration plant together with the University of
Freiberg, Germany. Gasification tests have been conducted successfully at
pressures of up to 100 bar. The results show that syngas for high pressure synthesis
such as methanol and ammonia can be produced more economically.
The Rectisol gas purification process yields ultra clean synthesis gas which is
required to avoid problems in the downstream synthesis. Rectisol removes all trace
components such as cyanide, ammonia, mercury, all sulfur types and metal
carbonyls, and no additional process steps for gas purification are required. Pure
carbon dioxide is produced as a separate stream and is readily available for
sequestration, enhanced oil recovery or other uses.
The reliability of the Rectisol process and the confidence of plant operators in this
process are acknowledged by the fact that more than 75 % of the syngas produced
world wide by coal, oil and waste gasification is purified in Rectisol units (reference
GTC Gasification Data Base 2004). Virtually all coal gasification plants currently
under construction rely on Rectisol.
The new, large GTL plants and hydrogen production facilities require effective CO2
removal. New developments make Rectisol attractive for this task.
LURGIS HISTORY IN GASIFICATION
Lurgis process know-how in gasification started with the development of the fixed
bed grate gasifier more than 70 years ago. This technology has been widely
exploited and more than 120 gasifiers are in operation worldwide. The technology is
especially advantageous for low-ranking coals and can handle very large ash and
moisture contents. Today, more than 75 % of the syngas from coal produced
GTC2005-Lurgi Presentation
worldwide is generated with this type of gasifier (reference GTC Gasification Data
Base 2004).
The joint development by Lurgi and British Gas led to the slagging type BGL gasifier.
The temperature at the bottom is raised above the ash melting point and the slag that
forms is routed via the proprietary slag valve at the gasifier bottom to the slag
hopper. This type of gasifier has been operated for more than five years now in the
SVZ plant in Eastern Germany with a feedstock mixture of municipal waste, petcoke
and coal.
The Multi Purpose Gasification (MPG) is Lurgis entrained flow gasification process
for converting hydrocarbon liquid feedstock such as refinery residues, chemical
waste streams and slurries to syngas. The MPG burner has been in commercial
operation for more than 30 years with a wide variety of feedstock, which is shown in
the following table.
GTC2005-Lurgi Presentation
Component
C
% wt
H
% wt
S
% wt
Cl
% wt
LHV
MBTU/lb(MJ/kg)
Toluene insolubles
% wt
Ash
% wt
W ater
% wt
Viscosity
cSt(at burner)
Particel size
mm
Trace components (selection only)
Al
ppmwt
Ag
ppmwt
Ca
ppmwt
Cu
ppmwt
Fe
ppmwt
Hg
ppmwt
Na
ppmwt
Ni
ppmwt
Pb
ppmwt
V
ppmwt
Zn
ppmwt
PCBs
PAK
600
5
3 000
200
2 000
10
1 200
50
200
10
1 200
200
20 000
ppmwt
ppmwt
70 000
10
170 000
800
40 000
25
8 000
500
10 000
100
10 000
65 90
9 14
6
50 ppm(wt)
15-18(35-42)
0,4
200
30
600
40 000
20
30
approx. 1000
0
approx. 2000
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GTC2005-Lurgi Presentation
Sat. HP-steam
77
Oxidant
(O2 Air)
Steam
666
A D A
FEBC)@9
77
Oxidant
(O2 Air)
Steam
Feed
Feed
7
77
Syngas
` c X
fI e dUb
a UWQWUT
` I Y X V I
R P I
SQEH
77
Quench
Water
Syngas
Soot Slurry
Quench Configuration
Boiler Configuration
at the bottom and is shock-cooled by the injection of water. If larger amounts of slag
occur and have to be transported with the wash water, the soot slurry is routed to a
slag lock system.
In the boiler configuration the energy of the hot syngas is used in a specially
designed boiler to produce valuable high-pressure steam.
The quench solution has to be selected for feedstock with higher salt and ash
content. It is also the process of choice for hydrogen production from gasification.
The major portion of the steam required for the CO shift conversion is produced in
the quench. This saves
Boiler Configuration
Quench Configuration
investment costs in the
CO shift unit and
Feedstock limitations due to
Feedstock flexibility
reduces
operating
possible Boiler fouling
costs
by
saving
HP-Steam available
MP-steam available
valuable high-pressure
highest thermal efficiency
trade off efficiency versus costs
steam.
g
500 m3/h
(0.5 MMSCFD)
Reactor:
Operating Pressure
100 bar
GTC2005-Lurgi Presentation
The
plant
is
designed as a multiprocess test facility
for catalytic autothermal
reforming,
so called ATR, and
the
non-catalytic
Water
Treatment
Liquid
Feeds
Storage
Natural
Gas
Compressor
Liquid O2
Flue Gas
Steam
Generator
Pump and
Vaporizier
Desulphurisation
Reactor
Soot Water
Cooler
Nitrogen
Supply
Instrument Air
Supply
Measuring
Station
Power Supply
Flare System
Fresh
water
Soot Water
Analytical
Area
The plant is designed as a stand-alone unit including all utility systems. Natural gas is
taken from the grid and compressed; liquid feedstock and oxygen are stored on site.
High-pressure process steam is produced in a boiler. The reactor is a quench type
reactor. The syngas produced is desulfurized and flared.
GTC2005-Lurgi Presentation
970 tpd of asphalt are gasified in 3 reactors to yield 115,000 Nm3/h of hydrogen (100
MMSCFD) which are converted to 1,350 tpd of ammonia.
The flow diagram below is applied in numerous ammonia plants worldwide operated
on the basis of heavy residue gasification. The asphalt is converted with pure oxygen
in the gasifier, the energy of the hot gas is used to generate high-pressure steam.
The steam is utilized as process steam in the gasification and CO shift units and to
Air
Air
Separation
O2
Feed
HP-Steam
Boiler
Refrigeration
Unit
Liquid
Ammonia
HP-Steam
Gasification
+ WHB
Rectisol
H2S Removal
Carbon
Recovery
Claus Unit
Sulfur
CO-Shift
Rectisol
CO2 Removal
Pure CO2
Liquid
N2 Wash
NH3
Synthesis
Urea
Synthesis
Urea
drive the large compressors and pumps. The raw gas is desulfurized in a H2S
Rectisol unit and then routed to the CO shift unit. The CO2 produced in the shift is
completely removed from the raw hydrogen in the CO2 Rectisol unit. Inert gases
such as argon, methane and unconverted CO are removed in a liquid nitrogen wash
GTC2005-Lurgi Presentation
unit where also the nitrogen for ammonia synthesis is added. The pure CO2
separated in the CO2 Rectisol plant is routed to the urea synthesis unit.
Rectisol
Turbine Gas
Raw Syngas
Purisol
Pipeline Gas
Pure Off-Gas
aMDEA
Off-Gas
MDEA / DEA
Others
Tail Gas
Treating
Sulphur
Purisol is a selective physical absorption process and competes directly with UOPs
Selexol process. These processes achieve on-spec pipeline gas and fuel gas with
regard to the total sulfur content remaining in the purified gas.
Lurgi also commands vast experience in amine gas treating processes such as DEA,
MDEA and aMDEA. The company performed the basic engineering for the worlds
largest natural gas acid gas removal unit for the Qatagas LNG project.
One major criterion for an appropriate process selection is the required gas purity.
Rectisol removes all sulfur components so, typically, a total sulfur content below
0.1 ppm is achieved. In addition, a pure CO2 stream with very low sulfur content can
be generated, which is suited for urea production, beverage industry sequestration or
just venting.
GTC2005-Lurgi Presentation
Rectisol
Impurities
0.1 1 ppm
10 50 ppm
5 ppm
Purisol
5 50 ppm
MDEA
3 50 ppm
1- 50 ppm
5 50 ppm
H2S
CO2
aMDEA
The sulfur content in the purified gas is higher with Purisol, this normally being
sufficient for fuel gas and pipeline gas qualities. The major portion of the sulfur
remaining in the gas is COS, which is only partly removed by Purisol. Selexol, as
the competing technology, exhibits a similar behavior in this respect.
Generic MDEA can be designed for selective sulfur removal. The achievable sulfur
concentration in the product gas is similar to that of the selective physical absorption
process Purisol. COS is not removed either. Where bulk CO2 removal is required,
activated MDEA (aMDEA) has to be selected. AMDEA also hydrolyses the major
portion of the COS in the feed gas which results in low total sulfur concentrations in
the purified gas. Acid gas with high H2S concentration suitable for the Claus process
can only be produced in a downstream concentration step as the CO2 is completely
removed by the aMDEA process. Due to the chemical nature of the absorption
process, amine regeneration consumes large amounts of LP and MP steam.
GAS PURIFICATION FOR GASIFICATION BASED HYDROGEN PLANT
Hydrogen can be economically produced from heavy residue feedstock. The
selection of the appropriate gas purification technology depends on the required
hydrogen purity, the value of by-products fuel gas and CO2, and the plant emission
regulations.
High BTU
Pure CO2
Feedstock
LP-Steam
O2
MPG
Quench
Raw Gas
Shift
Gas
Cooling
Rectisol
PSA
h
Steam
Low Sulfur
Fuel Gas
Hydrogen
H2S+CO2
Sulphur
ASU
MARS
Air
O2
Waste Water
Treatment
Metals/Ash
hh
Carbon
Slurry
OxyClaus
Process Water
The feedstock is
gasified in a quench
type
MPG
unit.
Carbon monoxide is
converted to hydrogen in a raw gas
shift, also referred to
as sulfur tolerant
shift.
After
gas
cooling
the
acid
gases have to be
removed. This can
GTC2005-Lurgi Presentation
In the first case, the Rectisol process produces an H2S-rich sour gas suitable for the
Claus unit. In addition, CO2 bulk removal is economical and a pure CO2 stream is
generated which can be used for sequestration, industry usage, and which can also
be vented without further treatment.
A PSA unit is used to free the raw hydrogen from trace components such as
methane, nitrogen, CO and argon. The PSA off-gas is a high BTU, low-sulfur gas.
In the second case
Rectisol is replaced
Feedstock
LP-Steam
by a selective acid
gas removal process
Steam
Hydrogen
Gas
MPG
Raw Gas
Selective
such as Purisol. The
PSA
Cooling
Quench
Shift
AGR
selective acid gas
O2
H2S+CO2
removal
also
Sulphur
OxyClaus
produces an H2S-rich
O2
Carbon
Slurry
sour gas suitable for
Process Water
the
Claus
Unit.
Waste Water
ASU
MARS
Treatment
Typically, 20 30 %
of the CO2 content of
Air
Metals/Ash
the raw gas is
removed
in
a
selective gas purification process. This CO2 is produced as a separate, impure CO2
stream with a significant sulfur concentration. This sulfur impurity is normally no
problem for sequestration purposes but simple venting is usually not permitted.
Low BTU
S > 100 ppm
Fuel Gas
Impure
CO2
Since the AGR is selective, a considerable amount of CO2 passes to the PSA unit
and is separated there. The PSA unit also separates the remaining sulfur impurities.
The PSA off-gas exhibits a low heating value due to the high CO2 content and also
contains a significant amount of sulfur.
In the third case, if the hydrogen is not required to have a high purity and the fuel gas
is of low value, the
PSA unit can be
Pure CO2
Feedstock
replaced
by
a
LP-Steam
methanation reactor,
97%
Steam
which converts CO
Metha- Hydrogen
Gas
MPG
Raw Gas
Rectisol
nation
Cooling
Quench
Shift
and CO2 to methane.
O2
The gas purification
H2S+CO2
Sulphur
unit has to remove all
OxyClaus
O2
Carbon
sulfur types to the
Slurry
ppb range and bulk
Process Water
Waste Water
ASU
MARS
CO2 removal to the
Treatment
low ppm range is
Air
Metals/Ash
required, since all
impurities end up in
the product hydrogen. Rectisol is the process of choice for this set up. A hydrogen
purity of 97% can be achieved and no fuel gas is produced.
p
ppp
GTC2005-Lurgi Presentation
10
FEATURES OF RECTISOL
Rectisol is often described as an expensive process for gas purification. This has to
be put into perspective considering the outstanding features of Rectisol which allow
to perform 5 tasks in one process.
Five in one
1. Trace contaminants removal
2. Deep desulfurization
4. CO2 purification
one Rectisol unit compares with five tasks to be performed in five process steps
Rectisol removes all trace contaminants contained in the raw gas from the
gasification unit such as organic sulfur compounds, ammonia and cyanide. Volatile
metal components such as carbonyls are also completely removed by Rectisol.
Mercury is equally trapped, which is important in coal gasification.
Rectisol directly delivers syngas qualities with an extremely low total sulfur content.
There is no need for any further gas purification.
Rectisol is suited for the economical removal of bulk CO2 and CO2 concentrations in
the low ppm range are achieved in the purified gas. Due to the physical nature of the
absorption process, the energy required to remove large amounts of CO2 depends
only on the total gas flow and gas pressure but not on the CO2 concentration in the
feed gas. The CO2 product stream is of a very good quality with a very low sulfur
content. It can be used for all purposes such as in the chemical industry (urea
production), beverage industry and for sequestration.
Rectisol produces H2S-rich acid gases even from raw gases with very high CO2 to
H2S ratios, which are typically found in gases downstream of CO shift units.
For an evaluation of the process economics one Rectisol unit has to be compared
against five process steps such as HCN and COS hydrolysis reactors and guard
beds.
GTC2005-Lurgi Presentation
11
Pure IGCC
Others
250
Rectisol
200
150
90 % of synthesis gas
produced by gasification
(non-IGCC use)
100
300
50
0
1960
1965
1970
1975
1980
1985
1990
1995
2000
2005
The advantages of the Rectisol gas purification process are reflected by its market
share as can be seen from the above diagram. Today, 75% of the syngas produced
from coal, heavy oil and wastes are purified in Rectisol units (source GTC Data
Base). The share of syngas purified by Rectisol increases to 90% for the syngas
produced for chemical synthesis such as ammonia and methanol (non-IGCC use).
Over the last two years Lurgi has been awarded orders for six new Rectisol plants.
GTC2005-Lurgi Presentation
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