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LURGIS MPG GASIFICATION PLUS RECTISOL GAS

PURIFICATION
ADVANCED PROCESS COMBINATION FOR RELIABLE
SYNGAS PRODUCTION

Gasification Technologies 2005


San Francisco, October 9 12, 2005
Ulrich Koss, Holger Schlichting - Lurgi AG, Germany

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.

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Actual Operating Ranges


Quench Configuration
Oil Mode
W aste/Slurry
Mode
65 90
90
9 14
14
6
6
2
8
15-18(35-42)
2-13(5-30)
6
45
3
25
2
5 30
200
300
2

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

Operating Lim its


Boiler Configuration

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
3

FEATURES OF MULTI PURPOSE GASIFICATION


The special features of the MPG process are the very reliable burner and the
quench. The burner uses a special diffuser nozzle system to atomize the feedstock
into fine droplets which are required for good conversion. The burner allows the
simultaneous feed of 2 or more different feedstock into the reactor via one burner.
This is important for
applications where the
feed are immiscible or,
Feed
worse, tend to react with
O2 + Steam
each other.


  
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The second feature is the


quench technology. It
allows the feed of ash
containing feedstock. The
Quench
Water
ash melts in the reactor,
Gas-offtake
forming a slag which flows
along the refractory lined
Soot Slurry
wall. The hot gas and the
slag are shock-cooled by
water injection in the
quench pipe. The slag is vitrified to a non-leachable solid and is routed with the water
to the solids separation system, designated as the MARS unit (Metals Ash Recovery
System).

GTC2005-Lurgi Presentation

ADVANTAGES OF THE MPG BURNER


The MPG burner affords a very high feedstock flexibility. No limitations exist
regarding the flash point of the feedstock. This is often an issue in the case of highviscous feedstock, which has to be heated to high temperatures before feeding it to
the reactor in order to obtain a low viscosity at the burner tip. If the feedstock has a
low flash point, vaporization of the low-boiling constituents of the feedstock starts in
the burner nozzle, which disturbs the feedstock flow and results in damage to the
burner tip. The MPG burner uses steam to atomize the oil into fine droplets in a
proprietary diffuser nozzle system. Additional hydrocarbon vapors generated by
heating the feedstock do not affect the feedstock flow at the burner tip.
Due to the atomization of the feedstock with steam the burner can handle highviscous feedstock and also particles in the mm range.
MPG reactors afford a very good availability and reliability. This is the result of a
combination of very long on-stream times and the option of restarting the reactor
without burner inspection. This increases the operational flexibility and reduces the
maintenance work.
The burner is equipped with a pressurized cooling water system. This gives an
inherent safety to the burner operation. A surveillance system detects and records
any deterioration of the front plate and the burner nozzles. This information is
analyzed and trips a safe shut down of the reactor, if necessary.
The burner creates a low pressure drop across the feed system. This allows the use
of inexpensive feedstock pumps.
The burner is equipped with an integrated heat-up burner so that handling at the hot
reactor is not necessary during start up.

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

COMPARISON OF QUENCH VS. BOILER CONFIGURATION


The MPG gasification reactor can be designed with either a quench or a waste heat
boiler for gas cooling. In the quench configuration the hot raw gas leaves the reactor
GTC2005-Lurgi Presentation

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

2 step gas cleaning

Fastest route to hydrogen


but weak Claus gas

The highest thermal


efficiency is achieved
with the boiler solution.
Higher costs for boiler
Lowest cost for hydrogen
(normally payback < 2 years)
The energy of the hot
production unit
raw gas from the
reactor is used to
produce valuable highpressure steam. This route is open for the low ash containing feedstock typical for
refinery residue streams such as vacuum residue and asphalt. The high-pressure
steam is used in the plant as process steam, to drive large compressors and pumps
or in an IGCC application to increase the overall plant efficiency.
strong Claus gas

THE HP-POX DEMONSTRATION PLANT


Lurgi built a demonstration plant for high-pressure gasification processes to further
improve syngas production processes. The plant was built by Lurgi for a joint
research project with Professor Meyer at the Technical University of Freiberg in
Saxony, Germany.
The
project
is
supported by the
German Ministry of
Multi Process Test Facility:
Economics
and
ATR, Gas-Pox,
Technology and by
MPG (liquid feedstock)
the Saxony Ministry
of State for Science
Feedstock:
and the Arts.
Liquid Feedstock
500 kg/h
Natural Gas

500 m3/h
(0.5 MMSCFD)

Reactor:
Operating Pressure

100 bar

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The
plant
is
designed as a multiprocess test facility
for catalytic autothermal
reforming,
so called ATR, and
the
non-catalytic

partial oxidation of natural gas, Gas-POX, as well as the gasification of liquid


hydrocarbon streams, heavy oil and residues, designated as MPG operation. The
maximum throughput is 500 m3/h for natural gas feedstock and 500 kg/h for liquid
feedstock, respectively. Tests have already been successfully performed with
pressures of up to 100 bar.

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.

APPLICATION OF THE MPG BURNER IN AN AMMONIA PLANT BASED ON


ASPHALT GASIFICATION
Fosfertils operates an ammonia plant based on asphalt gasification in Brazil. The
syngas plant was originally built by Lurgi in the early 80s. The MPG burner was
installed and commissioned in one of the existing reactors in 2001.
Feedstock to the gasifiers is residue asphalt. The asphalt is solid at ambient
condition and exhibits a high viscosity of 360 cSt at 180 It has to be heated to
C.
temperatures above 260 to lower the feedstock viscosity for operation with the
C
original burners. The low flashpoint of 170 results from blending in the refinery and
C
is frequently the reason for the short service life of the original burners.
The feature of the MPG burner to operate with high-viscous feedstock has the
advantage for plant operation that high-pressure steam for feedstock heating can be
saved as the asphalt can be fed at lower temperatures. The higher viscosity and the
low flash point do not affect the operation of the MPG burner.

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

Soot and Ash


Pellets

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.

LURGIS GAS PURIFICATION TECHNOLOGIES


The gas purification unit is the second most important process in a gasification plant,
which defines plant reliability and operating costs such as maintenance and
synthesis catalyst lifetime. Lurgi commands the full range of gas purification
technologies, partly as proprietary technology, and specialist know how for the openart technologies such as amine treating.
The most suitable gas purification process is selected with respect to the
specification of the final product syngas, fuel gas, pipeline gas and by-products
required such as pure CO2. Rectisol is the process of choice for chemical synthesis
and is also often beneficial for other applications.
Own Technology
Specific Expertise
Natural Gas

Ultra Pure Syngas

Rectisol

Turbine Gas
Raw Syngas

Purisol

Pipeline Gas
Pure Off-Gas

aMDEA
Off-Gas

MDEA / DEA
Others

Pure CO2 By-Product


Sulphur
Recovery

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

Product Gas Purity


Process

Purified Gas Quality

Rectisol

Impurities

0.1 1 ppm
10 50 ppm

Total Sulfur (H2S + COS)


CO2

5 ppm

H2S in CO2 by-product

Purisol

5 50 ppm

H2S, no COS removal

MDEA

3 50 ppm

H2S, no COS removal

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

be achieved with various processes.

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

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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

COS, CS2, NH3, HCN, Hg,

2. Deep desulfurization

Directly to synthesis feed quality


total sulfur < 0.1 ppm (only with Rectisol)

3. Bulk CO2 removal

100 % CO2 can be recovered

4. CO2 purification

Total S < 5 ppmV in CO2 Stream

5. Acid gas enrichment

Claus-suited acid gas even at a CO2/H2S


ratio of > 500

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.

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Capacity Installed & Operating


350

Pure IGCC
Others

250

Rectisol

200
150

Today, Rectisol purifies


q

90 % of synthesis gas
produced by gasification
(non-IGCC use)

100

75 % of the worlds synthetic


gas produced from
oil residue, coal, & wastes
q

Mio Nm3/day ex Gasifiers

300

50
0
1960

1965

1970

1975

1980

1985

1990

1995

2000

2005

Source: GTC Gasification Data Base

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.

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