ISSN 2176-3135
MODERN COKE OVEN GAS TREATMENT TECHNOLOGY
AT A NEW COKE MAKING PLANT IN BRAZIL*
Wolfgang Kern1
Mario Petzsch2
Antonio Esposito3
Helênio Resende Silva Júnior4
Abstract
The implementation of the Gas Treatment Plant (GTP) for CSPECEM, Ceara-Brazil
is a result of the closed partnership between Paul Wurth Italia S.p.A. and DMT, the
German leading company in Coke Oven Gas Treatment Plants. In addition to
technical issues reducing emissions, avoiding of waste and saving environment and
energy were technical challenges during the engineering phase. Below mentioned
three descriptions of technical solutions represents examples of a number other
innovations based on DMT’s know-how and experience in the field of by-product
plants. Generally the design of the complete GTP is based on the consideration of
modern features and design upgrading, with the aim of a safe operation with stable
conditions and a long-living cycle of the whole of the plant.
Keywords: By-product plant; Coke oven gas treatment plant.
1
Dipl. Ing., Head of Sales, DMT GmbH &. Co KG, Essen, Germany.
2
Dipl. Ing. (FH), Process Engineer, DMT GmbH &. Co KG, Essen, Germany.
3
Dott. Ing., General Manager Coke Making, Paul Wurth Italy S.p.A. Genoa, Italy
4
Process Department, Paul Wurth do Brasil, Belo Horizonte, MG, Brazil.
* Technical contribution to the 45º Seminário de Redução de Minério de Ferro e Matérias-primas, to
16º Simpósio Brasileiro de Minério de Ferro and to 3º Simpósio Brasileiro de Aglomeração de Minério
de Ferro, part of the ABM Week, August 17th-21st, 2015, Rio de Janeiro, RJ, Brazil. 842
ISSN 2176-3135
1 INTRODUCTION
Paul Wurth Italia S.p.A. in cooperation with DMT, the German leading company in
Coke Oven Gas Treatment Plants worked out the design, supplies of special
equipment and provides supervisors for erection and commissioning of the new Gas
Treatment Plant (GTP) for CSPECEM, Ceara-Brazil.
The plant as described will treat the crude coke oven gas of 87,500 Nm³/h for 1st
phase from the new coke oven batteries COB 1&2.The arrangement for 2nd phase
(COB 3&4) is also considered. The complete planed GTP (1st and 2nd phase) with all
units is designed for a max. quantity of 175,000 Nm3/h coke oven gas (COG) incl.
charging gas, respiration gas and tail gas.
The design of the gas handling and by-product facilities is utilising well proven
technologies, based on DMT’s know-how and experience in the field of by-product
plants and in addition on DMT’s long-term operational experience from various coke
plants, which were owned and operated by RAG AG.
The basic engineering has been started in February 2012. Currently the plant is
beiing built.
2 DESCRIPTION OF THE COKE OVEN GAS TREATMENT PLANT
2.1 General Overview
An overview of the entire by-product plant is given in the following scheme (figure 1).
The crude gas of the coke oven batteries (COB) of 1st phase (and later 2nd phase)
including the loaded flushing ammonia liquor, is taken over from the crude gas mains
at defined points.
Leaving the downcomer the gas is directed to the primary gas coolers (PGC). In the
PGC’s the coke oven gas (COG) is cooled down within two indirect cooling stages
using both cooling water and chilled water. Using a continuously operated flushing
system inside the PGC’s for cleaning purposes the operation time is optimised.
The tar-/ammonia water mixture leaving the down-comer is directed to the static tar
separation plant. From the tar separation plant the flushing liquor is returned to the
collecting main for flushing the COG coming from coke oven batteries, while coal
water is discharged via a tank to the gravel filter plant for final tar removal. Leaving
the tar separation plant the crude tar, as product, is led via the storage- and loading
station to further disposal. After collecting and preparing within the tar separation
plant, by tar solid decanters, solid particles are finally discharged into the battery feed
coal.
Coming from the primary gas coolers the cooled COG flows through the electrostatic
tar precipitators (ETP) for reducing the tar content upstream the gas exhausters. The
cooled and tar reduced COG passes the gas exhausters driven by electric motors.
The required performance and suction pressure of the gas exhausters have to be
considered for the pressure difference of the entire gas treatment plant, beginning
from coke oven batteries down to the inlet of the COG network.
* Technical contribution to the 45º Seminário de Redução de Minério de Ferro e Matérias-primas, to
16º Simpósio Brasileiro de Minério de Ferro and to 3º Simpósio Brasileiro de Aglomeração de Minério
de Ferro, part of the ABM Week, August 17th-21st, 2015, Rio de Janeiro, RJ, Brazil. 843
ISSN 2176-3135
Figure 1: Overview Flow Diagram of the By-product Plant
After leaving the gas exhausters the COG passes a scrubber system with integrated
final and internal cooling stages for reducing the H2S-/NH3-components. By these
cooling stages, operated indirectly with chilled water, the reached temperature level
secures the required performance values of the scrubber system. The scrubbing
liquor for the H2S/NH3 removal consists of stripped and deacidified water supplied by
the distillation plant.
As final gas cleaning stage a BTX-/Naphthalene scrubber is applied. In order to
reduce the BTX- and Naphthalene content the COG coming from H2S-/NH3-scubbers
is scrubbed by special tar based wash oil. For the regeneration of the wash oil and
the production of crude BTX as product a stripping system is provided.
In order to strip the H2S- and free ammonia-compounds from the enriched scrubbing
liquor coming from the H2S and NH3-scrubbers, a distillation plant consisting of
deacidifiers (DS) and ammonia strippers (AS) is provided with the capability to handle
the entire scrubbing liquor. The excess coal water, leaving the gravel filter plant, is
stripped under the presence of caustic soda (NaOH) in a fixed ammonia still column
section to remove the fixed ammonia compounds. The surplus outlet stream is led to
the biological effluent treatment plant (BETP).
The vapours leaving the distillation plant, mainly consisting of H2S, NH3, HCN, CO2
and hydrocarbons, will be treated in a combined NH3 cracking-/elementary sulphur
plant (Claus Plant). In this process the NH3-/HCN components are cracked while the
H2S content is converted to liquid sulphur. The tail gas flow of the Claus Plants is
returned to the crude gas mains upstream the primary gas coolers.
Below the following three technical descriptions of different units are given as
examples for implementation.
* Technical contribution to the 45º Seminário de Redução de Minério de Ferro e Matérias-primas, to
16º Simpósio Brasileiro de Minério de Ferro and to 3º Simpósio Brasileiro de Aglomeração de Minério
de Ferro, part of the ABM Week, August 17th-21st, 2015, Rio de Janeiro, RJ, Brazil. 844
ISSN 2176-3135
2.2 Chilled Water Plant
Corresponding state of the art high performance scrubbing system needs for the
absorption process a temperature decrease. Therefore a chilled water system is
designed (see figure below). This chilled water system allows keeping optimum COG
and process water temperatures even during hot periods.
The technical standard and the structure of the chilled water plant, comprising of
absorption type (e.g. lithium bromide system) or compressor type refrigerating units.
The type which should has been considered depends on the availability of steam and
electrical power as well as the required technical specifications. The chilled water
plant has to be designed with respect to naphthalene precipitation risks in the primary
cooling area and regarding the minimisation of heat exchanger areas. Feed
temperature of the chilled water is about 14 °C and return temperature amounts to
24°.
More detailed information and the structure of the chilled water plant are shown in the
attached scheme (figure 2).
Figure 2: Overview Chilled Water System
2.3 BTX - Scrubbing System and Recovery Unit
After leaving the NH3 scrubber the COG is directed to the BTX scrubbing system for
removal the BTX compounds. A schematic flow diagram is given below (figure 3).
The COG enters the scrubber at the bottom and moves upwards through the
* Technical contribution to the 45º Seminário de Redução de Minério de Ferro e Matérias-primas, to
16º Simpósio Brasileiro de Minério de Ferro and to 3º Simpósio Brasileiro de Aglomeração de Minério
de Ferro, part of the ABM Week, August 17th-21st, 2015, Rio de Janeiro, RJ, Brazil. 845
ISSN 2176-3135
scrubbing sections before it leaves the scrubber at the top. The COG, reduced by
BTX components, is directed to the COG distribution network.
The scrubbing procedure is carried out by wash oil, coming from the stripped oil
buffer tank, which enters at the top of the scrubber flowing downwards in counter flow
to the rising COG. The scrubbing sections consist of expanded metal or structured
packings and distribution trays.
The enriched wash oil leaves the scrubber at the bottom via a sealing pot by gravity
and is collected in a buffer tank before it is fed to the wash oil regeneration plant.
Figure 3: BTX Scrubbing System
Wash oil losses are to be compensated by adding fresh wash oil into the enriched
wash oil buffer tank. The fresh wash oil is supplied from fresh wash oil tank.
The enriched wash oil, leaving the BTX scrubbing system, is fed to the wash oil
regeneration plant to reuse it for further wash processes in the BTX scrubber.
Thereby, a saleable BTX fraction is produced.
Enriched wash oil from the BTX-scrubber (see figure 4), intermediately stored in a
buffer tank, is pumped to the BTX stripper, passing 2 heat exchanger groups for
indirect heating with hot stripped oil and steam, respectively. The BTX fraction is
stripped by adding steam in the bottom area of the distillation column. The BTX
fraction loaded with water vapour, leaves at the top of the BTX stripper and passes a
condenser / cooler, sequently, before entering a separation tank.
The separation tank is equipped with special packings to reach an excellent
separation between water/crude benzene. The crude benzene is fed to the storage
tank by means of pumps while the separation water is discharged to the distillation
plant. As a site fraction of the BTX stripper, the naphthalene oil fraction is drawn,
collected in a drain tank and mixed to crude tar coming from tar storage tanks.
* Technical contribution to the 45º Seminário de Redução de Minério de Ferro e Matérias-primas, to
16º Simpósio Brasileiro de Minério de Ferro and to 3º Simpósio Brasileiro de Aglomeração de Minério
de Ferro, part of the ABM Week, August 17th-21st, 2015, Rio de Janeiro, RJ, Brazil. 846
ISSN 2176-3135
Figure 4: Wash Oil Regeneration Plant
The stripped wash oil leaves the bottom of the stripper and is pumped through 3
groups of heat exchangers. In the first heat exchanger group the heat of the stripped
wash oil is used for indirect heating up the cold enriched wash oil, coming from the
BTX-scrubber plant. Applying the following 2 heat exchanger groups, the stripped
wash oil is indirectly cooled with cooling and chilled water. Then, the stripped wash
oil is directed to the buffer tank of the scrubbing system for further use in the BTX
scrubber.
Before feeding the hot stripped wash oil to the above mentioned oil-/oil heat
exchanger, a small part of hot wash oil is led to the pitch column, supported by
injected steam. By removing high viscose pitch components, the wash oil is kept in a
feasible range of viscosity.
The used wash oil is generated by a distillation fraction of crude tar from coke plants.
The discharged residuals from the pitch column are mixed to the naphthalene oil /
crude tar mixture, which is fed to the tar storage tanks. No additional treatment of
waste oil/muck is necessary.
2.4 Combined NH3-Cracking/Elementary Sulphur Plant (Claus Plant)
For processing the H2S/NH3 vapours coming from the distillation plant, a combined
ammonia cracking/elementary sulphur plant (see schematic flow diagram below,
figure 5) is provided. In this project a high efficiency process with a 2-stage Claus
reactors is installed.
Under the top pressure of the deacidifier and ammonia stripping system, the
H2S/NH3-vapours are led to the burner system of the cracking reactor. Operating at
sub-stoichiometrical combustion conditions, at a proper temperature for reaction, a
certain ratio of H2S is burned to SO2. The combustion air is supplied by an air blower.
After preheating in a steam operated heater the air is directed into the burner system.
Especially, for start-up operation and after process interruptions partly cleaned COG
* Technical contribution to the 45º Seminário de Redução de Minério de Ferro e Matérias-primas, to
16º Simpósio Brasileiro de Minério de Ferro and to 3º Simpósio Brasileiro de Aglomeração de Minério
de Ferro, part of the ABM Week, August 17th-21st, 2015, Rio de Janeiro, RJ, Brazil. 847
ISSN 2176-3135
or natural gas is used for heating up and stabilising the combustion. The
COG/natural gas is supplied by a gas blower.
Inside the catalyst bed of the crack reactor the NH3 and HCN compounds of the
vapours are cracked. Downstream of the catalytic bed secondary air is supplied to
adjust the stoichiometrical ratio of H2S/SO2 for the reaction in the following Claus
reactors.
The hot process gas leaves the crack reactor and passes the waste heat boiler
system. In this boiler system the process gas is indirectly cooled by generating steam
via boiler feed water, added by pumps. The parameters of the produced steam can
be selected in a certain range. As shown in the flow diagram, it is proposed to
generate HP-steam in combination with LP steam. During cooling down of the
process gas within the LP boiler, the first sulphur is condensed. After separation it is
directed to the sulphur sealing pot.
Figure 5: Combined NH3-Cracking/Elementary Sulphur Plant
By mixing the outlet gas of the HP boiler with the outlet of the LP boiler the required
inlet temperature to the 1st Claus reactor stage is adjusted. Within the first and
second stage of Claus reactors, the process gas passes a catalyst bed. By that, the
reaction between SO2 and H2S takes place to produce liquid elementary sulphur (Sx)
plus H2O.
Leaving the first stage of the Claus reactor, the process gas is directed to the first
stage of a sulphur condenser. Similar to the LP boiler, the process gas is indirectly
cooled by boiler feed water generating LP steam. Then the process gas passes a
separator for precipitation of the condensed sulphur. While the liquid sulphur is led to
the sulphur sealing pot, the process gas flows to a downstream gas heater. Using
produced HP steam of the HP boiler, the process gas is indirectly reheated up to
conversion temperature for the Claus reaction. After reheating the process gas is led
to the second stage of the Claus reactor to convert more H2S/SO2 and to produce
further sulphur according to above mentioned reaction. Subsequently, in the second
stage of the sulphur condenser the gas is indirectly cooled while LP steam is
generated. After cooling the process gas and sulphur precipitation in the downstream
* Technical contribution to the 45º Seminário de Redução de Minério de Ferro e Matérias-primas, to
16º Simpósio Brasileiro de Minério de Ferro and to 3º Simpósio Brasileiro de Aglomeração de Minério
de Ferro, part of the ABM Week, August 17th-21st, 2015, Rio de Janeiro, RJ, Brazil. 848
ISSN 2176-3135
separator, the process gas (tail gas) with residual contents of SO2 and H2S, is
directed to the crude gas collection main in front of the PGC. Leaving the separator,
the sulphur flows into the sulphur sealing pot.
The produced liquid sulphur, firstly collected in the sulphur sealing pot, is discharged
into a sulphur drain tank and from there pumped to the sulphur storage tank. Both,
the sulphur drain and the storage tanks are steam heated by coils. Periodically, the
liquid sulphur is fed into transport vessels for distribution to further disposal by a
loading station.
The surplus steam, produced in HP-/LP-boiler and sulphur condenser, is led to the
steam distribution network for further utilisation.
Beside on a higher efficiency by using a 2-stage Claus reactor, also the composition
of the tail gas should be considered. For avoiding additional organic based Sulphur in
effluent, the Claus Plant is designed as described below:
By using of a double stage Claus Plant the cracking of Ammonia and the
production of liquid Sulphur from H2S/NH3-vapour feed are realized.
Furthermore, the Hydrolysis reactions according to the following reactions take
place:
COS + H2O → CO2 + H2S
CS2 + H2O → CO2 + 2 H2S
Contrary to operating a double stage Claus Plant, during operating a Single
Stage Claus Plant above mentioned hydrolysis reactions are not executed.
COS and CS2 is not converted in a Single Stage Claus Plant and is recycled
via Tail Gas line to Primary Gas Coolers and downstream plant components.
These gas components react in downstream scrubber and distillation columns
and cause via Effluent the Thiocyanate problem in the BETP.
3 RESULTS
The impurities of crude COG in front of the gas treatment plant is given in following
Table 1.
Table 1. Impurities of crude COG (depending on the coals used)
Components Unit Value
Tar g/Nm³ 15
Hydrogen Sulphide g/Nm³ 8
Ammonia g/Nm³ 9
Naphthalene g/Nm³ 8
BTX g/Nm³ 33
After leaving the gas treatment plant the design of the impurities is given below
(Table 2).
Table 2. Impurities of cleaned COG
Components Unit Value
Tar g/Nm³ < 0.02
Hydrogen Sulphide g/Nm³ < 0.5
Ammonia g/Nm³ < 0.04
Naphthalene g/Nm³ < 0.1
BTX g/Nm³ <5
* Technical contribution to the 45º Seminário de Redução de Minério de Ferro e Matérias-primas, to
16º Simpósio Brasileiro de Minério de Ferro and to 3º Simpósio Brasileiro de Aglomeração de Minério
de Ferro, part of the ABM Week, August 17th-21st, 2015, Rio de Janeiro, RJ, Brazil. 849
ISSN 2176-3135
3.1 Subtitle – Application Example
Integrating a new chilled water plant (Pos. 2.2), coke making plant Prosper
ArcelorMittal, Germany, 2008
Installation of BTX - Scrubbing System and Recovery Units (pos. 2.3) in
the frame of designing a complete GTP, PT Krakatau POSCO, (Paul Wurth
Italia S.p.A.), 2013
Combined NH3-Cracking/Elementary Sulphur Plant (Claus Plant, pos. 2.4)
installation within existing GTPs at POSCO, Korea, 2007
4 CONCLUSION
The described plant applications can be integrated in gas treatment units of coking
plants and similar process applications with the aim
- of reducing pollutant- and impurity emissions into environment,
- to optimize process sequences and economical yields of gas cleaning plants,
- to prevent process disturbances,
- to save energy and material resources.
Above mentioned three descriptions of technical solutions represents examples of a
number other innovations based on DMT’s know-how and experience in the field of
by-product plants and in addition on DMT’s long-term operational experience from
various coke plants, which were owned and operated by RAG AG.
SOURCE
1 All documentation published in this paper are internal documents of DMT GmbH &. Co
KG.
* Technical contribution to the 45º Seminário de Redução de Minério de Ferro e Matérias-primas, to
16º Simpósio Brasileiro de Minério de Ferro and to 3º Simpósio Brasileiro de Aglomeração de Minério
de Ferro, part of the ABM Week, August 17th-21st, 2015, Rio de Janeiro, RJ, Brazil. 850
