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By
Keith Wright
It was Council’s intention to follow the COMA Coke Oven Textbook with an
accompanying COMA By-Products Textbook. However the latter was never
completed.
The following notes were prepared for inclusion in the By-Products Textbook.
_______________________________________________________________
Keith Wright was Process Engineering Manager at OSC Process Engineering until 2001. He is
currently working for MWH (Montgomery Watson Harza) as a Principal Process Engineering
Consultant primarily to the water industry,
THE COKE OVEN MANAGERS’ YEAR-BOOK 222
GENERAL
The gas is sprayed with flushing liquor as it leaves the individual oven
chambers, the objective being to reduce the temperature to a reasonably low
value and to condense the most easily condensable (high boiling point)
components. The gas is therefore cooled by adiabatic evaporation of some the
spray liquor and the mixed gases from the battery are reduced to approx. of
80–84°C water saturated, this temperature being sufficiently low for handling
in the gas collecting mains etc.
The gases, together with flushing liquor and condensed tar, pass along the
collecting main and through a butterfly control valve before leaving the battery
area. This control valve is set to maintain a slight positive pressure, approx.
100 mb, in the collecting main to provide safe working conditions in the coke
oven chambers.
Spraying the gas leaving the oven chamber with ammonia liquor will
condense from the gas the high-boiling tar vapour compounds and ammonium
chloride. The tar will form a separate liquid phase with the hot spray liquor
and the ammonium chloride will dissolve in the liquor. The tar and liquor are
separated from the gas stream at the downcomer and pass to the tar decanting
plant.
The flow of coke oven gas is withdrawn from the battery by a centrifugal
blower, the exhauster, and delivered through the gas vessels of the by-product
plant at a sufficient pressure for distribution as a fuel. Before passing to the
exhauster, the gas is cooled in the primary coolers to approx. 25°C. By this
means a large proportion of the condensable material is removed, e.g. tar and
naphthalene. Most of the water vapour is also condensed from the gas and the
gas contracts in cooling from approx. 80°C to 25°C. The volume of gas which
the exhauster has to handle is therefore very much reduced.
To ensure reliable and efficient coke production from the coke oven plant it
is absolutely essential to have continuous exhauster operation to remove the
THE COKE OVEN MANAGERS’ YEAR-BOOK 224
On most coking plants the exhausters are located in the gas stream
immediately following the primary gas coolers, however, some plants have the
exhausters located at the end of the gas train. Whilst this latter position
provides a cleaner gas for exhauster operation, location of the exhauster after
the primary coolers provides for most of the gas train to operate at a slight
positive pressure.
Following initial cooling and passage through the exhausters the coke oven
gas flows in sequence through a number of vessels which incorporate means
for removing undesired or saleable components. Throughout the by-product
plant and associated equipment it is always necessary to assume the presence
of both tar and naphthalene, even when these materials should not be present
in the system. Although these materials may be present in only trace
concentrations they can accumulate over a period of time to create blockages,
typically in plant drains and vents.
1. it is a poisonous component;
2. in association with other components it causes plant corrosion;
3. its combustion products (SO2/SO3) are very environmentally
undesirable if released to the atmosphere when the coke oven gas is
burnt.
THE COKE OVEN MANAGERS’ YEAR-BOOK 226
There are many hydrogen sulphide removal processes which basically rely
upon contacting the gas with a circulating absorbent, from which sulphur is
recovered by a controlled oxidation reaction.
The sequence may be varied if, for instance, two processes are
interdependent. For example, in some process streams the ammonia and
hydrogen sulphide removal processes are interdependent.
Following the primary gas cooling stage most of the gas treatment
processes are designed to operate at slightly above atmospheric temperature,
25 – 30°C. Since many of the absorption processes are very temperature
dependent, for example, ammonia, benzole and hydrogen sulphide removal, it
is advantageous to maintain the gas stream as cool as practical.
deposition into gas mains or water circulation systems. Both water and
naphthalene dew point temperatures correspond to the primary cooler exit
temperature and pressure, gas passage through the exhausters will raise these
temperatures typically by 2 – 3°C.
The design of many elements of modern coke oven plant by-product units
has been affected quite profoundly by modern personnel safety and
environmental pollution considerations. These features can be typified by
brief mention of the main characteristics.
In general terms the modern coke oven gas by-product plant consists of a
sequence of operations carried out on the main gas flow stream, together with
associated side-stream processing equipment. For almost every operation
several options of plant designs are available.
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229 KEITH WRIGHT
1. Introduction
Tar and ammonia liquor are produced in the coal carbonisation process
from materials contained in the coal feedstock and water added to the process.
The main tar and liquor combined flows in the by-product plant arise as a
result of the gas cooling as it leaves the oven chamber and the subsequent
primary gas cooling. Minor flows of these materials arise at various other
locations such as plant drains or where other plant condensates form.
The functions of the plant sections dealing with tar and liquor can be
summarised as:-
Because the flushing liquor supply is so important for good coking plant
operation it is normal for plant and equipment dealing with flushing liquor
decanting and recirculation to be sized and duplicated as necessary to provide
adequate standby resources when units have to be taken out of service for
maintenance.
The main sources for tar and ammonia liquor on a coking by-product plant
are indicated schematically in Fig 1, which also shows the flushing liquor
circulation.
On a typical coke oven plant the liquor production rate will be approx. 120
– 130 litre/te coal carbonised. The flushing liquor supply to the battery will be
approx. 4000 litres/te coal carbonised, depending upon the battery and
collecting main arrangement. The liquor contains dissolved ammonia as a
wide variety of compounds. These are generally grouped as ‘fixed’ or ‘free’
compounds are relatively stable whilst the ‘free’ compounds can be
decomposed solely by heating to approx. 100°C. The ‘free’ compounds
include the hydroxide, carbonate, bicarbonate, sulphide and cyanide; the
‘fixed’ compounds include the chloride, thiocyanate, thiosulphate and
sulphate. In addition, the ammoniacal liquor will contain smaller but
important concentrations of dissolved neutral oils, phenols, and tar bases
(pyridine etc).
The compounds present in the coal tar are formed ultimately from complex
organic materials in the coal charge. The heating process during coal
carbonisation breaks down some of these materials into simpler compounds,
and further reforming reactions also take place as these vapours pass through
the hot coke mass forming in the oven chamber and through the hot space
above the charge.
The first fraction to condense, when the flushing liquor cools the oven exit
gases to 80 – 84°C, corresponds to the heavier and more viscous fraction of the
higher boiling point compounds.
The types and properties of the coal tars vary considerably depending on
the nature of the coal charge and the coal carbonisation conditions. High
temperature carbonisation, such as in modern coking plants, subjects the tar
vapours to more rigorous thermal cracking than lower temperature processes.
Consequently the tars from the higher temperature plants contain higher
proportions of the aromatic types of hydrocarbons.
1.3 Solids
Each of the tar fractions collected on the by-product plant contain amounts
of solid materials. These range in size from near-colloidal particles to
appreciably large pieces. Whilst almost all the solids are generated in the
coking process some of the larger pieces are foreign, e.g., refractory materials
or substances inadvertently introduced by plant operators into the system.
The smaller particles are usually carbonaceous and can form agglomerates,
almost all of the larger particles can be separated from the liquid tar, by
sedimentation procedures, generally carried out in stages.
The very high flushing liquor circulation rate does not allow sufficient time
to make a thorough tar/liquor separation.
The high tar viscosity retards separation of small liquor droplets and fine
solids from the tar.
In the case of the flushing liquor requirement operating plants are able to
make a satisfactory compromise by using the decanting equipment to remove
larger solids and almost all of the tar by a high-rate gravity settling process.
Because the flushing liquor has to pass through spray nozzles at the point of
use any solids large enough to cause blockage problems are removed by a
strainer located in the flushing liquor pump delivery line. Whilst earlier plants
used basket type filters for this purpose, which required manual cleaning, the
modern equivalent motor-driven unit is continuously automatically back-
flushed and solids removed from the flushing liquor are returned to the
decanting plant.
In addition to the main use for cooling the gases leaving the individual coke
ovens, flushing liquor is used on by-product plants as a convenient liquid to
clean or maintain pipework and equipment free from blockage. There are
several advantages in using flushing liquor in this way. Because the
ammoniacal liquor contains only components dissolved from the coke oven
gas it is chemically compatible with most of the other condensates and process
liquors on the by-product plant, and does not introduce additional corrosion or
precipitation problems. For a similar reason it is advantageous if the flushing
liquor contains some free tar, because many of the plant piping and equipment
deposits contain such materials as naphthalene, these materials are usually
readily soluble in hot tar.
As described above in 1.3 all the tar streams generated on the plant contain
some types of solids. The larger particles and pieces are normally readily
separated from the tar in the initial flushing liquor decanting equipment.
Removal and handling of solids removed from tar is never an easy operation, it
is complicated by the ever-present tar. Although a substantial proportion of
the larger solids can be removed when the tar is held for a period of 6-12 hours
the finer particles are difficult to separate, even after days or weeks storage.
Over the years many attempts have been made to use centrifuges to eliminate
this problem. Whilst in some instances it has been possible to achieve useful
separations it has never been really acceptable for long-term adoption as a
235 KEITH WRIGHT
reliable process. Ultimately the near colloidal sized particles are present in the
tar shipped out from the plant and the downstream user has to be aware of the
situation and develop his process or plant accordingly. It is a normal objective
to remove the tar moisture content to 2 – 3% in the initial separation stage.
2.1 Rectangular
The mixture of tar, liquor and solids to be separated flow into one end of
the decanter and pass along the unit, bulk separation of the two liquid phases
taking place rapidly into an upper liquor and low tar layer. Individual units
can be up to approx. 350m3 capacity, normally the capacity allows up to 15-20
mins liquor residence time and several hours for the tar.
The settled tar is withdrawn via an adjustable overflow, this can be used to
raise or lower the interface between the tar and liquor in the decanter. Raising
this interface increases the volume, and hence the settling time available, of the
THE COKE OVEN MANAGERS’ YEAR-BOOK 236
237 KEITH WRIGHT
tar. This feature allows some control to be exercised over the tar moisture
content as it passes to storage.
2.2 Double-Cone
Solids fall to the bottom of this annular space and are discharged
periodically through a double-valved hopper arrangement, the upper valve of
which remains open in the solids collection phase.
Surplus liquor and tar flow up through a central riser and enter the inner
conical vessel. This arrangement provides good separation conditions for the
tar and liquor, positive features being that there is no moving mechanism
present and that in particular the tar section temperature is maintained by the
hot liquor in the annular space. Settled excess liquor flows continuously out
from the upper section of the inner cone, and settled tar is withdrawn
continuously from the bottom of this cone via an external line. The level of
the nominal tar/liquor interface is controlled by the variable height adjustable
overflow vessel on the tar outlet line.
THE COKE OVEN MANAGERS’ YEAR-BOOK 238
239 KEITH WRIGHT
THE COKE OVEN MANAGERS’ YEAR-BOOK 240
2.3 Vertical
The vertical type of decanter is shown in Fig 4, the decanting and separation of
tar and liquor taking place in a vertical cylindrical vessel. This vessel is of
simple construction, it is divided into two separate compartments by an inner
cone in the lower part.
Before entering the decanter the combined plant tar and liquor flows pass
through a solids pre-separator. This small vessel incorporates a scraper
conveyor to remove solids and any heavy tar from the system to prevent plant
blockages.
The tar and liquor flow enters the decanter chamber via an inlet pipe which
feeds it into the unit somewhat above the nominal tar/liquor interface. Tar
settles in the lower section and is withdrawn continuously from the base via an
adjustable overflow for transfer into intermediate and final storage.
Liquor overflows from the upper level of the chamber and passes into the
lower compartment, where it helps to maintain the tar temperature. Flushing
and excess liquors are withdrawn from this lower compartment continuously
for recirculation or storage respectively.
3. Storage
3.1 Liquor
The main ammonia liquor storage system on a coking plant has to be such
as to further prepare this material for the downstream processing. As indicated
above, the main impurities in the ammonia liquor at this stage will be small
quantities of tar droplets which will sink naturally frequently together with
some tar material having an apparent density less than the liquor and therefore
a floating fraction. Consequently the ammonia liquor storage tanks have to be
provided with a bottom tar withdrawal means, the liquor outlet being
somewhat above the tank bottom. Similarly, a top-level overflow can be
provided to remove any floating fraction.
241 KEITH WRIGHT
The tank vents have to be maintained free from solid naphthalene deposits,
e.g., by clean gas purging or heating – or both.
The number and capacity of ammonia liquor storage tanks are determined
by predicted upstream or downstream plant maintenance outage times as well
as the need to provide an extended period for settling to provide a clean and
tar-free liquor. It should also be remembered that this liquor will contain very
low but important concentrations of such dissolved organic materials as
benzole, naphthalene, phenols and tar bases.
3.2 Tar
The treatment and storage equipment for tar discharged from the primary
decanting system has to be designed to produce a tar of low moisture and
solids content to suit market conditions.
The first stage of storage/treatment for the tar is frequently carried out in
horizontal cylindrical tanks, sized to contain individually 24 hours plant tar
production. These units are heated by internal or external low-pressure steam
coils to bring the tar temperature up to 90 – 95°C, and are operated batch-wise.
The elevated temperature, and hence reduced tar viscosity, assist in allowing
the small water droplets in the tar to be separated; these are frequently referred
to as tar dehydrators.
Since most tar storage tanks have to be cleaned out by physical removal of
settled solids deposits, the tanks have to be fitted with large side doorways for
equipment access, and the steam heaters may take the form of layer coils in the
base or top-entry heater units. The latter type may be removed and cleaned
without taking the tank out of service.
THE COKE OVEN MANAGERS’ YEAR-BOOK 242
1. Introduction
The distillation of excess flushing liquor involves feeding the liquor to the
top of a trayed distillation column, usually called an ammonia still, and feeding
a counter current flow of stripping steam at the bottom. The stripping steam
distils off the ammonia which leaves with the overhead vapours and passes on
for further treatment. The stripped liquor is pumped from the bottom of the
still and cooled before discharge to the local sewer or on site BET plant.
Typical levels of total ammonia in stripped liquor range from <50ppm to
150ppm.
Not all the dissolved ammonia present in excess flushing liquor is readily
steam strippable. The many chemical species present in flushing liquor lead to
the formation of various ammonium salts in solution. These include
ammonium carbonate, chloride, and sulphate among others. Salts such as
ammonium carbonate are easily decomposed by heat in the still to yield free
molecules of ammonia. However, other salts such as ammonium chloride and
sulphate are not decomposed and retain the ammonia in a “fixed” form. The
fraction of fixed ammonia to total ammonia in excess flushing liquor is
typically 20 to 50%. To allow the distillation of the fixed ammonia, the excess
flushing liquor must be made alkaline. The following typical reaction then
takes place, liberating free molecules of ammonia:
THE COKE OVEN MANAGERS’ YEAR-BOOK 244
The form of alkali used in the distillation of excess flushing liquor has
changed over the years. For many years, a suspension of calcium hydroxide
(lime) was used. This material had the advantage of low cost and ready
availability, but the formation of insoluble calcium salts such as calcium
carbonate created a major problem with fouling. The ammonia stills required a
considerable marking of overdesign to allow continued operation while
partially fouled, but even so they had to be taken out of service regularly for
cleaning. To avoid the problem of fouling, sodium carbonate (soda ash) has
also been used. This has the advantage that insoluble salts are not formed, but
impurities can be present to cause fouling and on site storage and mixing
equipment is required. An environmental factor when using reagents such as
lime and soda ash is that any insoluble deposit formed can create a solid waste
disposal problem.
Materials of construction for ammonia stills are chosen for their corrosion
resistance. Cast iron has traditionally been sued, with generous allowances for
corrosion, although it is now often more economical to use materials such as
Hastelloy, a nickel based alloy, titanium and 316 stainless steel. The upper
sections of ammonia stills where both ammonia and acid gases are present
generally require the use of highly corrosion resistant materials.
245 KEITH WRIGHT
The presented used methods for removal of ammonia from coke oven gas
are variations of three basic processes. Those are the Ammonium Sulphate
process, the Phosam process and the Water Wash process.
The ammonium sulphate process removes ammonia from the coke oven gas
by absorption in a solution of ammonium sulphate and sulphuric acid. The
ammonium sulphate produced by the reaction of ammonia with sulphuric acid
is recovered by crystallisation. The crystals are then centrifuged, washed and
dried. The various ammonium sulphate systems in operation differ in the type
of gas/liquor contacting device and the type of crystallisation equipment used.
An early and still very commonly used system employs a dip tube
extending below the surface of the acid/ammonium sulphate solution in a
vessel referred to as a saturator (see Fig 5). The solution strength is
maintained around 4% acid. Coke oven gas is fed through the dip tube and
gas/liquid contact is effected as the gas bubbles up through the solution in the
saturator. Acid is continuously added to the saturator. The heat of reaction
between ammonia and sulphuric acid causes the evaporation of water into the
coke oven gas. The concentration of ammonium sulphate reaches saturation,
causing crystals to form directly in the saturator where they are allowed to
grow until they are removed from the system. By means of agitation and
circulation of the solution the fine crystals are retained within the process
solution of “mother liquor” as it is known.
The traditional material of construction for the saturator and all wetted
surfaces is lead lined carbon steel. Alloys such as Monel and 316 stainless
steel are also used. Brick lining is used to protect the lead lining, which suffers
from “creep” and damage by erosion.
THE COKE OVEN MANAGERS’ YEAR-BOOK 246
In the Phosam process, ammonia is selectively absorbed from the coke oven
gas by direct contact with an aqueous solution of ammonium phosphate in a 2-
stage spray absorption vessel (see Fig 6). The absorption solution actually
contains a mixture of the following: phosphoric acid H3PO4, mono ammonium
phosphate NH4H2PO4, di-ammonium phosphate (NH4)2HPO4 and tri-
ammonium phosphate (NH4)3PO4. The absorption reactions that take place are:
The overhead vapours from the stripper are virtually only water vapour and
ammonia. These vapours are condensed and then fed to a fractionating column
where anhydrous ammonia is recovered as the condensed overhead product.
The fractionator bottoms product, mainly water, leaves the system as effluent.
remaining rich solution is fed to the stripper. A subsequent step to deal with
any remaining acid gases and prevent them from contaminating the anhydrous
ammonia, is to add sodium hydroxide to the fractionator feed. The sodium
hydroxide fixes the acid gas compounds as non-volatile sodium salts which
remain in the fractionator bottoms effluent stream.
the ammonia is stripped from the aqueous liquor using steam. The ammonia
and water vapours leaving the top of the stripping column are passed on for
subsequent treatment in a variety of ways which are discussed in section 4.
After stripping, the absorption liquor is cooled and returned to the washer.
An advantage of the water wash process is that excess flushing liquor and
other aqueous plant streams (such as benzole plant effluent) can be used to
absorb ammonia in the washer. The advantage of doing this is that as the
excess liquor would be steam stripped in any case, there is a net saving of
stripping steam if the excess flushing liquor is also used to absorb ammonia.
For other plant effluent streams, it often makes sense to perform steam
stripping as a preliminary effluent treatment step. Combining this with the
ammonia absorption process minimises overall steam consumption for the by-
product plant. The excess flushing liquor is added at a point in the washer
253 KEITH WRIGHT
where its free ammonia concentration most closely matches the free ammonia
concentration of the absorption liquor. The presence of fixed ammonia does
not influence absorption of free ammonia from the coke oven gas. If excess
flushing liquor is used in the water wash process, the flowrate of the
blowdown effluent stream is increased to maintain the circulating liquor
inventory. The fixed ammonia can be removed in the stripping column by the
addition of caustic soda. Alternatively, the blowdown stream can be fed to a
separate fixed ammonia still. The use of a separate fixed ammonia still avoids
the presence of alkali in the recirculating absorption liquor, which can be
responsible for forming fixed compounds with acid gases such as hydrogen
cyanide and leading to the presence of these compounds in the plant effluent
stream.
4.1 General
Having removed the ammonia from the coke oven gas and generated a
vapour stream containing ammonia, water, and acid gases (H2S, HCN, CO2),
the following processes have been used or proposed for further treatment of
the vapours:
The latter two are modification of the previously described processes, the
Ammonium Sulphate process and the Phosam process. In each case, the
ammonia vapour stream replaces the coke oven gas feed stream. Naturally the
size of the equipment required for absorption of the ammonia is reduced. In
the case of production of ammonium sulphate, this plant arrangement is
referred to as the “indirect” process. The remaining three alternatives are
discussed in the following sections.
THE COKE OVEN MANAGERS’ YEAR-BOOK 254
4.2 Incineration
Incineration of ammonia vapours has been widely practised from the 1960’s
on. The process simply reacts the ammonia with air in specially designed
burners. The process is exothermic and no support fuel is needed other than
for a pilot flame to initiate the combustion. The incinerator is refractory lined
for heat resistance. The products of combustion, mainly nitrogen and water
vapour, are emitted to atmosphere through an elevated stack.
The presence of oxides of both nitrogen and sulphur in the stack gases has
led to a close review of the suitability of this process with regard to
atmospheric pollution regulations. New installations of this process are often
nowadays limited to standby or emergency applications as a short-term gap
measure, for example during a maintenance outage of a more environmentally
friendly process.
First developed and installed by the company Firma Carl Still in 1968, this
process has gained popularity due to its ability to dispose of the ammonia
removed from coke oven gas without the raw material cost of the sulphate
process and without the emission of pollutants.
The process begins with the ammonia vapours coming from the ammonia
distillation column. Normally, a partial condenser is used to reduce the
THE COKE OVEN MANAGERS’ YEAR-BOOK 256
The reaction kinetics favour the combustion of the coke oven gas with the
air. This results in a reducing atmosphere consisting of the ammonia vapours
and coke oven gas combustion products at a temperature of 1150°C.
With careful control of the coke oven gas and air flowrates, no oxides of
nitrogen or sulphur are formed, and no excess air is returned to the coke oven
gas main. The addition of the tail gas results in a small reduction in the
calorific value of the coke oven gas. This is due to the volume of nitrogen
which enters the process as combustion air.
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