221 THE COKE OVEN MANAGERS’ YEAR-BOOK

COKE OVEN GAS TREATMENT

TAR, LIQUOR, AMMONIA

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

When producing coke by coal carbonisation a large volume of gas is

produced; this gas is treated in the by-product plant to give a clean fuel gas
after removing condensable, corrosive or economically valuable components.
The gas is produced over most of the coking period, the composition and rate
of evolution changing during this period and being essentially complete by the
time the charge reaches 700°C. The final yield of clean gas after treatment in
the by-product plant is approximately 300 Nm3/te dry coal, the yield
depending upon a number of factors, including coal volatile material available
and the carbonisation conditions.

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.

The coke oven gas is a complex mixture and contains numerous

components, including typically:

Major components Approx. volume %

Hydrogen (H2) 48 – 55
Methane (CH4) 28 – 30
Carbon monoxide (CO) 5.0 – 7.5
Carbon dioxide (CO2) 1.5 – 2.5
Nitrogen (N2) 1.0 – 3.0
High paraffins and unsaturated hydrocarbons 2.5 – 4.0
Oxygen 0.0 – 0.5
223 KEITH WRIGHT

Minor components (NH3)

Ammonia (H2S)
Hydrogen sulphide (HCN)
Hydrogen cyanide (NH4Cl)
Ammonium chloride
Benzene, toluene, xylene and naphthalene and other aromatics
Tar components
Tar acid gases (phenolic gases)
Tar base gases (pyridine bases)
Carbon disulphide

Of these, the hydrogen, methane, carbon monoxide, paraffinic and

unsaturated gases are useful components of the final clean fuel gas. The small
amounts of carbon dioxide, oxygen and nitrogen are allowed to remain in the
final gas as inert but harmless components.

The remainder of the components are removed in the by-product plant as

far as is practical.

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

gas as it is generated, and also to have a reliable continuous supply of flushing

liquor to quench this coke oven gas to a reasonably low temperature.

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.

The gas components normally removed are:-

Tar - condensable vapour forming an essentially chemically neutral liquid,

containing however the tar acids (phenols) and tar bases (pyrides etc). The tar
consists mainly of a mixture of numerous aromatic hydrocarbons which range
from the volatile benzene to pitches which are solids at room temperature. Tar
is removed as a saleable material; in earlier times it served as a rich source of
mainly aromatic chemicals. In approximate terms 70% of the tars, including
the least volatile materials, are condensed in the gas quenching operation using
sprayed liquor. A further 20% are removed when the gases are cooled in the
primary cooler, and the remaining approx. 10% are removed in the
electrostatic precipitators. These latter are designed to remove the fine tar
droplets remaining in the gas after the exhausters and are normally located in
the gas stream immediately following the exhausters.

Naphthalene - present as a vapour which condenses directly to a solid,

chemically neutral aromatic material. The raw coke oven gas normally has a
naphthalene concentration corresponding to a dew point of approx. 50 – 55°C,
depending on the carbonisation conditions. Therefore there is almost no
naphthalene removal when the gas is quenched to 80 – 84°C, but substantial
removal when the gas is cooled to 25°C in the primary coolers. Naphthalene
dissolves freely in tar. Much of the naphthalene remaining in the coke oven
225 KEITH WRIGHT

gas as a vapour after the primary cooling stage is removed subsequently by

absorption in either mineral or creosote oil in the benzole washing stage or a
special unit. As a general principle it is necessary to reduce the naphthalene in
gas concentration corresponding to a dew point temperature appreciably below
any which may be experienced by the walls of the gas distribution pipework.

Ammonia - present as a vapour in the coke oven gas, readily dissolving in

water to form a weakly alkaline solution. Because the ammonia is associated
with corrosion problems when hydrogen sulphide and ammonia are present it
is normally removed at the earliest possible stage, immediately following the
tar precipitators. In earlier times coal carbonisation gases, town’s gas and coke
oven gas were the only source of ammonia. Then it was removed from the gas
as a most valuable by-product, currently there are few economically favourable
outlets for the ammonia or its associated compounds. Processes for ammonia
removal make use of its properties of a weakly alkaline compound to react
with acidic reagents of one type of another.

Benzole - volatile aromatic hydrocarbons, including mainly benzene,

toluene, xylene; these are removed currently as a valuable saleable commodity,
and also to reduce their concentrations in the coke oven gas used as a fuel in
the coke oven battery. The benzole vapour components are normally removed
from the gas by absorption in an oil fraction, derived either from coal tar of
mineral oil. The benzole absorption process will also remove a substantial
proportion of the naphthalene vapour still present in the gas in addition to
some of the carbon disulphide. Some of the benzole compounds initially
present in the gas leaving the ovens are absorbed in the early tar condensing
and primary gas cooling sections of the plant.

Hydrogen sulphide - weakly acidic gas, readily absorbed in alkaline

solutions and also readily desorbed as a gas from them. Hydrogen sulphide
has to be removed from the gas on three main accounts:-

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 general principle observed in deciding the sequence of operations in

the by-product plant is to follow the tar/liquor separation from the gas and the
primary gas cooling stages by sequential removal of components in such a way
as to minimise downstream disturbances. The operations on the gas stream are
normally carried out at a slightly positive pressure (70 – 150m bar); this avoids
the possibilities of undetected air in-leakage into the plant at sub-atmospheric
pressure without the expense and complexities due to high pressure plant
operation.

A normal sequence for a plant would therefore be:-

Tar and liquor separation

Primary gas cooling
Compression in exhausters
Electrostatic tar droplet removal
Secondary/final gas cooling (frequently combined with ammonia removal)
Ammonia removal
Benzole removal
Naphthalene removal (if necessary)
Hydrogen sulphide removal.

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.

It is most important to be aware of relevant dew point temperatures in the

gas scrubbing system in order to prevent undesirable condensation. Both the
water and naphthalene dew point temperatures are relevant, for example to
avoid condensing water into oil circulation systems and to avoid naphthalene
227 KEITH WRIGHT

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.

Some by-product plants have an entirely different operating basis, by

chilling the main gas stream to much lower temperatures than normal it is
possible to produce a clean stream of hydrogen for a synthesis process. Other
materials removed from the gas are separated from the condensed liquids.

The cleaned coke oven gas is normally available at a pressure of approx.

70mb and 25°C, it is then available for distribution to fuel consumers.
Frequently, for consumers at the same works, no further compression is
required. However, when necessary for more distant consumption, the gas
pressure can be increased by use of booster compressors. In this case it is also
necessary to reassess the relevant dew points to avoid downstream
condensation problems. It is normal to provide some means of cleaned gas
storage in a gasholder to provide a reliable source in case of gas treatment
plant delays or hold-up. The capacity, type and location of this facility is
decided from a study of operating plant and gas consumer characteristics.

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.

Acknowledgement of the carcinogenic properties of aromatic hydrocarbons

(benzole, tar compounds) means that equipment must be provided to prevent
release of these materials to the surroundings or exposure of plant operators to
them. In practice this means providing efficient vapour collection and
treatment facilities in addition to providing secured holding for any such
liquids.

Gas and vapours containing sulphur or sulphur oxides must be treated to

substantially reduce their release to the atmosphere.

In general all process liquids must be contained by drainage and recovery to

prevent leakage to the ground.
 THE COKE OVEN MANAGERS’ YEAR-BOOK 228

Combustion units must be designed to minimise release of oxides of

nitrogen gases to the atmosphere.

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.

******
229 KEITH WRIGHT

TAR AND LIQUOR DECANTING AND STORAGE

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:-

1. Continuous rapid separation of a suitable flushing liquor stream;

2. Separation of a clean and tar free excess ammonia liquor for further
processing;
3. Separation of a clean tar essentially free from water and solids for
sale.

The continuous separation of the flushing liquor stream is a particularly

vital feature, this flow being required to cool the hot oven exit gases down to a
temperature which can be handled in the gas collecting system.

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.

Because of the presence of hazardous and carcinogenic aromatic

compounds it is an essential feature of modern coking plant design and
operation that all vessels and equipment containing ammonia liquor or tar are
furnished with effective methods of preventing leakage or escape of vapours,
liquids or solids to the atmosphere or ground. Therefore all the equipment is
these sections should have efficient vent and drain collection systems, with
methods of treating materials collected.
 THE COKE OVEN MANAGERS’ YEAR-BOOK 230

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.

1.1 Source and composition of the ammonia liquor

The water in the excess flushing liquor originates from:

a) free moisture in the coal charge;

b) bound, or combined water in the coal;
c) additional water introduced to the plant, for example by
steaming during oven charging or for hosing down plant.

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 ammonium chloride content of the ammonia liquor is important,

because this compound represents almost the entire chlorine present in the coal
charge and the ammonium chloride is contained in the condensates arising in
the gas collecting main and the primary gas cooling. In view of the
particularly corrosive nature of chlorides, and the fact that they do not vaporise
readily at normal process temperatures, their concentration has to be avoided
in any systems for ammonia liquor treatment or disposal. For instance, use of
this liquor or derivative as a make-up source to coke quenching systems has
frequently aggravated the corrosion problems in these systems. Consequently,
particularly when new plant processes are being considered, it is necessary to
make a rough chloride balance to confirm that high concentrations are
prevented.
231 KEITH WRIGHT
 THE COKE OVEN MANAGERS’ YEAR-BOOK 232

1.2 Source and composition of the tar

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 tars are an extremely complex mixture of organic compounds which

condense to medium to dark liquids or solids at room temperature, mostly
aromatic compounds. Typically they range from light oils such as benzene, in
a fraction boiling up to 200°C, through to the pitches, the residue after
distillation up to 350°C. The tar normally has a specific gravity greater than
1.0 and is somewhat viscous, both values depending on the source of the
fraction within the plant and the coal carbonisation features.

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 second fraction, condensing in the primary gas cooler, has an

appreciably lower specific gravity and lower viscosity. The fraction removed
as droplets in the electrostatic tar precipitator has even lower specific gravity
and viscosity. Typically the collected bulk tar has a specific gravity of approx.
1.2 and viscosity in the range 300 – 3000 cS at 35°C, the viscosity reduces
rapidly as the tar temperature increases.

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.

The yield of coal tar is approx. 30 – 50 litres/te dry coal.

233 KEITH WRIGHT

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.

1.4 Tar/Liquor Separation

The initial separation of tar and liquor is performed in a flushing liquor

decanter, a unit based on gravity separation. Since the ammonia liquor has
specific gravity of approx. 1.0 and that of the tar is approx. 1.1 – 1.2 in
principle, such a separation is not difficult. There are, however, several
features in an operating plant which make the process more complex. These
features include the following:-

The very high flushing liquor circulation rate does not allow sufficient time
to make a thorough tar/liquor separation.

The presence of solids in the system must be taken into account.

Because of the low liquor viscosity and reasonable difference of tar/liquor

densities it should be easy to obtain a tar-free liquor. However, some tar has
an apparent density less than that of water and will therefore float.

The high tar viscosity retards separation of small liquor droplets and fine
solids from the tar.

The operating temperature (approx. 75 – 80°C) of the decanting plant

means that the vapours above the ammonia liquor and tar contain corrosive,
condensable and toxic components such as hydrogen sulphide and cyanide,
water, benzene and naphthalene.
 THE COKE OVEN MANAGERS’ YEAR-BOOK 234

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.

A most important advantage to using flushing liquor to keep plant free,

rather than use fresh water, is that it helps to maintain a tight plant water
balance. In modern by-product plant practice it is necessary to minimise plant
effluent discharges, any additional water added to the process appears
ultimately as extra aqueous effluent flow which has to be treated before
discharge.

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.

As indicated above the separation of a relatively tar-free flow of

ammoniacal liquor is helped by the low liquor viscosity and normally heavier
tar density. The large flow required for return to the coke oven battery as
flushing liquor is separated at an early stage, the remaining liquor flow
represents the surplus, or production, quantity and passes forward to a
secondary decanting/settling stage which takes place over a longer period.

2. Types of Flushing Liquor Decanters

2.1 Rectangular

By far the most widely used type of decanter is that shown

diagrammatically in Fig 2. This is basically a flat-bottomed rectangular
container. At one end the base slopes upwards at an angle to house the solids
discharge mechanism.

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.

Separated liquor flows over an outlet weir and out to an intermediate

storage tank, from which the flushing liquor is pumped to the battery and the
surplus liquor is transferred to main storage before processing. Solids and
heavy tar, a mixture of solids and viscous tar, fall to the bottom of the
decanter. This material is moved along the decanter base and over the sloping
outlet riser by a very slow-moving scraper conveyor to be discharged into a
receiving hopper.

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.

Plant designs include low pressure steam heating probes or coils to

maintain tar temperature to reduce tar viscosity. The operating temperature of
these units is in the range 75 – 80°C, depending mainly on the temperature of
the tar and liquor stream entering. Some plants have been built to operate
under a slight positive pressure in order to allow the tar temperature to be
higher so that solids and water separation are easier. These units were built as
horizontal cylindrical vessels, rather than rectangular, but otherwise retained
the same general configuration for separation and decanting.

2.2 Double-Cone

This type of unit is shown schematically in Fig 3, it consists of an inner

conical tank mounted within an outer vessel, the primary rapid separation of
tar and liquor to produce the flushing liquor return flow taking place in the
annular space between the cones. The flushing liquor flow is withdrawn from
a point diametrically opposite to the introduction of the combined tar and
liquor input. The main rapid flow is therefore around the conical annulus.

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

It is normal to provide a common flushing liquor tank to collect liquor from

all the decanters, this tank will only have a capacity corresponding to a few
minutes of the recirculation rate but provides a valuable buffer storage volume
to allow for example pump changeover.

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.

Tar from the dehydrators, if used, is transferred to larger intermediate and

final storage tanks. These tanks are normally provided with a form of low
pressure steam heating to maintain tar temperature at about 60 – 80°C. Tar
storage is frequently operated stage-wide to allow finer solids particles to be
deposited before final discharge. The finest particles may be almost
impossible to remove by gravity settling. At this stage the storage tanks may
be fitted with slow moving side-entry mixers to prevent further solids
settlement.

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

AMMONIA REMOVAL PROCESSES

1. Introduction

Ammonia (NH3) is a by-product of the coking of coal. It is a constituent of

the coke oven gas leaving the ovens, with a typical concentration in raw coke
oven gas of 6g/Nm3. The solubility of ammonia in water leads to its presence
in the coke battery flushing liquor with a typical concentration of 5.0 – 6.0 g/l
total ammonia. Consequently, due to the net production of flushing liquor in
the coke plant, referred to as excess flushing liquor but also know as coal
water, virgin liquor or weak ammonia liquor, there arises a liquid stream as
well as a gas stream from which ammonia must be removed. The quantity of
excess liquor is approx. 12% by weight of the dry coal throughput, depending
on the coal moisture content.

Ammonia removal from gas streams remains a universal feature of coke

oven by-product plants. The reason for this is that ammonia, in the presence of
the other coke oven gas contaminants hydrogen cyanide, hydrogen sulphide,
oxygen and water, is extremely corrosive to carbon steel. In former times, an
added incentive was the profitable sale of by-products such as ammonium
sulphate, anhydrous ammonia and concentrated ammonia solutions. With the
possible exception of anhydrous ammonia, the reduced market value of these
by-products, especially in the industrialised nations, no longer makes their
production profitable. Ammonia removal from liquid streams is performed
mainly for environmental reasons.

The primary ammonia handling equipment in the coke oven by-product

plant deals with the removal and disposal of the ammonia present in the coke
oven gas. However, these systems often include facilities to handle the
ammonia arising in the excess flushing liquor. To help understand how such
facilities are incorporated into the overall ammonia handling system, this
review of ammonia removal processes begins with the treatment of ammonia
in the excess flushing liquor. The main processes for removal of ammonia
from coke oven gas are then described. As these processes generate in many
cases a concentrated ammonia vapour stream, the final section covers the
alternatives available for treatment of this stream.
243 KEITH WRIGHT

2. Treatment of Excess Flushing Liquor

2.1 Available Options

In some locations, excess flushing liquor can be disposed of without prior

treatment, using deep well injection. A once common practice is to use the
excess flushing liquor for quenching the hot coke, although for environmental
reasons this practise is no longer acceptable. In the absence of such simple
disposal methods, the remaining alternatives are the removal of the majority of
ammonia from the liquor by distillation, usually followed by final treatment in
a Biological Effluent Treatment (BET) plant. The BET plant may be on site or
it may be operated by the local authority in which the coke plant is located. It
is possible to use biological effluent treatment alone to remove ammonia from
excess flushing liquor, however, the size and operating cost of a BET plant is
considerably reduced when preliminary removal of ammonia by distillation is
performed.

2.2 Distillation of Excess Flushing Liquor

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

NH4+ + OH → ΝΗ3↑ + Η2O

In addition of alkali is determined by mass balance, based on chemical

analysis of the excess liquor to give the concentration of the fixed ammonia
present.

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.

The generally ready availability and ease of handling of sodium hydroxide

(caustic soda) solution has made this the alkali of choice for present day design
of ammonia stills. Caustic soda is the most expensive of the alkalis
traditionally used, but is consumption can be closely controlled which is of
great benefit where limitations are imposed upon still effluent pH. The non-
fouling characteristics of caustic soda allows the use of more economical still
designs, incorporating valve trays in place of the traditional bubble cap trays.
In practice, the caustic soda is injected into the ammonia still near to, but not
at, the top tray. This allows dissolved acid gases such as hydrogen cyanide
and hydrogen sulphide to be stripped from the liquor first, before they can
react with the caustic soda to form fixed salts.

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

A common operating problem in the distillation of excess flushing liquor is

the presence of tar carryover which can lead to serious fouling in the still. The
usual solution to this problem is to install sand or gravel bed filters in the
excess flushing liquor supply line. These are manually or automatically
operated. The removed tar is back-flushed to the tar and liquor decanters.

3. Ammonia Removal from Coke Oven Gas

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.

3.1 The Ammonium Sulphate 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

Fig. 5 Ammonium Sulfate System

247 KEITH WRIGHT

The availability of acid resistant materials such as 316 stainless steel

allowed the development of the modern ammonia absorber systems. In these
systems, a circulating stream of ammonium sulphate/sulphuric acid solution is
sprayed counter currently to the coke oven gas flow in an absorber vessel.
Absorption of ammonia from the gas takes place on the spray droplet surfaces.
A portion of the circulating liquor is continuously withdrawn and fed to a
separate continuous crystalliser. Here, the liquor is concentrated using heat
and negative pressure to evaporate the water and so promote crystallisation.
The crystals are removed and a stream of mother liquor is continuously fed
back to the absorber circuit.

The operation of ammonium sulphate systems results in an increase in the

heat content of the coke oven gas leaving the absorber or saturator. The reason
for this is that to maintain the water balance in the system, especially in the
case of saturators, water must be evaporated into the gas stream. In addition to
the water added to the system with the acid, regular desaturations are necessary
in which water is added to the mother liquor to dissolve crystal deposits and
reduce fouling. In some installations, gas heaters are provided upstream of the
ammonia absorbers/saturators. The evaporation of water into the coke oven
gas results in an outlet gas with a higher dew point than at the inlet. In order
for downstream gas cleaning processes such as naphthalene, benzole and
hydrogen sulphide removal to be operated effectively, the gas must be cooled
in “final” or “secondary” gas coolers.

The ammonium sulphate processes accommodate ammonia from excess

flushing liquor be feeding the overhead vapours from flushing liquor
distillation into the coke oven gas main upstream of the ammonia
saturator/absorber.

The major economic disadvantage with ammonium sulphate processes is

the price relationship between sulphuric acid and ammonium sulphate. The
sulphuric acid required to make ammonium sulphate can cost up to two times
the value of the ammonium sulphate product.

3.2 The Phosam Process

The Phosam process was developed by United States Steel as a means of

producing a saleable, commercially pure anhydrous ammonia product from the
ammonia present in raw coke oven gas. This high value product makes the
 THE COKE OVEN MANAGERS’ YEAR-BOOK 248

process much more economically viable than the ammonium sulphate

processes described earlier.

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:

H3PO4 + NH3 ← → NH4H2PO4

NH4H2PO4 + NH3 ←→ (ΝΗ4)2HPO4
(NH4),2HPO4 + NH3 ←→ (ΝΗ4)3PO4

The ammonia absorbed is recovered by steam stripping. This regenerates

the absorption solution which is returned to the spray absorber.

The steam stripping is performed at high pressure, around 13 bar. The

reason for this is that the reversible reactions which liberate the ammonia from
solution are favoured by higher temperatures. Therefore by operating at high
pressure (and hence higher temperature) the consumption of stripping steam is
minimised.

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.

The Phosam process can become contaminated by tar and by absorption of

acid gases (HCN, H2S and CO2) in the recirculated solution. To remove the
tar, a froth flotation device is installed in the solution circuit between the
absorber and the stripper. Acid gases are removed by preheating the ammonia
rich solution and feeding it into a vessel referred to as a contractor. In this
vessel, the preheat causes vaporisation of water and acid gases from the
solution. These vapours are vented back to the coke oven gas main and the
 249
KEITH WRIGHT

Fig. 6 Phosam System

 THE COKE OVEN MANAGERS’ YEAR-BOOK 250

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.

An important operational feature is the control of the water balance in the

system. Substantial amounts of steam are condensed in the solution stripper,
and this condensate must be re-evaporated from the circulating solution into
the coke oven gas stream. The temperature of the solution returning to the
absorber is approx. 60°C, and therefore the coke oven gas becomes heated as it
flows through the absorber. The increased gas temperature usually makes it
necessary to install a final gas cooler after the Phosam absorber.

The addition of phosphoric acid to the absorption solution is required only

to account for operating losses such as spillage. It is added at weekly intervals
at a rate equivalent to 0.0075kg H3PO4 per kilogram ammonia produced.

The Phosam process is very efficient, capable of achieving greater than

99% recovery of ammonia from coke oven gas. Other plant configurations are
possible in which, for example, aqueous ammonia solution is produced instead
of the anhydrous ammonia. Materials of construction are stainless steel for all
areas in contact with phosphate solution of aqueous ammonia, and carbon steel
for other areas.

As in the sulphate process, ammonia present in excess flushing liquor is

handled first by distillation, with the vapours being fed to the coke oven gas
upstream of the Phosam absorber.

3.3 The Water Wash Process

One of the simplest and most frequently used methods of removing

ammonia from coke oven gas is to absorb it in water. Aqueous absorption
liquor is fed counter currently to the flow of coke oven gas in an ammonia
washer vessel (see Fig. 7). The vessel can be designed as a spray type
absorber with several liquor respray stages, or as a packed tower as is common
in many German designed plants. The type of packing generally used is
vertically arranged expended metal sheets which promote gas/liquor contact
but resist playing and fouling. The rich ammonia solution formed, with a
typical concentration of 5 to 8g/l, is then fed to a distillation columns where
 251
KEITH WRIGHT

Fig .7 Water Wash Process

 THE COKE OVEN MANAGERS’ YEAR-BOOK 252

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.

There is a continuous blowdown of stripped liquor from the circuit which is

equivalent to the volume of steam condensed in the stripper column. This
blowdown is plant effluent and requires biological effluent treatment to fully
remove the residual ammonia.

As no chemical reactions are involved, other than the dissolving of

ammonia in water, the water wash process is temperature dependent and is
most efficient at low coke oven gas temperatures (20-30°C). The ammonia
washer vessel is usually placed immediately after the tar precipitator in a
typical coke oven by-product plant. At this point, the gas retains some
superheat from the gas exhauster, if the by-product is plant operated at positive
pressure. To promote ammonia removal efficiency, gas cooling is required to
remove this superheat and to cool the gas to the optimum temperature range.
The gas cooling stage is often incorporated into the ammonia washer vessel
itself. The ammonia washer must not be operated at a lower temperature than
the outlet temperature of the gas cooling stage, otherwise fouling by
naphthalene can result.

Use of aqueous absorption liquor results in the simultaneous absorption of

significant quantities of acid gases (H2S, CO2, HCN) from the coke oven gas.
Therefore, the ammonia stripping column is nowadays often constructed of
corrosion resistant materials such as titanium and 316 stainless steel, although
many plants continue to operate cast iron stills. The stripping columns is
equipped with bubble cap trays or with more economical valve trays. Due to
the lower liquor temperatures in the washer and hence the reduced rate of
corrosion, this vessel can be constructed entirely in carbon steel.

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. Treatment Alternatives for Ammonia Vapour Streams

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:

• Incineration of the vapours

• Production of concentrated ammonia liquor
• Catalytic ammonia destruction
• Production of ammonium sulphate
• Production of anhydrous ammonia

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.

Depending on the source of the vapours to be incinerated, they may contain

significant quantities of the acid gases hydrogen sulphide and hydrogen
cyanide. These components are also incinerated, with any sulphur compounds
present producing sulphur dioxide.

The single stage combustion of ammonia occurs at high flame temperatures

in excess air. These circumstances promote the formation of oxides of
nitrogen (NOX) which leave with the stack gases. To combat this effect, “low
NOX” incinerator design use a two stage combustion with intermediate cooling
(by water sprays) between the stages. The first stage is used to incinerate most
of the ammonia, with carefully controlled air flowrates so that excess air is
avoided. In the second stage, excess air is allowed to complete the incineration
but at relatively low flame temperatures. By these means the NOX content in
the stack gases can be held to less than 100ppm.

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.

4.3 Production of Concentrated Ammonia Liquor

Concentrated ammonia liquor in various grades of purity can be prepared

from the ammonia vapour stream. Usually, a preliminary condensation is
performed to reduce the amount of water vapour present. The condensate is
returned to the ammonia distillation column. The remaining vapours are then
condensed to form the product ammonia liquor. The vapour temperature after
the preliminary condensation determines the remaining water content and
hence determines the concentration of the ammonia liquor produced.
255 KEITH WRIGHT

With the presence of acid gases in the ammonia vapours, particularly

carbon dioxide, the concentration of ammonia liquor produced by
condensation of the vapours is limited to 15-20% ammonia. This is because
ammonium carbonate is also formed and crystallises on the condenser surfaces
at higher concentrations.

The problems caused by acid gases can be alleviated to an extent by a prior

removal of these compounds from the enriched wash liquor before it is fed to
the ammonia still. This is done in a “deacification” column, which is a steam
stripping column. Relatively small flowrates of steam are used to strip the
more volatile acid gases from the wash liquor, leaving the ammonia largely in
solution. The acid gases can be returned to the coke oven gas main, and the
deacified solution then passes to the ammonia distillation column.

A common method of cooling and condensing ammonia vapours is by

direct contact with recirculated cooled ammonia solution in a packed column.
This method avoids localised sub-cooling of the condensate which can lead to
crystallisation and fouling.

Carbon steel can be used to handle concentrated ammonia liquor below

50°C. At higher temperatures more corrosion resistant materials such as 316
stainless steel, Hastelloy and titanium may be necessary.

The production of concentrated ammonia liquor is also used to provide a

low cost standby in plants where the normal ammonia handling facilities are
out of service for maintenance.

4.4 Catalytic Ammonia Destruction

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

Fig. 8 Catalytic Ammonia Destruction

257 KEITH WRIGHT

content of water in the vapours. The condensate is returned to the column.

The remaining vapours, including any acid gases, flow into a top mounted v
burner installed on a refractory lined ammonia destruction reactor. Coke oven
gas support fuel and a stoichiometric amount of combustion air are also fed to
the burner, at closely controlled flowrates. Within the reactor is a nickel
catalyst bed (see Fig. 8).

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.

Over the nickel catalyst, ammonia is cracked to nitrogen and hydrogen.

Hydrogen cyanide reacts with the water vapour present to form nitrogen,
hydrogen and carbon monoxide. Hydrogen sulphide passes through the
catalyst bed unreacted. The reactor gases then flow through a waste heat
boiler where they are cooled to around 300°C, by raising high pressure steam.
The gases may then be passed directly to the raw coke oven gas main, closing
the process loop, or they may first be further cooled by water quenching in a
tail gas cooler vessel.

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.

Materials of construction in the ammonia destruction plant are primarily

carbon steel, with Hastelloy or titanium for the ammonia vapour feed lines.
Refractory lining is used where necessary for heat protection.

******