The Coke Oven By-Product Plant

Contributed by Mick Platts, ThyssenKrupp EnCoke USA

Table of Contents

● What is it and what does it do?

● Coke oven / by-product plant interface
● Composition of coke oven gas
● Duties of the by-product plant
● The by-product plant gas train
● Primary cooler
● Tar precipitators
● Exhauster
● Ammonia removal
● Final cooler
● Naphthalene removal
● Light oil removal
● Coke oven gas desulfurization
● Tar and Liquor Plant
● Conclusion

WHAT IS IT AND WHAT DOES IT DO?

The coke oven by-product plant is an integral

part of the by-product cokemaking process. In
the process of converting coal into coke using
the by-product coke oven, the volatile matter
in the coal is vaporized and driven off. This
volatile matter leaves the coke oven chambers
as hot, raw coke oven gas. After leaving the
coke oven chambers, the raw coke oven gas is
cooled which results in a liquid condensate
stream and a gas stream. The functions of the
by-product plant are to take these two streams from the coke ovens, to process
them to recover by-product coal chemicals and to condition the gas so that it can
be used as a fuel gas. Historically, the by-product chemicals were of high value in
agriculture and in the chemical industry, and the profits made from their sale were
often of greater importance than the coke produced. Nowadays however most of
these same products can be more economically manufactured using other
technologies such as those of the oil industry. Therefore, with some exceptions
depending on local economics, the main emphasis of a modern coke by-product
plant is to treat the coke oven gas sufficiently so that it can be used as a clean,
environmentally friendly fuel.

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Coke oven / by-product plant interface

In a by-product coke oven the evolved coke oven gas leaves the coke oven
chambers at high temperatures approaching 2000()()F. This hot gas is
immediately quenched by direct contact with a spray of aqueous liquor (flushing
liquor). The resulting cooled gas is water saturated and has a temperature of 176()
()F. This gas is collected in the coke oven battery gas collecting main. From the
gas collecting main the raw coke oven gas flows into the suction main. The
amount of flushing liquor sprayed into the hot gas leaving the oven chambers is
far more than is required for cooling, and the remaining unevaporated flushing
liquor provides a liquid stream in the gas collecting main that serves to flush away
condensed tar and other compounds. This stream of flushing liquor flows under
gravity into the suction main along with the raw coke oven gas. The raw coke
oven gas and the flushing liquor are separated using a drain pot (the downcomer)
in the suction main. The flushing liquor and the raw coke oven gas then flow
separately to the by-product plant for treatment.

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Composition of coke oven gas

Raw coke oven gas coming from the coke oven battery has the following typical
composition:

Actual composition
Dry
(water saturated at
basis
176°F)
Water vapor - 47%
Hydrogen 55% 29%
Methane 25% 13%
Nitrogen 10% 5%
Carbon Monoxide 6% 3%
Carbon Dioxide 3% 2%
Hydrocarbons (ethane,
2% 1%
propane etc.)

Raw coke oven gas also contains various contaminants, which give coke oven gas
its unique characteristics. These consist of:

● Tar vapors
● Light oil vapors (aromatics), consisting mainly of benzene, toluene and
xylene (BTX)
● Naphthalene vapor
● Ammonia gas
● Hydrogen sulfide gas
● Hydrogen cyanide gas

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Duties of the by-product plant

In order to make raw coke oven gas suitable for use as a fuel gas at the coke
oven battery and elsewhere in the steelmaking facility the by-product plant must:

● Cool the coke oven gas to condense out water vapor and contaminants
● Remove tar aerosols to prevent gas line/equipment fouling
● Remove ammonia to prevent gas line corrosion
● Remove naphthalene to prevent gas line fouling by condensation
Other duties may include:
● Remove light oil for recovery and sale of benzene, toluene and xylene
● Remove hydrogen sulfide to meet local emissions regulations governing the
combustion of coke oven gas.

In addition to treating the coke oven gas, the by-product plant must also condition
the flushing liquor that is returned to the coke oven battery, and treat the waste
water that is generated by the coke making process.

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The by-product plant gas train

The gas treatment processes in the by-product plant typically consist of the
following plant items, arranged in the order in which they are described.

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Primary cooler

The first step in the

treatment of raw coke oven
gas is to cool it to remove
water vapor and so greatly
reduce its volume. This is
done in the Primary Cooler.
There are two basic types,
the spray type cooler and
the horizontal tube type. In
a spray type cooler the coke
oven gas is cooled by direct
contact with a recirculated
water spray, with the contact
cooling water being itself
cooled externally in heat
exchangers. In the tubular
type, the coke oven gas is
cooled indirectly by flowing
across horizontally mounted
tubes through which cooling
water is pumped. In this
case, the cooling water does not come into contact with the coke oven gas and so
it can be cooled in a cooling tower for example.
As the coke oven gas is cooled, water, tar and naphthalene condense out. The
condensate collects in the primary cooler system and is discharged to the tar &
liquor plant.

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Tar precipitators

As the raw coke oven gas is cooled, tar vaporcondenses and forms aerosols which
are carried along with the gas flow. These tar particles would contaminate and
foul downstream processes and would foul gas lines and burner nozzles if allowed
to continue in the gas stream. The tar precipitators typically use high voltage
electrodes to charge the tar particles and then collect them from the gas by
means of electrostatic attraction. The tar precipitators can be installed before, or
after the exhauster. The usual practice in North America is to place them
immediately after the exhauster.

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Exhauster

The exhauster is a large blower that provides the motive force to induce the coke
oven gas to flow from the coke oven battery and through the by-product plant.
The exhauster is of prime importance to the operation of the coke oven battery. It
allows the close control of the gas pressure in the collecting main, which in turn
affects the degree of emissions, for example door emissions, from the battery. A
failure of the exhauster will immediately result in venting to atmosphere, through
the battery flares, of all of the raw coke oven gas produced.

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Ammonia removal

Because of the corrosive nature of ammonia, its removal is a priority in coke oven
by-product plants. Historically the removal of ammonia from coke oven gas has
yielded one of the more profitable by-products, that of ammonium sulfate. The
ammonium sulfate process can take various forms but all basically involve
contacting the coke oven gas with a solution of sulfuric acid. Variations include the
use of an absorber, in which the sulfuric acid solution is sprayed into the gas, or
the use of a saturator in which the gas is bubbled through a bath of sulfuric acid
solution. The sulfuric acid reacts readily with the ammonia in the coke oven gas to
form ammonium sulfate. This is then crystallized out, removed from the solution
and dried for sale typically as a fertilizer. Nowadays the cost to produce
ammonium sulfate often outweighs the revenue from the product, however there
are still very many coke plants around the world producing ammonium sulfate.

More modern processes for

ammonia removal include the
water wash process in which the
coke oven gas is scrubbed by
water, which dissolves the
ammonia, along with some
hydrogen sulfide and hydrogen
cyanide. The resulting scrubbing
solution is pumped to an ammonia
still where steam is used to strip
out the ammonia. The ammonia
vapors from the still can be
processed to form ammonium
sulfate similar to the processes
described above, condensed to form a strong ammonia solution, incinerated or
catalytically converted to nitrogen and hydrogen which are then recycled back into
the coke oven gas. The incineration of the ammonia vapors is usually not an
option in areas where environmental laws restrict the emission of NOx and sulfur
dioxide.
Another process for ammonia removal from coke oven gas is the PHOSAM process
developed by US Steel. This process absorbs the ammonia from the coke oven gas
using a solution of monoammonium phosphate. The process produces saleable
anhydrous ammonia.

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Final cooler

The duty of the final cooler is to remove the heat of compression from the coke
oven gas that it gained on flowing through the exhauster. This is necessary
because the efficiency of many of the by-product plant processes, including the
water wash ammonia removal process, is greatly improved at lower temperature.
The final cooler is therefore placed upstream of water wash ammonia scrubbers if
these are installed. Final coolers typically cool the coke oven gas by direct contact
with a cooling medium, either water or wash oil. An important aspect of final
cooler operation is that when the coke oven gas is cooled below the outlet
temperature of the primary cooler, naphthalene will condense from the gas. This
naphthalene readily crystallizes out from the cooling medium and will foul
equipment if not disposed of. In wash oil final coolers the naphthalene dissolves in
the wash oil and a side stream of oil is steam stripped to remove the naphthalene.
If water is used to cool the coke oven gas, the condensed naphthalene must be
absorbed using tar. The tar is either entrained in the cooling water, with a portion
of the flow being continuously blown down for treatment, or it takes the form of a
tar layer through which the cooling water flows. The tar is continuously exchanged
with fresh tar from the tar and liquor plant to dispose of the absorbed naphthalene.

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Naphthalene removal

Naphthalene is removed from coke oven gas using wash oil in a gas scrubbing
vessel. The vessel may be packed or it may be the "void" type in which the wash
oil is sprayed into the gas in several stages. The wash oil is regenerated by
stripping out the naphthalene from the wash oil using steam in a still. In many
plants, naphthalene removal is integrated with the similar process of light oil
removal. The naphthalene is typically recovered as a heavier oil stream that is
then often mixed with the tar that is produced in the by-product plant.

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Light oil removal

Light oil is a general term for a mixture of similar chemicals consisting mainly of
benzene, toluene and xylene. The removal of light oil from coke oven gas uses
wash oil in a similar process to that described for naphthalene removal. The light
oil is stripped from the wash oil in a still and is then condensed to form crude light
oil. This can be sold for further refining offsite or it can be refined in the by-
product plant using several distillation steps in the light oil plant. The light oil can
actually be left in the coke oven gas, where it increases the calorific value. Its
removal has historically been extremely cost effective, as benzene toluene and
xylene from coke oven gas were once vital raw materials for the developing
chemical industry. However these materials can nowadays be obtained at lower
cost and in greater quantities from other sources
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Coke oven gas desulfurization

There are several different processes for removal of hydrogen sulfide from coke
oven gas. The specific process determines where in the gas train it is installed.
The main desulfurization processes in use are

Hydrogen Sulfide is absorbed from

Vacuum Carbonate the coke oven gas using a solution of
Process Potassium Carbonate, then stripped
out in a still
Hydrogen sulfide is absorbed from
the coke oven gas using a solution of
Ammonia Wash
ammonia, then stripped out in a still
Process
- this process is often combined with
the ammonia removal system
Hydrogen sulfide is absorbed from
the coke oven gas using a solution of
Sulfiban Process
Monoethanolamine (MEA) then
stripped out in a still

The hydrogen sulfide is converted into elemental sulfur, using the Claus process,
or it can be used for the production of sulfuric acid.

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Tar and Liquor Plant

The tar and liquor

plant handles the
flushing liquor that
circulates between
the by-product
plant and the coke
oven battery. It
also processes the
waste water that is
generated by the
cokemaking process
and which results
from coal moisture
and chemically
bound water in the
coal. The flushing liquor flows into tar decanters where the tar separates out from
the water and is pumped to storage for later sale. Heavier solid particles separate
out from the tar layer and these are removed as tar decanter sludge (TDS). The
aqueous liquor is then pumped back to the battery, with a portion bled off from
the circuit which is the coke plant "excess liquor" or waste water. This contains
ammonia and, after the further removal of tar particles, it is steam stripped in a
still. An alkali such as sodium hydroxide is added in the still to decompose
ammonia compounds dissolved in the liquor. The ammonia vapor from the still is
then either fed into the coke oven gas upstream of the ammonia removal system,
or the still itself is often integrated into the ammonia removal system. Either way,
the ultimate fate of the ammonia removed from both the coke oven gas and the
waste water is the same. The stripped still effluent is either discharged to a
municipal sewer or it can be treated in an on-site biological effluent treatment
plant to remove residual ammonia, phenol and cyanides.

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Conclusion

The above describes the main features of the majority of coke oven byproducts
plants around the world. The resultant main output streams are shown in the
table below. The quantities shown are intended to be indicative only and relate to
a typical facility producing 1 million tons per year of blast furnace coke. Coal
properties and plant design and operation influence the actual quantities.

Stream Destination Typical

quantities, based
on 1 million tons
per year coke
Coke Oven Gas Used as fuel gas 50 million std.cu.
at the coke oven ft./day
battery and steel
works
Flushing Liquor Recirculated back Varies with plant
to the coke oven design
battery
Waste Water Discharged to Varies with plant
treatment plant design
Tar Sold as product 29,000 gallons/day
Ammonia/ Sold as product 12 tons/day (as
Ammonium Sulfate ammonia)
Light Oil (if Sold as product 12,500 gallons/day
recovered)
Sulfur/Sulfuric Sold as product Varies with coal
Acid (if gas is properties and
desulfurized) local requirements

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