THE COKE OVEN MANAGERS’ASSOCIATION 225

THE PRODUCTION OF CONCENTRATED AMMONIA

LIQUOR (C.A.L.)

By

Louise Hutson

Introduction

Concentrated ammonia liquor or CAL is a typically 20-25%

ammonia solution generated by fully condensing vapours from the
ammonia stills on the By Products Plant. The feed to the stills are weak
and strong ammonia liquors arising from the gas washing process.
CAL is a corrosive yellow coloured liquid with a highly irritant odour.
It is sold by the tanker load to Brunner Mond who manufacture soda
ash, sodium bicarbonate and related products for use in many
industries, from the manufacture of glass, detergents and biscuits to the
production of dialysis treatments and the purification of drinking water.
Brunner Mond use CAL as a source of ammonia in the feedstock for
the soda ash manufacturing process but the other components in the
product are also important. The sulphide and ferrocyanide content
helps prevent corrosion throughout their process and the phenolics are
relevant in the distiller stage.

Ammonia Feed Liquors:

Gas generated from the coke making process is cooled and cleaned
on the By Products Plant. There are two arising ammonia liquors that
feed the ammonia stills to produce CAL, weak liquor and strong liquor.

Weak Liquor:

_______________________________________________________________________________

Louise Hutson is a Process Engineer at the Dawes Lane Coke Ovens

Byproducts Plant.
226 THE COKE OVEN MANAGERS’ASSOCIATION

Three main components are removed from the gas as it passes

through a series of gas washers, naphthalene, ammonia and benzole.

There are two gas washers in series that absorb ammonia from the
gas stream (Fig 1). Stripped liquor is fed to No.2 ammonia washer at
the top diaphragm which is resprayed down the washer absorbing
ammonia at each stage; each washer has 3 spray banks. The liquor is
then pumped from the base of No.2 washer to the top diaphragm of
No.1 washer and similarly, the liquor is resprayed down the washer
absorbing ammonia from the gas stream. The liquor, now termed weak
liquor as it has a higher ammonia concentration, is pumped to a bulk
storage tank on the ammonia plant to be processed through the
ammonia stills. Once distilled the liquor is termed stripped liquor and
this is pumped via a bulk storage tank to No.2 ammonia washer for the
process to begin again. These bulk storage tanks provide a “buffer
zone” for plant stoppages and flow alterations without compromising
quality.

The quality of the gas, ultimately the effectiveness of the washers, is

measured by the gas slips. This is measured by an online gas analyser
which gives the amount of ammonia for example in the gas stream after
each washer. The specification for the ammonia slip is less than
73mg/m3 to control the corrosive nature of the gas and condensate.
Main factors affecting this slip are temperatures of gas and liquor,
flowrate and quality of stripped liquor to No.2 washer, spray patterns in
both washers, amount of ammonia in gas stream.

Strong Liquor:
As the gas enters the By products plant from the Battery it passes
through the “downcomer”. This vessel forces the gas to change
direction which encourages the tar and strong liquor to drop out of the
gas stream. This tar and strong liquor passes through 4 separators
which operate in parallel. The tar is pumped to storage for decanting
and despatch or to the primary coolers for naphthalene removal. A
large proportion of the strong liquor is pumped back to the Battery
collecting mains as flushing liquor used to cool the gas stream. The
overflow strong liquor from the separators is pumped via a bulk storage
tank to the Fixed and Free ammonia still where it is processed.
 THE PRODUCTION OF CONCENTRATED AMMONIA LIQUOR (C.A.L.) 227

The Ammonia Stills:

Weak liquor arising from the gas washers and strong liquor arising
from the separators are processed using the Free still and the Fixed and
Free still respectively.

The free still is a 15-tray distillation column using LP steam to

remove the ammonia (one still in use, one standby). The ammonia is
removed in the vapour phase and the stripped liquor is taken from the
still base and pumped via storage back to the washers.

The fixed and free still is a two-leg distillation column (one in use,
one standby) using caustic solution to turn the fixed ammonia salts into
free ammonia. The free ammonia is then removed in the vapour phase
by LP steam. The effluent from the still base is transferred to the toxic
effluent pond for processing at the BET plant.

Ammonia Plant Operation:

The ammonia vapours arising from both stills pass through

dephlegmators (plate heat exchangers) which cool and partially
condense the vapours to form reflux for optimum still operation. The
ammonia vapours can then go one of two process routes - CAL
production or Incineration (Fig 2). CAL production is necessary
because of a single incinerator operation.

In terms of proportion, the ammonia plant normally produces CAL

for approximately one fifth of the operating time although this depends
upon customer requirements. For the remainder of the operation, the
ammonia vapours are incinerated.

The switch between CAL and incineration is achieved by swinging

spectacle plates to positively blank off relevant sections of vapour
pipework, diverting the flow of ammonia vapour.
228 THE COKE OVEN MANAGERS’ASSOCIATION

When on CAL production, the vapours are fed to the CAL

condenser which fully condenses the vapours to form the liquid
product. The condenser is an Alfa Laval plate heat exchanger
consisting of 54 x 0.5mm titanium plates with RCB rubber seals using
secondary cooling water at approximately 16°C as the cooling medium.
The CAL product leaves the condenser via a knock out pot, any
vapours generated from this are returned to the downcomer through a
vent line under suction. The product is transferred to the make tank, a
small intermediate storage tank before it is pumped to bulk storage.
There are two main storage tanks for CAL of 130 tonnes capacity and
also 550 tonnes extra capacity available in a dual function liquor tank
but the availability depends on plant operation. From empty, there is
capacity on site normally for 260 tonnes which approximately equates
to 8 to 10 days make depending on the strength of the product (weaker
product equates to more volume). A typical CAL campaign lasts for 5
to 7 days and ultimately the frequency depends on customer
requirements and unplanned incinerator outages (incinerator
maintenance is normally planned around CAL campaigns).

Control & Monitoring:

The stills are monitored and controlled via the Ferranti system in the
main By Products control room.

The formal specification for the product is yet to be confirmed with

Brunner-Mond, although discussions are underway. The product
specification currently being worked to was agreed with Brunner-Mond
some 3 years ago and was requested to increase the H2S content in the
product to help prevent corrosion within the soda ash process. The
CAL product is analysed for NH3 and H2S content every two hours
from the CAL make tank. The product strength is monitored using an
at-line analyser (Although trialed, online analysis was found not to
work as effectively) and plant adjustments made accordingly. The NH3
content would be expected to be in the region of 19-21% and the H2S
from 3-4.5% which normally follows a ratio. This used to be in the
region of >0.15 H2S/NH3 but more recently this has been running
slightly higher at 0.19 to 0.22.
 THE PRODUCTION OF CONCENTRATED AMMONIA LIQUOR (C.A.L.) 229

The strength of the product depends on the following factors:

Flowrates through the stills

Still top temperatures (amount of LP steam to still)
Amount of Reflux/Dephlegmator temperatures
Temperature of the CAL condenser/Amount of cooling water
through condenser

Typical Ammonia Plant operating parameters are shown in the table

below:

Parameters Free Still Free/Fixed Still

Flow Rate (Litres / min) 425 Min 300
Max 450
Feed Temperature (oC) 80 -
Vapour Temperature 101 101.5 max
(oC)
Reflux Temperature 90 88
(oC)
Stripping Analysis <300 <100 (pH 9 - 10)
(PPM Ammonia)

Two key trends which are closely monitored to ensure good quality
products are the level in the plenum sump and the level in the CAL
make tank (Fig 3). The plenum sump receives liquids from the
ammonia vapour system and pumps them to the liquor storage tank.
Pumping is on level control. Excessive volume in the sump is an
indication of the stills priming and carry over of liquid into the product.
The rate at which CAL is produced as indicated by the rate of increase
in the make tank level is a good indication of the product strength. If
the CAL condensor is not operating correctly, the level rises more
rapidly indicating a weaker product. On a recent campaign, cooling
water began to pass into the product side of the heat exchanger due to a
seal failure. This was noticed by an abnormality in the above trend and
product quality and the condenser had to be changed.

If the CAL is too weak, the NH3 and the H2S content being too low,
the still operation may need to be optimised. This may mean
230 THE COKE OVEN MANAGERS’ASSOCIATION

decreasing the still feed flowrates (Flowrates generally kept on the low
end of the operating range for CAL production) or increasing the still
top temperatures (This is limited depending on 3 factors - Expense of
using excess steam, too much pressure on the still by using excess
steam to the point where liquor is “blown” over the top with the
vapours and the vapours being too hot to obtain an effective reflux
temperature). One of the main and most common factors affecting
effective still operation is reflux. Reflux increases the concentration of
NH3 and H2S on the top tray of the still, therefore altering the
equilibrium in the still to perform better.

There are practical difficulties in producing very strong CAL.

Pieces of kit used in the CAL production process (knock out pot from
condenser, separators, plenum sump) are all connected to a common
vent line under suction from the downcomer. Making stronger CAL
precipitates greater crystal growth, ammonium carbonate, within this
vent line and the condenser itself causing blockages in the system.
Intermediate pressure steam (8 Bar) and flushing liquor are
permanently piped to both the vent line and the condenser as a means of
clearing such blockages by melting deposits out. Initially, only steam
was installed until an idea volunteered through the suggestion scheme
to include an additional liquor line was introduced, liquor was found to
more effective at clearing carbonate blockages than steam. As a
routine, the CAL condenser is steamed out and flushed out with liquor
at least once a shift, although this may be necessary more frequently
due to product strength and ambient temperature (cold weather also
encourages blockages). The CAL vent line is normally steamed clear
and liquor flushed at the beginning and end of every campaign unless
plant indications dictate otherwise - A blocked vent line and/or
condenser would give an increased pressure on the free still (measured
on Ferranti, normal plant operating pressure would be 250-300 mBar),
the T piece vent on the plenum sump would blow vapours to release the
pressure, still stripping would become difficult and CAL quality would
deteriorate. The normal course of action would be to clear the CAL
vent line blockage on detecting an increased pressure in the still before
seeing this deterioration in operation and quality.
 THE PRODUCTION OF CONCENTRATED AMMONIA LIQUOR (C.A.L.) 231

Safety:

CAL is a yellow coloured liquid in appearance with a highly irritant

odour. It is extremely corrosive and causes burns. If it contacts skin,
area should be drenched with water immediately. Medical attention
should be sought if any injury from CAL arises. When there is a risk of
skin/eye injury due to liquid contact, suitable PPE must be worn.
Respiratory protection must be worn when subject to high
concentrations of vapour.

OES for NH3 is 25ppm based on an 8 hour TWA.

Flammable/Explosive range of 16-25%.
Vapour is lighter than air, density is 0.6 relative to air.
Can spontaneously ignite at temperatures above 650oC (auto ignition
temperature).

Despatch:

Brunner-Mond take the CAL product by tanker load, approximately

25 tonnes. A loading schedule is provided by the Records Dept the
week previous informing us of Brunner-Mond’s requirements for the
following week.

There is a designated loading bay on the By Products plant for

loading CAL. An elevated platform provides access to a pneumatically
operated loading arm which is lowered into the tanker top. The driver
positions his tanker and connects the earth line to the vehicle. The
driver is required to wear suitable PPE consisting of a chemical suit and
an ammonia mask due to exposure to both liquid product and fumes.
The ammonia plant team member selects the storage tank to load out of,
opens the air operated valve on the loading arm and starts a loading
pump when ready. There are safety interlocks on this system. The
tanker must be earthed, the emergency trip switches must be set
correctly in the “on” position and 2 pressure switches on the air to the
pneumatic arm must be correct. If these interlocks are not met, then the
loading process will not begin. The driver “dips” the tanker to indicate
when loading is complete and then the loading pump is stopped.
During the tanker loading, a sample of despatched product is taken for
232 THE COKE OVEN MANAGERS’ASSOCIATION

the labs to analyse. The analysis results are sent electronically to

Brunner-Mond as the tanker will already be on route to the customer’s
site. The despatched CAL should have a similar analysis to that made
during the last campaign, however, it is known that CAL forms layers
when settled out in the storage tank so some variations can occur.
The loading arm and platform is currently being redeveloped. The
tanker size has become larger and the platform needs to be modified to
accommodate this change. The loading arm has recently become
increasingly difficult to manoeuvre due to the swivel joints being badly
seized. These have been refurbished and operation has improved but
consideration is being given to a bottom loading system which would
significantly reduce the amount of fumes present during loading. It is
also a possibility that the loading area could be moved. At present, the
loading bay is at the other end of the ammonia plant to the storage tanks
and loading pump. The reason for the location is that the ex loading
pump was located here and part of the deacidifer structure was used for
a loading access platform. The caustic bund was also convenient for
containing spillages. The loading line runs through the plant gully
system and frequently develops leaks due to the corrosive properties of
the product. This pipework is made from stainless steel. There would
be a potential saving in reducing the length of pipework for loading
CAL as maintenance costs would be lower maintaining a shorter
pipeline. It would also be feasible to run a reduced length of pipe in a
more corrosion resistant material such as titanium.
THE PRODUCTION OF CONCENTRATED AMMONIA LIQUOR (C.A.L.) 233

Fig 1
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Fig 2
THE PRODUCTION OF CONCENTRATED AMMONIA LIQUOR (C.A.L.) 235

Fig 3