IChemE SYMPOSIUM SERIES NO.

153 # 2007 IChemE

HAZARD ANALYSIS – FILTRATE STORAGE TANK

Joseph Weber1 and Benjamin Sagiv2

1
Safety Consultant, Weber Safety Engineering Ltd., Raoul Wallenberg 10, Haifa 34990 Israel; e-mail: weberyos@netvison.net.il
2
Safety Manager, Rotem Amfert Negev Ltd. – ICL Group, Mishor Rotem Plants, M.P. Arava 80500 Israel;
e-mail: benny_s@rotem-group.com

Plant design and changing in existing plants are relying on engineering approach focussing on the
technical design and production effectiveness. Process Safety issues have to be taken into account
in the various design stages. Process hazard analysis methods are use to determine possible
causes of an events or incidents issues in order to prevent hazardous states that might lead to
future incidents.
Changes and redesign in an exist plan, installing a new Filtrate Storage Tank, lead to perform a
detailed Process Hazard Analysis, as part of the Management of Change procedures. For the new
Filtrate Storage Tank design a Hazard and Operability (HAZOP) analysis was performed. Based on
the operation and safety expertise of the HAZOP team, it came out with a comprehensive list for
possible hazardous situation, which might lead.

KEYWORDS: hazard analysis, accident, root causes

INTRODUCTION HAZARD ANALYSIS FOR POTENTIAL

The process industry has to maintain and improve the
level of safety to its employees, the public and its stake-
holders. Using Risk Assessment and Control methods for
hazard identification are a way to improve the safety of
new or revamp process plants. Hazard and Operability
Analysis studies are using the knowledge and experience
gained from successful approaches in other plants translat-
ing it into practice, by improving the design of new units.
Knowledge learned from accidents and near misses can be
translated into practice. Process Hazard Analysis studies
with a multi-discipline team can gain the knowledge
and implement it the new unit or plant design. A major
role in safety operation and maintenance in the process
industry is performing of management of change for
each major change in the system, by analyzing the poten-
tial hazards.
THE PROCESS INSTALLATION
The process system consists of a phosphoric acid raffinate
tank, which is fed from the solvent extraction (Liquid-
Liquid Contact) section, a sulphuric acid tank, a mixer
that blends phosphoric acid (H3PO4) and sulphuric acids
(H2SO4), and then fed to a reactor. The reactor is
feeding two filter presses, where calcium sulphate is fil-
tered out. Having two filter presses, working on cycle.
The acid liquor filtrate from the filters is passed to the
filtrate storage tank. Overflow line from the reactor is
going into the filtrate storage tank. The sulphuric acid
raffinate may include solvent remains from the previous
section.
After filtering, air is blown through the filters, to dry
the filter cake. The air also passed to the storage tank, and
left it via 600 overflow line, being exhausted to atmosphere
in a pump sump alongside the thickener tank.
ROOT CAUSES
Process Hazard analysis was performed for the unit, by
using the HAZOP method, in order to determine the root
causes and consequences for an event or incident.
Here are some root causes for incident of overpres-
sure and explosion, which might cause an incident.
OVER PRESSURING BY AIR
Overpressure could be derived from the blower air used for
drying the filter cake. The air compressor delivers air at 4.5
bar (g). This is ample to cause damage.
The tank was designed with an overflow of the
tank, which was a fairly long 600 pipe, the tank
original vent nozzle is used for filtrate inflow.
The overflow pipe serves as a vent for the
airflow, although it is not designed as a vent.
There were low points in the pipe, so that
blockage with liquid or with slurry would not
only be possible, but might be inevitable at
some stage.
EXPLOSION OF HYDROGEN
Hydrogen can be present in acid tanks, because of the reac-
tion of acid with steel. The reaction is
Fe þ H2 SO4 ) FeSO4 þ H2 "
As can be seen, about 1/2 kg of hydrogen is sufficient
to cause an explosion, which could project the tank to the
observed distance.
In order to confirm the possibility an inspection
should be done to determine whether significant loss of

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IChemE SYMPOSIUM SERIES NO. 153
steel could be found, sufficient to generate the necessary
hydrogen.
The hydrogen could in principle come from another
source, but no obvious source was found, in the analysis.
Gradual accumulation of hydrogen in the tank is also
unlikely, because the air blowing of the filters provides good
ventilation.
SOLVENT VAPOR EXPLOSION
A possibility for explosion is the ignition of solvent vapor in
the tank.
Solvent is necessarily present in solution in the acid,
because of the use of the solvent in the raffinate source
process section. Free solvent may be transferred if disturb-
ances arise in the source process, leading to low level in
the vessel there. Under normal acid temperatures, the
solvent vapor pressure is sufficiently high to bring the
vapor concentration above the upper explosion limit
(UEL). With storage of acid alone, the tank would be full
of vapor. Air would enter the tank only when the tank was
drawn down, (acid transferred out of the tank) and only if
the draw down were rapid.
With the use of filter cake drying with air, the amount
of air in the tank is increased significantly. With free flow, it
is likely that a large part of the solvent vapor would be ven-
tilated out of the tank. There would be an interval both at the
start and end of the blowing, when the concentration was
between LEL and UEL.
As the overflow line also served as a vent, which
might be at least partially blocked, this may reduce the
degree of ventilation, and increased the explosion potential.
POSSIBLE SOURCES OF IGNITION
Some general potential sources of ignition were identified.
This potential ignition sources might lead to an ignition
and explosion. This may happen in various systems
involved with flammable liquids, such as solvents and alco-
hols. With these number of potential ignition sources,
ignition is likely to propagate and explosive conditions
are allowed to arise.
(1) Blown droplets. Droplets blown by air during the filter
cake drying could be charged electrostatically, and
might ignite vapor on discharging.
Special design improvement should take electro static
discharge (ESD) into account.
(2) Acid droplets in solvent. If a slug of solvent might be
transferred into the tank, via the overflow line, droplets
of acid in the solvent could have become charged.
This is a generally possible cause, this has to be
checked relatively to solvent conductivity and flow
velocity.
(3) Leyden charging of the tank. The tank is structured like
a large Leyden jar (capacitor), with an outer conduc-
tion layer (the tank shell) a resistive inner layer (the
rubber) and an inner conductive layer (acid).
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# 2007 IChemE
Without a method of shorting, the acid could acquire a
very large charge. The charge would be bled off by
conduction through any cracks in the rubber lining,
or slowly, through the rubber itself. The degree of
the problem depends on the rate of charging versus
the actual rate of conduction. This cannot be predicted,
and needs to be measured.
(4) Electrical failure. Electrical, control and instrumenta-
tion accessories, with electrical power supplies, are
fitted on tanks. On most tank level indication and
switched are installed. Electrical failure on either of
theses accessories might produce overheating or elec-
trical sparking.
The instruments should be designed and checked
periodically for use in flammable zone.
(5) Chemical decomposition. Adding acid to with organic
residue may lead to organic material residuals that
might collect on some surfaces, or that charring of
organic material, presumably solvent or organic
impurities.
Mix of concentrated acid with solvent might form
ether by dehydrolisation. Higher degrees of charring
to a tar may also occur. If ether is formed then there
is also a possibility of forming unstable peroxides,
by oxidation with air.
Although it is unlikely that such a reaction would take
place with large yields, because of the rapid dilation of
the acid, sufficient material might be produced due to
the large scale of the operation, and the material
would tend to collect in the storage tank.
(6) Electrical discharge from other equipment. Electrical
conduction from other equipment, such as the air com-
pressor or pumps, is a possibility. Inductive current
from cables to piping could also, in principle lead to
a discharge. In the actual circumstances this seems
extremely unlikely, in view of the fact that most
piping are plastic, PE, PP or PVC.
(7) Lightning. Induction from lightning could in principle
cause an explosion. In the actual case, the weather situ-
ation at the site has to be checked for possibility of
lightning. In a more general context, lightning could
cause ignition.
(8) Electrical charging from the filter press. The filter cloth
of the filter press is a synthetic fiber, and could presum-
ably cause charging of liquid droplets during filter cake
drying. This cause may be checked and measurement
should be taken.
(9) Ignition from electrical equipment in the sump. The
discharge location of the tank overflow line should
be carefully examined. With discharge of an air/
solvent vapor mixture into the sump, there would be
a frequent or regular presence of explosive atmosphere
in the sump. Electrical equipments in the sump are not
designed as explosion safe, so ignition might been a
possibility. This potential for accidents has impli-
cations for any plant, where sumps exist which can
contain a flammable atmosphere.
IChemE SYMPOSIUM SERIES NO. 153
Figure 1. Plan of process system feeding filtrate storage tank
GENERAL LESSONS LEARNED
Yet again we learn that all plant changes require a Process
Hazard Analysis (such as HAZOP – Hazard and Operability
Analysis). On the basis of cost alone, savings on HAZOP are
a bad form of saving. Safety analysis may be regarded as
costly, but accidents cost hundreds of times more.
It should be considered whether an actual accident
could be prevented by a prior HAZOP study. A safety
design review process should be added to the HAZOP
studies. The actual procedure and knowledge base for
HAZOP studies is probably not good enough for prevention
of all accidents.
A HAZOP and a pre-startup safety review are
recommended step for Management of Change in the
plant. Prior to each new unit or equipment startup safety
consideration and studies has to take place. Process Safety
Management guidelines are including this methodology.
Plant management has to take care for implying good
company standards and procedures, in order to keep a
high safety level at each of the plant units.
CONCLUSION
The following are the main Hazard Analysis conclusion:
– Overpressuring might be caused by acid overflow into
the overflow pipe, or to collection of splashed droplets
at a low point in the overflow line.
– Vapour explosion might be caused by alcohol vapour,
mixed with air.
– The possibility of an explosion with hydrogen mixed
with air is less likely, but there is a possibility for hydro-
gen accumulation.
– Several design weaknesses were found, which need to be
eliminated and approved in the tank design, as well in
any future design.
# 2007 IChemE
– There were many potential sources of ignition, which
might be removed or reduced before unit start-up.
Each of the possible causes of the incident may lead to
be depended on technical issues and human factor aspects.
(a) Detail design.
(b) Management of Change.
(c) Process Hazard Analysis.
(d) Operation procedures and Safety instructions.
The evidence of a potential accident in an acid storage
tank should lead for deep safety analysis of the system. A
full Process Hazard Analysis, as part of Management of
Change, should be done on each system, even if ignition
or explosion in an acid tank might be overseen.
The system was regarded as non flammable and is
located in the inorganic section of the plant.
The system was introduced as a full scale pilot, in
experimental mode, as for these a lot of changes were per-
formed with no related safety overview.
For each design or mechanical changes in a plant
safety analysis should be performed.
Management of Change procedure should be
implemented for changes in an experimental plant as well
as in process plant. Even change of tank overflow line
location might cause a hazard.
There were many potential sources of ignition. A
safety analysis should be done, prior to plant operation, to
identify potential ignition sources. The analysis should
include survey of ignition source and potential causes for
explosion, especially when operating with flammable sub-
stance, even when dissoluble in inorganic material.
No explosions occur at the operation of the Filtrate
Storage Tank, either due to a special combination of ignition
circumstances, or to the time needed for overflow line block-
age to accumulate.