Operating Manual for Dual Pressure Nitric Acid Plant, DFPCL

Chapter 8: Health and Safety Hazard Data

8 Health and Safety Hazard Data

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Chapter 8: Health and Safety Hazard Data

8 HEALTH AND SAFETY HAZARD DATA 1

8.1 Guiding Principles for Safety 3

8.2 Noxious properties of process fluids 4

8.2.1 Ammonia 4
8.2.2 Nitric Acid 7
8.2.3 Nitrous Gases 9

8.3 Protective Equipment 11

8.4 General Measures to Reduce the Danger of Accidents 12

8.5 Special Measures to Prevent accidents 14

8.5.1 Special Measures to Prevent Explosions of Ammonium Nitrate and Ammonium Nitrite 14
8.5.2 Special Measures to Prevent Accidents when Working on Electrically Driven Equipment and
Machinery 15
8.5.3 Special Measures to Prevent Accidents during Sampling 16
8.5.4 Special Measures to Prevent Accidents while opening and inspecting Vessels and Equipment 17

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8.1 Guiding Principles for Safety

The guiding principles for safety contained herein are an extract from official
regulations of particular importance. These principles are therefore by no means
complete, and the relevant regulations for the prevention of accidents should be
studied in conjunction with them.
For start-up, shut-down and operation the following safety regulations should be
strictly followed.

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8.2 Noxious properties of process fluids

8.2.1 Ammonia

8.2.1.1 Noxious Properties of Ammonia

Under normal circumstances, ammonia is a colourless gas and its density is less
than that of air. It is easily recognisable by its extremely pungent odour. Ammonia
is easily liquefiable under pressure. At atmospheric pressure, ammonia will
evaporate at a temperature of about -33 oC, while absorbing heat from ambient
matter.
Ammonia is easily soluble in water; such solutions can contain up to 35 %
ammonia (ammonia water). Liquid ammonia, high-percentage ammonia water
and highly concentrated gaseous ammonia will irritate human skin and cause
severe burns. Gas of high concentration will paralyse respiratory organs.
The following are particularly endangered:
(a) eyes
(b) mucous membranes (mouth, throat, respiratory ducts, lungs, genitals)
(c) larynx, gullet and stomach, particularly if aqueous ammonia solution is
swallowed.
Injuries to the larynx and lungs can be fatal. The pungent odour is an adequate
warning and will therefore prevent severe injuries to health, since the real danger
begins when the endurability limit is exceeded. The maximum permissible
concentration in a working area over eight hours is acc. to German regulations 20
ppm, equivalent to 14 mg/m3. Irritation of the larynx and the eyes will be
noticeable when the concentration is ten times as great. At an ammonia
concentration of 0.15 %, uncontrollable coughing will set in, and at a
concentration of 0.5 % paralysis of the respiratory ducts will begin.
Concentrations of around 2 % will perceptibly irritate uncovered skin.
If liquid ammonia comes in contact with human skin, there is a danger of
undercooling.
Great care should be exercised when handling ammonia.
A mixture of air and ammonia can be explosive. This is particularly the case,
whenever the ammonia content of air at normal temperatures and pressures is
from 15.5 to 27 % by vol.

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In the presence of other combustible substances, such as hydrogen or acetylene,

at higher oxygen contents of air or at abnormal pressures and temperatures, the
hazard limits cover a greater range, thus the danger will be bigger.
Explosive mercury compounds (azides) may be formed if compressed ammonia-
bearing gases come in contact with metallic mercury. Thermometers, pressure
gauges, and the like installed on ammonia-bearing equipment or piping should
therefore not be of the mercury type.

8.2.1.2 Protective Measures

Whenever ammonia is escaping from a piece of equipment or a pipe, the room
must be evacuated at once, using gas masks. The endangered zone should be
thoroughly ventilated as soon as possible. In view of the fact that ammonia is
lighter than air, ventilation by upward draught will be most effective.
If any work has to be carried out in rooms contaminated with ammonia (e.g. for
lessening the hazards), respiratory equipment and protective clothing must be
worn.
A gas mask can be regarded as limited respiratory equipment. Providing there is
sufficient oxygen in the atmosphere, the gas mask fits tightly and the special
ammonia filter has been screwed into the gas mask, contaminated rooms may be
entered for a limited period of time, if certainty exists, that the ammonia content is
below 2 %. The filter manufacturer's data will give precise information on the time
limit, the maximum permissible ammonia concentration and the life of a new gas
mask filter the container seal of which has not yet been broken.
A sufficient number of gas masks should be available at all points where
ammonia might possibly escape to enable operating personnel to evacuate the
plant quickly.
If, for any reason, a gas mask should not be available, the next best protection
will be afforded by holding a wet rag over nose and mouth. In emergencies, a dry
handkerchief or a sleeve will afford some protection. In all such cases it is
important to choose a route of escape against the wind.
The breathing apparatus is used whenever the ammonia concentration exceeds
the limit value mentioned above or if it is not known (or if it is likely to alter), if the
oxygen content is too low, or if the life of the gas mask filter is likely not to be
adequate. Breathing apparatus of the type connected by means of a hose to an
air intake located in a non-contaminated area will frequently have a too high line
resistance and will mechanically impede both the work and the radius of action.
Better manoeuvrability is achieved with breathing apparatus incorporating
compressed-air bottles. Any person using such breathing apparatus should, prior
to use, ensure that sufficient air is contained in the bottle, the valve is set
correctly, the hose connection is properly fixed, and that the mask fits properly.

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In addition, it is important that persons working in rooms contaminated with toxic

gases are observed from the outside and that suitably equipped personnel is
standing by to rescue such persons in emergencies.
Over and above the respiratory equipment mentioned, personnel in hazardous
areas should wear protective clothing covering the whole body.
Such protective clothing comprises:

- a long-sleeved working jacket,

- long trousers and underwear,

- if possible, made from cotton, since cotton is more

- resistant to alkalis than wool,

- rubber boots,

- rubber gloves,

- protective helmet with rim.

The sleeves should be worn outside the rubber gloves and the trousers outside
the boots. Certain areas of skin can also be protected by an ointment or oil.
If necessary, the above-mentioned protective clothing can be replaced by a tight
anti-gas suit covering the whole body.

8.2.1.3 First Aid

It is of primary importance to take the injured person out of the endangered area
as quickly as possible. In case of serious injuries or of any injuries to the eyes, a
medical practitioner must be summoned at once. In the meantime, as much
ammonia as possible must be eliminated, e.g. by dousing with plenty of water,
discarding contaminated clothing including underwear. The patient should then
be made to lie down and wrapped in blankets to keep him warm.
Eyes affected by ammonia must immediately be washed with plenty of clean
water. This can be followed by an eye bath in diluted acetic acid (0.5 %) or boric
acid (3 %), after which the eyes should again be washed with clean water.
If ammonia has been breathed in, inhalation of steam or vinegar vapour is
recommended. Artificial respiration is forbidden.
If possible, the breathing air should be enriched with oxygen. If ammonia-bearing
water has been swallowed, the patient may be given milk to drink providing he is
fully conscious.

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8.2.2 Nitric Acid

8.2.2.1 Nitric Acid Properties Injurious to Health

Nitric acid is a colourless liquid which gradually turns yellow owing to
decomposition phenomena under the influence of light or heat. When the acid is
kept in open vessels, it will discharge vapours which generally contain nitrous
gases.
Nitric acid figures among the strong acids; in addition, it features marked
oxidising characteristics and will seriously attack numerous metals and organic
substances. In case of contact with the human skin, it will produce burns whose
seriousness depends on the concentration of the acid. The affected zones of the
skin assume a yellow colour.
Large-area acid burns of the skin might be lethal, serious injury of the eyes might
lead to a loss of the eyesight. When drinking nitric acid, mucous membranes will
suffer burns that might be lethal.

8.2.2.2 Protective Measures

Persons working on piping or vessels containing nitric acid must wear protective
goggles. Better safety is achieved through the use of protective globes of
transparent plastics that cover head and neck. Hands can be protected through
rubber gloves which, however, have only a limited resistance to concentrated
acid.
Suits of felt or special plastics (acid suit) are adequate for use as protective
clothing.
It is imperative to wear a gas mask when working in any area where nitrous
gases or nitric acid vapours might be encountered. Respiratory equipment should
be used even when a slight increase in nitrous gas concentration is detected
because normal filter elements might break down.
Concerning the maximum permissible nitrous gas concentration, the
specifications furnished by the manufacturers of gas mask filters shall be
observed.
Spilled acid shall not be taken up with the aid of cloths, sawdust, clean or oil-
bearing cleaning waste. For removing the acid, it might be advisable to neutralise
with lime or soda ash (pay attention, however, to the evolution of CO2) and flush
the whole into the sewer with large quantities of water.

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8.2.2.3 First-Aid Measures

After contact of nitric acid with the skin, flush immediately with large quantities of
running water and subsequently with a dilute sodium carbonate solution (5 to 7 %
concentration). Clothing soaked with nitric acid shall be removed immediately.
For large-area burns it is recommended to flush the skin under a shower or with
the aid of water hoses and water-filled bath tubs. The personnel must be clearly
aware of the location where flushing facilities are installed. To avoid sub cooling
of the body, it is recommended to use lukewarm water if flushing must be
continued for any appreciable time. No oil, ointment, tar or flour shall be
administered to acid burns on the skin. Any person who has suffered acid burns
shall consult a physician.
Immediate and intense flushing with large quantities of water shall also be done
in the case of acid burns in the eyes. The eye lids shall be held apart to ensure
full exposure to the flushing water. Immediate subsequent medical aid is
imperative.
If nitric acid has penetrated into the mouth of a person, the patient should
immediately be allowed to drink large quantities of lukewarm water to dilute the
acid swallowed. Early medical aid is absolutely necessary.
A stomach tube shall be administered by a physician only, because any organs
that have suffered acid burns are easily bound to be injured.
First-aid measures to be applied after inhaling nitrous gases are outlined in the
following Chapter "Nitrous Gases".

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8.2.3 Nitrous Gases

8.2.3.1 Properties Injurious to Health

The oxidation of ammonia, the reaction of nitric acid with reducing substances,
and the decomposition of nitrate-bearing substances are accompanied by the
formation of the extremely poisonous "nitrous gases" which are a mixture of
various oxides of nitrogen.
Nitrous gases are a very malicious poison because the immediate nuisance after
inhaling is negligible and the seriousness of the poisoning does not appear
before expiration of several hours.
Few breaths in a fairly poisoned atmosphere might be sufficient to destroy the
tissue of the lungs to a point where a lethal oedema of the lungs might occur
even 8 hours or more after exposure, unless adequate aid is administered in
good time. The symptoms of serious affection, such as headaches, fatigue, low
blood pressure, will sometimes commence after several hours only. Subsequent
effects are the blueing of the lips, shallow breathing, death from suffocation.
It is absolutely imperative that any person who has inhaled nitrous gases consults
a physician even if no signs of indisposition are apparent.
The maximum permissible concentration of oxides of nitrogen at the working
place is about 9 mg/m3 (5ppm). A short-time exposure to an atmosphere
containing 25 ppm NO2 might be injurious to health; a lethal effect must be
expected at 200 ppm.

8.2.3.2 Protective Measures

In case of an eruption of nitrous gases, the personnel shall leave the place of
eruption as quickly as possible and in a direction opposite to the wind direction.
Actions to be taken for eliminating the evolution of oxides of nitrogen depend on
the cause of such evolution. Personnel shall approach the point of leakage from
a direction which is opposite to the wind direction. As mentioned before, the
protective effect of gas masks is limited by the gas concentration and the time of
exposure.
For further details, reference should be made to the specifications furnished by
the manufacturers of the gas masks. Better safety is achieved with respiratory
equipment. The use of suitable gas protective clothing is also recommended.

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8.2.3.3 First-Aid Measures

Any person who has inhaled nitrous gases should immediately be removed to
fresh air and should be covered with blankets and kept quiet until the physician
arrives. The patient shall not move even if he feels able to do so. It is
recommended to enrich the breathing air with oxygen and to allow the patient to
inhale the fumes of an ammonium bicarbonate solution. Artificial respiration
should not be administered.
If no physician is available at short notice, the patient should be taken on a
stretcher to the nearest hospital.

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8.3 Protective Equipment

In order to prevent accidents and to lessen their effect, suitable clothing should
be worn covering the whole body other than head and hands and, in addition, the
following items of protective clothing and respiratory equipment should be readily
available:

- Protective helmets

- Goggles and acid-proof hoods

- Gloves, partly of rubber, wool and leather

- Rubber boots

- Rubber protective suits

- Gas masks with appropriate filters

- Breathing apparatus

- Tight anti-gas suits and acid suits

- Shower-baths for washing off corrosive substances

- Sodium carbonate solution (5-7 %) for post-treatment after acid burns on skin

- Eye-bath flasks with clean water

- Eye-bath flasks with 0.5 % acetic acid or 3 % boric acid

- First-aid outfits

- Stretchers with blankets

Instructions on the first aid to be given in case of addidents, poisoning and burns
caused by the chemicals used in the plant.
It is extremely important to check continuously the protective equipment and to
maintain it in a fully serviceable condition at all times.

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8.4 General Measures to Reduce the Danger of Accidents

Accidents can be avoided if:
The production plant is always kept clean and in technically proper condition. Any
cotton rags, paper, other waste, tools, instruments no longer used, and similar,
must be kept in special containers or at special places.

- Escape ways and fire escapes must be kept free.

- Absorption towers must only be mounted if a serviceable gas mask is carried

along.

- Protective covers on mobile parts of the equipment must be orderly fixed.

- Cleaning works on running machines should not be made.

- Stays under pending loads should be avoided.

- For works which cannot be carried out from firm platforms skeletons must be
expertly erected, or if possible, steps as prescribed by directions can be used.

- In case of open erection holes, handrails must be provided.

- For works in some height safety belts must be worn.

- A protective helmet should always be worn in the production plant.

- Entering of the production plants is not admitted to unauthorised persons.

- All persons not concerned with the operation of the plant, must leave the plant.

- All necessary repairs must be carried out at once and only by the competent
personnel after contacting the shift foreman and previous checking of the
respective aggregate.

- To avoid misunderstandings the order is best given in writing and completion

of the work is also confirmed. Hints about suitable protective measures,
marked on this order, can be very useful. This applies especially for welding
works and the use of open flames in the production plant.

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- When using solvents, the appropriate instructions to avoid explosive ratios or

health injuries must be followed.

- The personnel must be informed of the safety regulations and accident

instructions at regular intervals.

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8.5 Special Measures to Prevent accidents

8.5.1 Special Measures to Prevent Explosions of Ammonium Nitrate and

Ammonium Nitrite

The mixture of nitrous gases and unburned ammonia can lead to formation of
ammonium nitrate and ammonium nitrite. During start-up for a short period this
gas mixture cannot be avoided.
To avoid the formation of ammonia water in the gas cooler which might possibly
result into an explosion in case of subsequent ammonium nitrate resp.
ammonium nitrite formation, nitric acid is injected during the ignition phase.

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8.5.2 Special Measures to Prevent Accidents when Working on Electrically

Driven Equipment and Machinery

When working on electrically driven equipment and machinery the shift foreman
must order, via the competent electrician, the shut-off resp. the protection against
not allowed switching in.
This comprises proper switching off, taking out of fuses, resp. locking of switches
with safety locks or disconnecting of the cut off knifes.
At the appertaining switch a sign "Switching on prohibited" must be hung up.
Only after having taken these measures the shift foreman may allow the repair.
After completion of repair works the shift foreman must convince himself of the
correctness and determine whether the equipment can be switched on again
without danger.
If there is no danger, he has the machine tripped again by the operating
electrician. During this procedure the shift foreman must be present.

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8.5.3 Special Measures to Prevent Accidents during Sampling

Sampling is done by specially trained personnel.

The person taking samples must wear protective equipment as goggles, gas
masks etc., which corresponds to the special situation and material.
The sample must be filled only into the special sampling container.
Special care must be taken when the agent is on pressure or has a very high
resp. very low temperature.
If the sampling valve is not movable, great power strains should be avoided. It
must be brought into proper operating condition in due time.
Transport of the sample must be made with the necessary care. Dangerous
materials must be protected against splashing, e.g. when stumbling on stairs etc.,
and should be put into containers which can be locked.

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8.5.4 Special Measures to Prevent Accidents while opening and inspecting

Vessels and Equipment
8.5.4.1 Opening of Vessels and Equipment
Before opening vessels and equipment, these must be drained as far as this is
required for safety reasons.
If the vessel was under pressure, it must be expanded effectively beforehand.
When opening the vessel, the bolts of the flange connection or the lid on the
remote side and opposite to wind direction have to be loosened first. Thereafter
the lid or the flanges still held by some screws equally distributed on the
periphery, must be slightly vented and loosened that much, that it does not stick
or rest on the gasket seat. If there is no overpressure anymore, the flange
connection can be fully loosened, the lock completely unscrewed or the lid taken
off.
If the vessel was containing toxic material before drainage, health can be
endangered by the streaming out agent; or if the material showed a very high
resp. very low temperature, corresponding protective clothes must be worn.

8.5.4.2 Special regulations for the inspection of vessels, equipment etc

Before inspection of a vessel etc. this must be drained first, and if possible,
cleaned by flushing from outside. By interrupting the feed lines, in exceptional
cases by inserting blind flanges, the feed of any endangering materials must be
eliminated.
If toxic or narcotic gases can collect in the vessel or equipment, the personnel
can only inspect this when wearing proper gas masks.
If inflammable gases or explosive gas mixtures can form up in the vessel, a good
venting must be carried out to remain below the ignition limit.
When using electric lamps and instruments in vessels of good conducting
materials, protective measures against contact potential become necessary.
Portable lamps must only be used up to low voltage of 42 V. The electric
instruments and their supply lines must be checked for their irreproachable
condition before use. It must be secured, that the electric supply lines cannot be
damaged during work.
Before inspection of vessels or equipment which are movable or have movable
internals, i.e. drying drums, centrifuges, tube vessels, bucket elevators, etc.
measures must be taken against not allowed and unintentional starting or
moving. For this purpose the electric drive can be switched off by disconnecting
all conductors, by locking the switch or by interrupting the corresponding electric
fuses. An unintentional moving of the internal parts can for instance be avoided
by arresting the brakes of the drive or by blocking the movable parts.

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The person entering the vessel must be tied to a safety belt and watched by
somebody outside. This person must not leave, and in case of need further
assisting persons must be made available. Any persons also entering the vessel
must be equipped correspondingly, in case of need also the watching person.
After completion of the work the vessel must only be brought into normal
operating condition, after the supervisor has convinced himself, that the
personnel has left the equipment and that order was given to the personnel, not
to enter the vessel or equipment again.
If any work is done on the NH3-gas system or in case of a long shut-down the
spectacle blank in the line 6"-AG1-12031-EB57 should be installed and by this
the gas system is blinded from the liquid NH3-system. Shortly before start up the
spectacle blank should be turned, so that the NH3-gas can pass.

8.5.4.3 Special Measures to Prevent Accidents during Welding Works

Rooms where welding works are to be carried out, should be vented
correspondingly. Small rooms or vessels must be constantly vented with fresh air,
or the personnel must use oxygen equipment. Before starting work it must be
made sure that no danger of fire or explosion exists.
When working on containers and vessels, these must be opened and cleaned
beforehand.
When working on hollow bodies the formation of a dangerous overpressure must
be avoided.
During welding works in the neighbourhood of inflammable building parts, i.e.
wood or similar, safety precautions must be met to avoid fires, e.g. by covering all
inflammable parts, disposal of extinguishing water or other suitable fire
extinguishing instruments. The heated spot or the endangered neighbourhood
must be watched until there is no longer a noticeable over-temperature.

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8.5.4.4 Fire Protection Devices

The operating personnel must be made familiar with the fire protection and fire
extinguishing equipment. The fire extinguishing equipment should be easily
accessible and clearly marked. A use for other purposes should be prohibited.
In case of fires to the aggregates which are under electric voltage, the use of
foam extinguishers or the spraying with water should be waived due to the
connected danger of accident (electric shock). In this case carbon dioxide or dry
extinguishers are suited for use.
Carbon dioxide- and foam extinguishers can also be used in case of oil fire. Fire
extinguishers containing tetrachlorine dioxide, often develop toxic gases. For this
reason use of these instruments is appropriately waived.
If the fire stretches over to the nitric acid tanks, it is recommended to use water, if
this is not prohibited due to special circumstances.
Due to-gases and vapours forming up during fires, and also due to the fire
extinguishing agents applied, the wearing of proper gas masks is absolutely
necessary.

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