4.

1 Process Safety

Formula of Chemical 𝐍𝐇𝟑 𝐍𝐇𝟒 𝐎𝐇

compounds
Name Ammonia Ammonium hydroxide
Physical state, appearance Ammonia is a colourless gas or Ammonia is a colourless liquid and
liquified gas. It has a prominently has a prominently sharp odour. It is
sharp odour and it can easily unstable and shows the same
undergo a reaction with water and features with weak bases. It can
form ammonium hydroxide in a easily be decomposed to ammonia
normal condition. and water in a normal condition.
Physical properties Boiling temperature= 240 K Boiling temperature= 311 K (25%
Freezing temperature=195.45K solution), 52 K (32% solution)
Vapour density relative to air=0.6 Freezing temperature=215.65 K
Steam pressure at 300 K =10 atm. (25% solution), 181.65 K (32%
Solubility in 𝐻2 𝑂 (𝑤𝑎𝑡𝑒𝑟) at 300 K solution)
=54g 𝑁𝐻3 per 100ml 𝐻2 𝑂 Ammonium hydroxide can easily be
Lower explosive limit=16% dissolved in water in any proportion.
Upper explosive limit=25%
Autoignition temperature=924 K

Chemical features, impacts Ammonia shows the same chemical As mentioned, ammonium
and hazards properties as strong bases and can hydroxide demonstrates weak basic
easily go into a reaction with acidic properties and it can vigorously go
feature compounds as a corrosive into a reaction with strong acids,
reactant. In addition, it can strong oxidants, silver oxide, silver
strenuously react with both nitrate, mercury, hypochlorite,
halogens and oxidants. As cited, halogens, some organic substances
ammonia has a corrosive property such as acrylic acid, acrolein,
and it can cause corrosion of dimethyl sulphate and so on. As
aluminium, zinc, copper and their ammonia, its solutions, ammonium
alloys if any contact happens. hydroxide as well have a corrosive
Ammonia has a high solubility rate property and it can cause corrosion
in water and during the dissolving of aluminium, zinc, copper and their
process great amount of heat is alloys if any contact happens.
produced. Ammonia has optimal
properties in the temperature range
between 223 and 283 K. The only
drawback is that ammonia is
considered dangerous.
Undoubtedly, it is toxic and
combustible. Ammonia burns, but
does not explode. It burns if its
concentration in air is above 15%.
Furthermore, ammonia is a natural
product, but it is very toxic in high
concentration. It has irritating effect
on the mucosa of the eye, nose,
throat and lungs.
Table 4.1.1 Properties of both ammonia and its solution in water [1]
Prior to taking some precautions of hazards may take place during the ammonia
production, it is necessary to indicate chemical and physical properties of ammonia,
and its impacts to humans and environment. The table given above shows those
properties and impacts.

4.2 Potential Hazards Related to Refrigeration systems [1]

Depending on chemical properties of refrigerants and also on key variables
(temperature and pressure in the refrigeration cycle), some possible hazards and
accidents can occur. Any negligence and irresponsibility can lead the following
accidents and hazards related to refrigeration systems to happen.
 The risk of flying particles can cause damage in fittings and if it is not prevented
on time, explosion of fittings can take place.
 Because of rupture in the system or another reason, refrigerant can leak out. It
happens usually due to wrong design, deficiency, repair or recharge of facilities,
inappropriate operation condition etc.
 As a result of leakage, fire risk increases if leaking refrigerant is combustible or
explosive.
In refrigeration equipment, the refrigerant can impact materials both physically and
chemically along with the result of temperature and pressure changes if the refrigerant
has hazardous features. Anhydrous ammonia and its compounds with other
substances can directly and indirectly put the workers, facilities and equipment, even
population, and the environment in danger.
In order to avoid the accidents and reduce the risk proportion, it is highly recommended
to follow the steps and safety instructions given below for protection against any
hazard or accident.
 Training programs should be established that’s why it reduces the risk of
hazard if the refrigeration system and other equipment are operated and
controlled by the knowledgeable and responsible stuff participated in the
training programs and knows all safety rules and regulations.
 In order to safeguard refrigeration equipment, barriers should be supplied from
impact in areas in which forklift are utilized, for example refrigeration coils,
valves, lines. As a result of forklift accident, ammonia leakage can take place.
 For all parts of the refrigeration unit, maintenance program should be developed
as follows: [2]
a)Control valves
b)Condensers It is important to check
c)Evaporators and list these parts of unit
once a week, and
d)Compressors
problematic parts must be
e)Pumps recorded and informed.
 f)Safety regulations for electricity usage-if any problem related to following
conditions happens during the operation, break the proper cutout and reset the process.
1)High temperature cutouts
2)High pressure cutouts
3)Low temperature cutouts
4)Low pressure cutouts
5)Automatic purge systems-eventual step for safety against any failure in
vacuum pump such as flooding or moisture build-up.
6)Low oil pressure cutouts
g)Emergency response equipment-all employees must use the equipment within
whole operation process
1)self-contained breathing apparatus(SCBA)
2)air monitoring equipment
3)air-purifying respirators
4)Level A suit
h) Ammonia detectors- is used to find and determine the location or unit part where
ammonia leakage occurs.

4.3 Risk analysis and Hazard identification [3]

Using this method, the objective is to get ahead of any accidents resulting in human
and property losses during the operation and management procedure, to make a safe
and insecure condition for all employees working in the process plant with anticipating,
analysing all possible risks, identifying all hazards systematically, and taking
precautions for protection against any danger. Risk analysis contains several
important steps given below;
 Hazard Determination- in this part, all sources and origins of accidents resulting
in leakage and release of dangerous material and refrigerants to air and their
risk scenarios are determined.
 Result Estimation or Probability-this part mentions about probability of affects
of accidents and damages to plant equipment or other structures, as well as
injury or loss of human beings.
 Accident Frequency Evaluation- in this part, average value of accidents
happened in this plant with respect to optional time interval (monthly, yearly,
during 10 years etc.) are calculated.
 Risk Estimation- in order to get risk distribution all accident results and
frequency in and out of the process plant are combined. [4]
The following figure describes risk analysis schematically.
 System Specification

Hazar Determination

Scenario Description

Result Estimation or Outcomes of

Probability of Accident
Accident

Risk Identification

Hazard
and/or Edit or Change Design
Risk
Validation

Operate and/or Build

system

Figure 4.3.1 Identification of Hazards and Risk Assessment layout. [5]

Risk of exposure-can happen usually unexpectedly and suddenly. Anhydrous
ammonia can leak out from the valves or transfer hose throughout transferring it from
the tank to the applicator or it can happen due to malfunctions of valves or faulty in
connection.
Injury and Death rate- Anhydrous ammonia has a pungent odour ant it can be easily
detected by human nose in concentration of 5 parts per million (ppm) In fertilizers,
anhydrous ammonia has a high concentration approximately 1000000 ppm and if its
concentration is above 5000 ppm, can cause death. is widespread cause of chemical
injuries, and it commonly happens accidentally during the plants and predominantly
these injuries happen in agricultural regions. Each year, several farmers are injured
because of exposure. Past three years, 55 people have been exposed by anhydrous
ammonia and 19 of them needed hospitalization. Third degree burns, permanent loss
of eyes can be counted in the most serious injuries. Anhydrous ammonia is extremely
harmful for respiratory system, integument, and eyes and it can cause lung damage,
burns, blindness and death. [6]
The following figure shows hazard degree of anhydrous ammonia

1
3 0
ALK

Health Ammonia has corrosive effect and it is

very dangerous and harmful for skin,
respiratory system and eyes
Fire Ammonia has specific flammable range,
it burns in a special condition, so it is
difficult to burn ammonia
Reactivity Reactivity capacity of ammonia is very
low ant it cannot react with lots of
substances violently
Specific property Ammonia has properties same with
alkaline and bases.

Figure 4.3.2 Hazard value of anhydrous ammonia

4.4 Environmental Impacts [7]
As mentioned before, from the properties of ammonia, it is obviously clear that
ammonia is a colourless, alkaline gas and water solubility of ammonia is very high.
Also, ammonia is very dangerous gas environmentally. Some environmental problems
or disasters for instance eutrophication and acidification are directly correlated to
pollution of water and soil with ammonia and it leads sensitive vegetation systems to
damage, biodiversity to disrupt, and water quality to reduce correspondingly. As can
be clearly seen from the figure 4.4.1, the agricultural sector makes up the highest
proportion (93.3%) of overall ammonia emissions in the European Union (EU) and
approximately 59% of these agricultural ammonia emissions involve livestock manure
management (accumulating, shopping, disseminating on land) whereas rest of
agricultural emissions (about 34%) are covered by agriculture soils.

Figure 4.4.1 Ammonia emissions, EU, 2013, European Environment Agency.

Birds themselves in a poultry house make ammonia. If nitrogen is not used, urea(5%),
uric acid(80%) and ammonia(10%) are extracted. If ammonia gas is kept in a humid
place, a basic, abrasive solution named ammonium will be formed and this aqueous
solution is very harmful for birds. It erodes wing lining and respiratory tracts of the birds
and causes paralyses or demolishes the cilia located in the epithelial cells. In this case,
with the aid of cilia, it is difficult to clean mucus located on the mucosal surface of the
trachea of respiratory system. Therefore, bacteria is considered being trapped and
when this bacteria is absorbed by lungs or air sacs, infection appears.
To take human and animal health under protection against ammonia emission, in
many countries, exposure levels of ammonia is regulated to set to 20-25 ppm.
Notwithstanding to this, in practice, this level can be easily exceeded and especially
in wintertime, concentration of ammonia is changes between 30-70 ppm in some
broiler houses.
If ammonia concentration in air is high enough, it will directly impact to birds’ health.
As a consequence of high atmospheric ammonia rate, birds’ immunity and intestinal
histomorphology will be under a threat. It can be resulted in dying out of some birds’
kind.

References
[1] Kocsis Z, Dobor J, Korodi Gy, Kuk E, Industrial Safety Analysis of Accidents
involving Ammonia,2015, Page 277-278
[2] EPA, Hazards of Ammonia Releases at Ammonia Refrigeration Facilities
(update), 2001
[3] Risk Assessment of Ammonia Production Unit of a Fertilizer Plant, by Harish
Mahawar,
[4] Guidelines for Hazard Evaluation Procedure, American Institute of Chemical
Engineers, New York, 1985
[5] Crowl and Louvar, 1990, The Hazard Identification and Risk Procedure
[6] The National Institute for Occupational Safety and Health, Centers for Disease
Control
[7] Mark Karimi, MSc, 5 Tips to Successfully Manage Poultry House Ammonia
Levels