College of Engineering

Department of Chemical Engineering

Chemical Process Safety CME464

Fall 2017/2018
Project I

Student Name Student ID Section

1 Salma Al-Nowahi 1045971 52
2 Zaina Al-Dhaheri 1046702 52
3 Sumaita Rahman 1050771 52
4 Saniha Aysha Ajith 1051470 51
5 Laila Owda 1052119 51

Submitted to: Dr. Chandra Mouli M.R.

Submission Date: Sunday, December 3rd 2017

List of tables:
Table 1: Urea ………………………………………………………………………………… 3
Table 2: Carbon dioxide ……………………………………………………………………...4
Table 3: Ammonia …………………………………………………………………………....5
Table 4: Chemicals and potential hazards ……………………………………………………7
Table 5: Control techniques ………………………………………………………………..10
Table 6: HAZOP …………………………………………………………………………….11

List of figures:
Figure 1: Carbon dioxide capturing and urea synthesis PFD ……………………………….. 6
Figure 2: Reactor selected for HAZOP study ……………………………………………….. 6
The capstone project assigned to our group is the production of urea from the reaction of
ammonia and carbon dioxide.

Urea is an important nitrogenous fertilizer and is of great importance to the agricultural

industry. The production process of large amounts of urea is extremely detailed with a large
number of equipment such as absorption columns, reactors, heat exchangers, etc. A urea
production plant can give rise to many risks and hazards such as equipment failure due to
corrosion, explosion hazard, and leakage of toxic ammonia fumes. Corrosion protection is
achieved using stringent material and fabrication specifications in addition to frequent
monitoring and inspection of equipment [1].
It is necessary to take precaution while storing ammonia in storage tanks as it is a highly
voltaic and toxic liquid and emission of these in the atmosphere can be deadly. The process
also includes auxiliary equipment such as pumps and compressors which require regular
inspection and maintenance to assure everything is working efficiently.

Writing from the safety perspective of each chemical, the following tables give an idea about
the potential hazard of each chemical used in this plant.

Urea

Urea’s physical state is white crystals with a special odour. There are many ways in which
people can be exposed to it like inhalation and ingestion. Short term exposure may lead to
eye, skin, and respiratory tract irritation, and long term exposure may lead to a skin condition
called dermatitis. It produces toxic gases in case it decomposes on heating that is above its
melting point, and it reacts violently with strong nitrites and oxidants that are of a specific
strength, and inorganic chlorides and chlorites to cause fires and explosion hazards. Presented
below is a table that explains the characteristics of urea from a safety perspective [2].
Table 1: Urea

Type of Exposure Prevention First Aid

Hazard/Exposure Symptoms
Fire Not combustible. - - Any type of fire
extinguisher is
allowed.
Explosion - - -
Inhalation - Cough. Placement of a local - Getting exposed to
- Sore throat. exhaust. fresh air.
- Shortness of - Resting.
breath.
Skin - Redness. - Protective - Rinse and clean skin
- Skin irritation. gloves. with cold water.
- Protective
overall clothing.
Eyes - Redness. - Protective - Remove contact
 - Eye irritation. glasses. lenses.
- Rinse eyes with cold
water several times.
- Visit eye doctor
immediately.
Ingestion - Headache. - Don’t eat/drink/ - Get plenty of water.
- Vomiting. or even smoke. - Rest.
- Nausea. - Visit the hospital.
- Convulsions.

Carbon dioxide
Carbon dioxide is a gas with a molecular mass of 44 g/mol that is found to be odourless and
colourless compressed liquefied gas in its physical state with a TLV of 5000 ppm. People are
usually exposed to it by inhalation. Short term exposure to carbon dioxide causes suffocation
and unconsciousness since it plays a role in the deficiency of oxygen, while long term
exposure to it affects the human’s metabolism directly. Presented below is a table that
explains the characteristics of carbon dioxide from a safety perspective [3].
Table 2: Carbon dioxide

Type of Exposure Symptoms Prevention First Aid

Hazard/Exposure
Fire Not combustible. - - Use only the
appropriate type of
extinguisher.
Explosion May explode in case - - Keep the carbon
of fire. dioxide cylinder
cool by spraying it
with water.
Inhalation - Unconsciousness. - Placement of a - Getting exposed to
- Headache. good ventilation fresh air.
- Dizziness. system. - Resting.
- High blood - Artificial
pressure. respiration.
- Increased heart - Medical attention.
rate.
Skin - Frostbite. - Cold insulating - Rinse and clean skin
protective with cold water.
gloves. - Do not take clothing
- Protective off.
overall clothing. - Medical attention.
Eyes - Frostbite. - Protective - Remove contact
glasses. lenses.
 - Face shield. - Rinse eyes with
cold water several
times.
- Visit eye doctor
immediately.
Ingestion - - -

Ammonia

Ammonia, the other reactant, has a molecular weight of 17.03 g/mol is a colourless
compressed liquefied gas, but has a strong odour. It is a very strong corrosive base, especially
when it reacts with acids. It has a TLV of 25 ppm, and is usually absorbed through the body
by inhalation. Short-term exposure is corrosive to eyes, skin, and respiratory tract. It can also
cause lung oedema and frostbite. Presented below is a table that explains the characteristics
of urea from a safety perspective [4].
Table 3: Ammonia

Type of Exposure Prevention First Aid

Hazard/Exposure Symptoms
Fire - Flammable. - No open flames. - Use only the
- No sparks. appropriate type of
- No smoking. extinguisher.
Explosion - Gas/air mixtures - Closed system. - Keep the ammonia
are explosive. - Placement of cylinder cool by
ventilation spraying it with
systems. water.
- Explosion-proof
electrical
equipment.
Inhalation - Burning - Placement of a - Getting exposed to
sensation. good ventilation fresh air.
- Coughing. system. - Resting.
- Shortness of - Placement of a - Artificial respiration.
breath. local exhaust. - Medical attention.
- Sore throat. - Breathing
protection.
Skin - Redness. - Cold insulating - Rinse and clean skin
- Skin burns. protective with cold water.
- Pain. gloves. - Do not take clothing
- Blisters. - Protective off.
overall clothing. - Medical attention.
Eyes - Redness. - Protective - Remove contact
- Pain. glasses. lenses.
 - Severe burns. - Face shield. - Rinse eyes with cold
water several times.
- Visit eye doctor
immediately.
Ingestion - - -

The following figure shows the PFD of the production of urea from carbon dioxide and
ammonia.

Figure 1 - Carbon dioxide capturing and urea synthesis PFD

For the purpose of the project, the reactor to which carbon dioxide and ammonia are fed is
considered as shown in the figure below:

Figure 2: Reactor selected for HAZOP study

Industries nowadays place a lot of importance on reducing environmental and personnel
damage resulting from accidents. This particular science devoted to the identification and
control of occupational conditions that cause sickness or injury is called ‘industrial hygiene’
[5]. The four phases of industrial hygiene are as follows [5]:

1. Anticipation: expectation of the presence of workplace hazards and worker exposures.

2. Identification: determination of presence of workplace exposures.
3. Evaluation: determination of magnitude of exposure
4. Control: application of appropriate technology to reduce workplace exposures to
acceptable levels.

Anticipation and Identification

Knowledge of the material being used, processes, operation parameters and conditions are
important to anticipate the potential hazards that may arise. It is also necessary to understand
the safety reviews, equipment vendor descriptions, information from operating personnel and
quality of identification.

One of the key things to note at this stage is the Material Safety Data Sheet (MSDS) of the
chemicals being used. This lists the physical properties of a substance which is required to
determine the potential hazards. They are available from the chemical manufacturer, a
commercial source or from the private library of the production plant. For this process, the
MSDS of urea, ammonia and urea are needed to identify the potential risks.

The production process mainly deals with three chemicals: urea, ammonia and carbon
dioxide. The following table is useful to identify the potential hazards these chemicals can
cause:
Table 4: Chemicals and potential hazards

Chemical Description and potential hazard

Colorless compressed liquefied gas with strong odor. Entry into body by
Ammonia inhalation. Short-term exposure is corrosive to eyes, skin, and respiratory
tract.
Compressed liquefied gas. Entry into body by inhalation. Short term
Carbon dioxide
exposure to carbon dioxide causes suffocation and unconsciousness
White crystals with a special odor. Entry into body by inhalation and
Urea ingestion. Short term exposure may lead to eye, skin, and respiratory tract
irritation, and long term exposure may lead to dermatitis

Evaluation
This phase determines extent of employee exposure to toxicants and physical hazards in the
workplace. During evaluation, the likelihood of small and large leaks of the chemicals from
the storage tanks/ reactors/ columns must be considered. After exposure data is obtained, it is
necessary to compare actual exposure levels to acceptable occupational health standards such
as TLV, PEL or IDLH concentration.
Exposure to volatile toxicants by monitoring

A direct method for worker exposure is by continuously monitoring air concentration of

toxicants in the work environment using the following equation:
The TLVs of this particular process are 5000 ppm for carbon dioxide and 25 ppm for
ammonia and can be used to calculate the worker exposure depending on the length of time
the worker has been exposed to the toxicant.
Exposure to dusts

Dust evaluation calculations are performed similar to volatile vapors. It is necessary to

conduct these evaluations to estimate the concentrations that are inhaled and deposited in the
lungs. Particles larger than 5µm are usually unable to penetrate the lungs; whereas those
smaller than 0.2 µm settle out too slowly are exhaled out with air.
This urea production process does not use solid processing units; hence reducing the
exposure to dust and solid particles.
Exposure to noise

Noise problems are common in chemical plants and should be evaluated and controlled for
the safety of the workers. . Noise level calculations are in dBA. Due to the large number of
industrial equipment such as pumps, reactors and absorption columns, the noise levels
increase causing potential environmental hazard.
Exposure to toxic vapors vaporization rate of liquid
The best procedure to determine exposure to toxic vapours is to measure toxic concentrations
directly.

Liquids with high saturation vapour pressure tend to evaporate faster and can be estimated
using the following equation:

𝑀𝐾𝐴𝑃 𝑠𝑎𝑡
𝑄𝑚 =
𝑅𝑇

In this production process of urea, there is a risk of vaporization of liquid ammonia from its
storage tank which is used as one of the reactants. Ammonia is an extremely volatile liquid
and is assumed to be stored at room temperature. In case such a situation does arise, the
evaporation rate can be calculated as follows:
18 1
 K = (0.83 cm/s) (17)3 = 0.846 cm/s = 1.665 ft/ min
 Paat of ammonia at room temperature = 9.894 atm
Assuming diameter of the storage tank to be 5ft
𝜋𝑑2
Area = A = = 19.6 ft2
4

𝑀𝐾𝐴𝑃 𝑠𝑎𝑡
𝑄𝑚 =
𝑅𝑇
(17)(1.665)(19.6)(9.894)
𝑄𝑚 = = 𝟗. 𝟎𝟏𝟕 𝒍𝒃𝒎/𝒎𝒊𝒏
(0.7302)(833.67)
The concentration can then be estimated using the following equation if vaporization rate is
known:

𝐾𝐴𝑃 𝑠𝑎𝑡
𝑘𝐶𝑝𝑝𝑚 = 𝑥 106
𝑄𝑣 𝑃

Exposure to vessel filling operations

For vessels being filled with a volatile liquid like ammonia in this case, volatile emissions are
generated from the two sources:

 Evaporation of liquid
 Displacement of vapor in vapor space by liquid filling the vessel.

Control
After the potential hazards are identified and evaluated, appropriate control techniques must
be developed and installed. Keeping the chemicals used in mind, the following control
techniques can be applied:
Table 5: Control

Type Typical explanations

Enclosures:  Make sure the ammonia storage
vessel is enclosed safely
 Seal sewers and ventilations
 Shield high temperature surfaces like
the outer wall of reactor
Local ventilation:  Use properly designed hoods while
transporting ammonia.
 Use ventilation at the storage tank of
ammonia
 Use local exhaust at sample points
Good housekeeping:  Provide lines for flushing and
 cleaning
 Provide water and steam connections
for area washing
Personal protection  Use safety glasses and face shields
 Wear appropriate respirators to curb
the effects of the toxic vapors

HAZOP is a common hazard analysis method which is a mostly structured on the orderly
examination of exiting processes and operations that identify and evaluate the problems that
represent risks to the equipments or staff.

The main aim of the HAZOP study is to review the design thoroughly, understand it and have
an idea of all the risks that may occur and provide solutions to overcome them. The main
technique behind HAZOP is to break down the complex design of the process to simpler
sections.
The HAZOP process is happens due to four main steps:

i. Forming a HAZOP team.

The HAZOP team should include a variety of experienced engineers and workers
that have a good understanding of maintenance, instrumentation, operations,
process and safety engineering. The team is very crucial to the process, since one
has to understand the system as a whole and its reasonable variations before
putting in any risk assumptions.

ii. Identifying risk elements and their parameters.

This is done by creating a plan for the whole work process and identifying each
individual step and the elements that make it happen. It involves using P&ID, or a
plant model as a guide for examining every single section and process component.
For each element, planned operating parameters of the system are identified like
the flow rate, temperature, pressure, and vibration.

iii. Considering the variation effects.

In this step, the team will consider the deviation effects like asking what will
happen if the pressure was too high or too low at the valve and so on.

iv. Identifying the hazards and failure points.

Here, the hazards are identified and the points of failure are understood, and the
issues are reported in order to estimate the failure impact.
Results of hazard and operability study of the reactor
Table 6: HAZOP conducted for reactor
Guide Word Deviation Possible Causes Consequences Action Required
NONE No flow - Reactants are not - No feed - Add the
available at comes into reactants.
storage the reactor.
- Add a
- Control valve to - Pressure in pressure
the reactor is reactor will relief valve.
closed. increase

- Ammonia pump - System - Turn on

fails. overheats. standby
pump.

- Blockage/ - System
fracture in the shutdown.
pipe.

- Operator stops
the ammonia
pump or carbon
dioxide
compressor.

No agitation/ - Agitator motor in - Decreased - Chemically

mixing reactor is not conversion control
working of reactants. runaway
reaction
- Increasing
reactor - Add
pressure/ pressure
temperature safety relief
valve
- Runaway
reaction

No cooling of - Cooling jacket - Temperature - Install an

reactor malfunction increases alarm for
inside the high
reactor temperature

- Forms
 undesired
product
MORE OF More flow - Valve to reactor - Reactor - Valve
is left open overfills control.

- Excessive pump - Incomplete - Install a

speed reaction level control
indicator
- Product valve
unacceptable
and goes to
waste

More pressure - Compressor - Reactor will - Trigger

control failure. be operating emergency
at a high system shut
pressure. down.

- Explosion of - Use a fail –

delivery tube open or fail
– close valve

- Install high
pressure
alarm

More - Temperature - Higher - Set high

temperature. control failure. pressure in temperature
delivery line alarm.
- Storage tank of and reactor
ammonia stored
outdoors in heat. - Damage of
(environmental reactor seals
conditions) causing leak

- Control valve - Reactor - Cooling

More cooling failure cools too flow
flow in reactor much temperature
jacket - Operator fails to adjustment
take action on - Forms alarm
alarm undesirable/
intermediate
 product
LESS OFF Less time for - Possible valve - Inconsistent - Usual valve
reaction to opening. concentratio check up.
take place. n

- Less amount
of yield.

Less flow. - Possibility of a - Loss of - Regular

leakage in the reactants/ patrolling
reactor/pipes product. and
checking of
delivery
lines

Less - Temperature - Decreased - Use

temperature control failure. selectivity insulated
pipes and
reactor
- Winter column
(environmental
conditions)
MORE More - Disturbance in - Increased - Keep
THAN ammonia the pump from risk of appropriate
vapour present ammonia storage volatile inert gas
tank liquid spills inside
storage tank
to prevent
evaporation
to vapour.
OTHER Material flow - Wrong delivery - Incorrect - Strict
THAN other than from vendor. reaction protocol in
ammonia or takes place plant to
CO2 in - Wrong material inside check the
delivery line chosen. reactor to chosen
form material.
undesirable
product.
PART OF High - Overworking of - Undesired - Turn on
concentration the pump or product standby
of one of the compressor. produced. pump.
reactants.
- Can lead to - Make sure to
explosion if have annual
 highly pump
exothermic. maintenance
.
REVERSE Reverse - Failure of - Product off - Install check
process fluid process fluid set valve
flow inlet valve
OTHER Maintenance - Equipment - Line cannot - Regular
failure, cooling be maintenance
jacket leak, etc completely checks on all
drained or the
- Over purged. associated
pressurization of equipment.
reactor
References:
[1] Productstewardship.eu, 2017. [Online]. Available:
http://www.productstewardship.eu/fileadmin/user_upload/user_upload_prodstew/documents/
Booklet_nr_5_Production_of_Urea_and_Urea_Ammonium_Nitrate.pdf. [Accessed: 02- Dec-
2017].
[2] "CDC - UREA - International Chemical Safety Cards - NIOSH", Cdc.gov, 2017.
[Online]. Available: https://www.cdc.gov/niosh/ipcsneng/neng0595.html. [Accessed: 16-
Nov- 2017].

[3] "CDC - CARBON DIOXIDE - International Chemical Safety Cards - NIOSH", Cdc.gov,
2017. [Online]. Available: https://www.cdc.gov/niosh/ipcsneng/neng0021.html. [Accessed:
16- Nov- 2017].

[4] "CDC - AMMONIA (ANHYDROUS) - International Chemical Safety Cards - NIOSH",

Cdc.gov, 2017. [Online]. Available: https://www.cdc.gov/niosh/ipcsneng/neng0414.html.
[Accessed: 16- Nov- 2017].

[5] D. Crowl and J. Louvar, Chemical process safety, 3rd ed. Upper Saddle River, NJ:
Prentice Hall, 2014.
[6]"What Is HAZOP", Graphic Products Info, 2017. [Online]. Available:
https://www.graphicproducts.com/articles/what-is-hazop/. [Accessed: 02- Dec- 2017].