HAZARDS OF AMMONIUM NITRATE

The main commercial use of ammonium nitrate started as an ingredient in numerous types of explosives.
its use as a component in fertilizers did not take place until the start of the 20th century. In spite of the
potential hazards associated with AN, (especially fire, decomposition and explosion hazards) ammonium
nitrate can be produced, stored and transported safely and reliably! However, that safety and reliability
depends on a number of factors which are described below:

1. APPROPRIATE ENGINEERING AND DESIGN

Ammonium Nitrate can be easily handled at normal conditions. Good design makes safe operation
and maintenance much easier and is vital for the safety of ammonium nitrate processes. A number of
industry events have root causes related to the following design points:

1.1 Designs Must Consider Ammonium Nitrate Hazards and Special Characteristics.

Engineers involved in changes to the AN plant should familiarize themselves with AN hazards.
When making changes to the process, the input of ammonium nitrate technical resources is
essential. For major changes, an experienced process licensor review is required. For other
changes to the process, input from outside the site, where appropriate, is recommended to provide
a third party view of the plant. Design considerations would include:

1.1.1 Non-trapping and easy clearing systems, including free draining or low point drains.
1.1.2 Avoiding dead lines.
1.1.3 Providing good pump protection.
1.1.4 Robust process and relief venting of Neutralizer and other AN equipment, where relevant.
1.1.5 Avoiding salt-up conditions.
1.1.6 Nitric acid flanges tend to leak: avoid putting nitric acid flanges above or near walk ways
and susceptible equipment.

1.2. Designs Must Look Beyond Normal Operation:

Though our plants may spend 90+% of their time operating normally, many industry events have
occurred in startup, shutdown, and off-line situations. Designing for normal operation may be
easy: design and instrumentation for robust operation and good
monitoring during startup, shutdown, and offline times is more
challenging. Considerations would include:

1.2.1 Meeting minimum feed-rates to establish or maintain good

circulation in the Neutralizer,
depending on the type of design.
1.2.2 Determining how to monitor properly a large Neutralizer
during off-line situations.
1.2.3 Providing flexibility to obtain full strength product: the
operators should have enough process flexibility so that
dilution is not discouraged by an inability to work off the
resulting dilute products.

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 1.2.4 Providing good drains/sumps to direct AN materials to a safe system.
1.2.5 Good circulation for shutdown or offline, and/or effective dilute and draining, depending
on the type of design.
1.2.6 Providing easily accessible and uncontaminated sources of dilution water.
1.2.7 Providing barriers to improper operation, such as alarms on high steam temperature or
pressure, lack of or incompatible fittings for potable water sources (which contain
chloride).
1.2.8 Considering proper procedures, monitoring, and control on a power or steam outage.

1.3 Designs Must Insure Materials Compatibility and Avoid Contamination.

Stainless materials are normal for wetted parts. New types of materials should be confirmed as a
prudent choice by testing. Copper, aluminum, zinc (galvanizing), titanium use is not normal for
wetted parts. Corrosive conditions should be avoided as they add sensitizers to the process, and
must be considered on startup, shutdown, and offline situations as well as normal operation.
Provide separate areas for combustibles storage and forklift truck refilling/maintenance.

1.4 Designs Must Protect Beyond a Single Instrument Failure.

Redundant pH probes and temperature monitors are used at our sites in critical areas. The
operator should be warned of problems by dual readouts and/or alarms.

2. APPLYING THE PRINCIPLE AND TOOLS OF PROCESS SAFETY MANAGEMENT.

2.1 Any and all changes to the Operating Parameters, Standard

Operating Procedures, design, piping additives, etc. must
be addressed by the MOC (Management of Change)
Process. A thorough and formal PHA (Process Hazard
Analysis) must take place. The PHA must involve
management, supervision, engineering, operations and
maintenance personnel. Any concerns raised during the
PHA process must be addressed and appropriately
resolved. This also applies to any and all upstream
Processing units where changes in operating conditions,
additives, etc. may result in contamination of any of the
feedstock supplies to the AN Plant. Particular attention
should be given to the Nitric Acid and Ammonia Plants.

2.2 Written Standard Operating Procedures must be kept up-to-date. They are to be reviewed
periodically and authorized by signature by the Supervisor responsible for the area and also the
Plant Production Manager.

2.3 The Standard Operating Procedures must include what actions to take when critical process
operating parameters deviate beyond acceptable limits. (“Deviations from Normal”).

2.4 Process and instrumentation drawings must be kept up-to-date.

2.5 Safe operating parameters for all activities in the UAN Solution’s Plant must include but not be
limited to pH, temperature, AN concentration and acceptable contaminant levels.

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 2.6 Preparation for Start-up, Start-up, Normal Operations, Deviations from Normal, Emergency
Shutdown, Shutdown and Preparation for Maintenance procedures must take into consideration
all critical operating parameters. These procedures must be reviewed regularly as part of the
Process Management Safety System and authorized by signature by the Supervisor responsible
for the area and also the Plant Production Manager.

2.7 If new equipment is installed, design or piping changes made or changes made to operating
procedures, operating parameters or limits then a pre-commissioning review must take place
before start-up to address the implications of the changes that have been made. If the change
involves new or modified facilities (equipment) a pre-start-up safety review (PSSR) must be
completed and documented in accordance with the PSM standard.

2.8 Operations and maintenance personnel should be re-trained on a regular basis. This will involve
the review of existing procedures and document as well as exposure to new information that
may become available.

3. EFFECTIVE COMMUNICATIONS.

3.1 Effective and formal lines of communication must be developed between operations,
supervision, management, engineers, operations and maintenance personnel. Management
must monitor the effectiveness of the communications and also ensure that all appropriate
actions are being taken to ensure the safe maintenance and operation of the Plant.

3.2 Terra Safety Management/Supervision must provide local Safety and Emergency organizations
with information on the hazards of the chemicals handled, what preventative measures in-place
to prevent accidental releases and the emergency response measures to be taken in the event of
a major failure in the production facility.

4. SAFE PRODUCTION AND STORAGE

4.1 Qualitative and quantitative analysis of any and all additives must be performed to ensure that
no contamination/sensitization of the Ammonium Nitrate can take place. Suppliers of
additives are to be advised to communicate to Terra Courtright any changes in the additives
that they supply to Terra. This includes any additives for Boiler Feed Water and De-
Mineralized Water.

4.2 The product from the Nitric Acid Absorption Tower should be tested weekly for chlorides, and
more frequently if there is a known or suspected source of contamination.

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 4.3 The feedstock streams to an ammonium nitrate plant must be monitored and sampled regularly
for contamination (especially from oil or chlorine).

4.4 Special attention must be given to recycle streams and/or any recovered solutions streams in
an ammonium nitrate or UAN Solutions Plant or upstream plants to prevent contamination of
the A.N. Solution.

4.5 All trips and interlocks must be tested regularly. Trip and interlock settings must be reviewed
regularly as part of the Process Management Safety System.

4.6 All oil traps and drains should be checked a least once per shift to ensure that there is no oil or
other organics and to clear the traps and drains of any contaminants.

4.7 Any significant loss of oil in upstream units that is not accounted for otherwise must be
investigated immediately and samples taken of the relevant feed stock to the AN or UAN
Solution’s Plant

5. PROPER PREPARATION OF EQUIPMENT FOR MAINTENANCE.

5.1 After any vessels, piping or pumps are shutdown and the isolation of the system is completed,
hot condensate or 75-psig de-superheated steam should be the only mediums used to flush
out piping and related equipment for maintenance preparation. All the effluent should be
directed into a high-risk drain or contained for safe disposal.

5.2 Potable water or raw water that may contain chloride or other contaminants should not be used
for flushing equipment unless in special circumstances and only with proper authorization.

5.3 Special attention must be given to flushing lines or

equipment that may contain deadheads, drains, nozzles,
lutes, goosenecks, chambers in valves or seals, etc. where
A.N. may be confined. This is especially important where
hot work or cutting may be performed. If there is any
doubt as to whether or not a line or piece of equipment is
properly flushed, especially for hot work, it may be
necessary to start a small hot condensate flow through the
piping or vessel and sample the inlet and outlet flows for
AN content. It must be noted that this does not guarantee the absence of any A.N. as there
may be some in “pockets” where the flush cannot reach.
Before issuing a Work Permit, maintenance should be made aware of the possibility of the
presence of AN, especially where hot work is involved. If the presence of AN cannot be ruled
out, cold-cutting may be required.

5.4 If maintenance activities to be performed include the disassembly of steam tracing lines,
steam jacketing and/or flush lines to pumps seals etc. ensure that the lines do not contain A.N.
and that they are not under pressure.

5.5 If the internal support structure inside any vessel (or elsewhere) is constructed of piping,
ensure that the piping does not contain confined A.N before any hot work or cutting is
allowed. If such a hazard exists and cannot be corrected it should be noted on the Safe or Hot
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 Work permitted and visually pointed out to the Maintenance personnel performing the work.
Where necessary, provisions should be made for facilitating the flushing of such lines in the
future. (i.e. Install flush and drain holes in the piping)..

5.6. Do not apply external heat by any means to a line that may contain frozen and or confined
A.N. Steam to tracing or steam-jackets on a line containing frozen or confined A.N. should
be shutoff and the line should be cleared using condensate inside the line while ensuring
that the line is not over-pressured or overheated. (i.e. it should not exceed the decomposition
temperature of the A.N).

CAUTION:

It must be noted that under very unusual circumstances, the steam on a jacketed line containing
confined A.N. may actually be absorbing heat and preventing a runaway decomposition
reaction of the A.N. Caution must therefore be exercised when shutting steam off of a jacket
that is know to contain confined A.N and the temperature and pressure of the process side line
must be monitored very closely.

5.7 Prior to any maintenance taking place all repair or replacement materials should be inspected
to ensure that the materials used are approved ones, having been assessed for compatibility
with A.N.. The material of preference is stainless steel. At no time should copper, titanium or
other readily oxidizable/reactive/catalytic metals ever be used (Unless authorized by Senior
Management).

5.8 When vessels entries are performed or other equipment is opened, operations should inspect
the internals of the equipment just before it is closed up to confirm the removal of all
materials, tools etc.

5.9

Check area for removal of any and all organics or combustibles

when maintenance is finished and before the Safe Work Permit,
Hot Work Permit or Vessel Entry permit is accepted as
complete.

5.10 Ensure that systems can be taken off-line safely, and cleared effectively for maintenance work.

5.11 Communicate with maintenance crews: make sure they are aware that AN may be present and
that safe work practices are planned.

5.12 Make sure that maintenance crews clean and return equipment appropriately for AN operation,
including operations participation in clean-up inspection.

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6. GOOD MAINTENANCE PRACTICES

6.1 Maintenance personnel should be aware of all possible relevant hazards of AN, with special
attention being given to confinement, contamination and high temperatures/overheating.

6.2 If scaffolding must be erected prior to a shutdown or major turnaround wood scaffolding
planks and kick-plates must not be installed on the scaffolding until the plant is shutdown and
all AN and/or UAN solutions have been flushed/removed from the process equipment.

6.3 Prior to any maintenance taking place all repair or replacement materials should be inspected
to ensure that the materials used are compatible with AN. The material of preference is
stainless steel. At no time should copper,
titanium or other oxidizable metals ever be
used.
-Gasket material must be considered as well.
-Pump seals should be carbon-free.
-Organic material should not be used as gland
packing material.

6.4 Organics and combustible material should not

be stored in the A.N. Production or Storage
Areas. Any such materials that are used
during maintenance activities must be removed
when maintenance is complete.

6.5 Ensure that all materials, solvents, gloves, personal protective equipment, wood planks,
ladders, tools etc. are removed from any equipment that has been opened before equipment is
closed up. This includes metal dust, corrosion products, and metal filings. This includes
upstream plants. Advise operations that you will be closing up the equipment.

6.5 Minimize the storage of pallets, bags, etc. in the A.N. Production or Storage Areas during
shutdowns.

6.6 Any fuel or oil spills from maintenance vehicles, forklifts, etc must be cleaned up
immediately.

6.7 When performing hot work or cutting it should be noted that A.N. can be built up and
confined:
- Under bolts and rivets.
- Between walls of double walled or jacketed vessels or hoppers.
- - In steam jacketing or steam tracing.
- Between gaskets and flange faces.
- Between flange faces.
- In pump seals.
- In deadheads, drains, nozzles, lutes, goosenecks, chambers in valves, etc..
- Hollow equipment shafts.
- On any maintenance vehicles that may have come into contact with A/N. It is even more
hazardous if the A.N. is contaminated with fuel or oils
- Any area to where A.N. may have leaked.

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 Special care must be taken to ensure that all AN has been removed.

6.8 Always take precautions against the sudden and unexpected release of hot A.N. solution from
flanges, lines, pumps, drains and vents, especially during disassembly.

6.9 If the internal support structure inside any vessel (or elsewhere) is constructed of piping,
ensure that the piping does not contain confined A.N before any hot work or cutting is
allowed. If such a hazard exists and cannot be corrected it should be noted on the Safe or Hot
Work permitted and visually pointed out to the Maintenance personnel performing the work.
If a Hot Work Permit cannot be issued, only “cold-cutting” should be allowed.
When necessary, provisions should be made for facilitating the flushing of such lines in the
future. (i.e. Install flush and drain holes in the piping).

6.10 Written procedures should be in place for all maintenance work inside the Primary Neutralizer
or Neutralizer Overhead Scrubber with special attention being given to hot work, cutting, the
hazards of confined or contaminated A.N. and incompatible material whose use should be
allowed.

6.11 Maintenance is to take a “pro-active” approach to ensure the mechanical integrity of AN and
UAN Solutions Plants. A formal preventative maintenance program (including predictive
failure analyses) should be implemented.

Exercise care at all times and review safety considerations and maintenance procedures at
the commencement of any job. Never assume that maintenance personnel or operations
understand the dangers. Supervisors must make sure that they do. Maintenance personnel
must take it upon themselves as well to understand the safety hazards involved. Continuous
vigilance and periodic training will continue to be required to ensure safe maintenance
activities.

7. SAFE SHIPPING AND HANDLING

7.1 Cross-contamination with previous loads must be avoided when transporting AN and UAN
Solutions. Appropriate procedures must be in place to eliminate the possibility of cross-
contamination.

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7.2 Whenever possible, customer returns on AN and UAN solutions should not be accepted.
However, there should be a procedure in place for the re-working of off- spec /returned
product and that procedure must be followed. The procedure must take into consideration the
possible presence of any organics, contaminants or additives.

7.3 Caution must be taken when mixing bulk dry AN with other fertilizer compounds to avoid
possible contamination, acidity, fire or decomposition.
(See Section on Containment-Blended and Compound Fertilizers).

7.4 All personnel involved with the loading, transportation and unloading of AN and UAN
solutions and bulk dry AN must be aware of the hazards of the products with which they
are dealing and must be properly trained as to what action to take in the event of a fire
or spill.

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 Physical Properties of Ammonium Nitrate

Ammonium nitrate (AN) is the ammonium salt of nitric acid. Its chemical formula is NH4NO3. The
pure material is a white, crystalline salt at room temperature that melts to a clear, colorless liquid at
170 O C. During manufacturing, it is necessary to maintain temperatures above the melting point to
keep the ammonium nitrate liquefied in vessels, pipes and tanks. It is very soluble in water and its
melting point decreases as its water content increases such that, for example, 1% water lowers the
melting point from 170 O C to 158 O C. A slight ammonia odour may be present.

Ammonium nitrate solutions are a mixture of ammonium nitrate and water. The pH will vary
between 1.0 and 6. 0 depending on the amount of free ammonia or free nitric acid present. If the
water is allowed to evaporate out of the solution, high concentrations of AN can result. The AN will
start to decompose at temperatures above 338 O F /170 O C. When decomposing it emits oxides of
nitrogen and water vapours and may explode if confined. If the product has been contaminated with
another substance the decomposition temperature and effects of decomposition may be varied. The
ammonium nitrate is incompatible with organic substances, titanium, zinc, and copper and many
other substances. See the MSDS sheet for a complete list.

UAN Solutions: are a mixture of ammonium nitrate, urea and water.

Physical and Chemical Properties of AN and UAN Solutions

AN UAN 28 % UAN 30% UAN 32%
% AN 75-99% 37-41% 40-44% 42-47%
% Urea N/A 29-32% 31-44% 34-37%
% Water 1-25 % 34-27% 29-22% 24-16%
Free Ammonia < 0.5% < 0.5% < 0.5% < 0.5%
Free Nitric Acid < 0.5% N/A N/A N/A
pH 1.0 to 6.0 6.8 to 7.5 6.8 to 7.5 6.8 to 7.5
O O O O O O
Boiling Point 266 F / 130 C 225 F/107 C 225 F/107 C 225 O F/107 O C
Melting Point
168 O F / 75.5 O C -1 O F/-18.3 O C +16 O F/ - 8.9 O C +32 O F/ 0 O C
(Crystallization)
Molecular Weight 80.05 ----------- ------------ -------------
Specific Gravity 1.37 1.281 1.304 1.330
Density in lbs per gal
11.43 10.67 10.86 11.08
@ 60 O F / 15.6 O C
Decomposition 338 O F /170 O C

Vapour Density ------------- App. 1.07 @ 60 OF/ 15.6 OC

Vapour Pressure --------------- 8.6 to 17.5 mm Hg @ 100 OF/37.8 OC

N.B. See relevant MSDS for more detailed information.

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 Health Hazards from Physical Contact with AN

- As AN and UAN solutions are hot when produced and shipped, a thermal burn hazard is always
present. Contact with the skin may cause de-fatting, drying and cracking of the skin if the AN or
UAN solution is not promptly removed.
- Ammonia and NOx vapours from decomposing AN from the solutions are irritating to the eyes,
nose, throat and respiratory tract.
- Contact with eyes may cause irritation, corneal burns, conjunctivitis and possible corneal
damage.
- Ingestion of the solutions AN can cause internal burns, irritation, and a burning sensation of the
mouth, throat and gastrointestinal tract.
- The AN is a respiratory irritant and a methemoglobin inducer.
Methemoglobin occurs when the iron, which is part of the hemoglobin in the blood, is altered in
such a way that it does not carry oxygen well. Nitrates and nitrites can cause this condition. As
AN is in Class A + as a reproductive hazard, pregnant women should not have chronic long-term
exposure to AN. Ammonia, ammonia vapours and nitric acid may all be present during the
production, storage or handling of AN or UAN solutions. NOX fumes may be present if
decomposition is taking place.
Proper personal protective equipment must always be worn. This may include such items as
gloves, rubber gloves, monogoggles, face shield, rubber apron, rubber boots, protective clothing
made of rubber, neoprene or viton, cartridge respirators or positive pressure self contained
breathing apparatus (as circumstances dictate).

Exposure Limits for Components

Component TWA STEL PEL IDLH
Ammonia 25 ppm 35 ppm 50 ppm 300 ppm
Nitric Acid 2 ppm 4 ppm 2 ppm 25 ppm

N.B. See relevant MSDS for more detailed information.

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 Fire Hazards of AN
Ammonium nitrate by itself is not combustible; it is an oxidizer and hence it can accelerate the
burning of fuels or organic materials. Hot AN solution may also ignite combustibles such as wood,
paper, oil, clothing etc. As it is an oxidizer, fires involving AN cannot be extinguished by
conventional firefighting methods that “smother” a fire by excluding oxygen (air).

NH4NO3 → N2 + 2H2O (as vapour) + 1/2 O2 (generates heat at 316 BTU/LB).

Dry chemicals, CO2, halogen or foam should not be used. Large quantities of water should be used
when fighting fires involving AN.

Decomposition Hazards of AN
At elevated temperatures ammonium nitrate decomposes according to various reactions. The most
common reactions are:

Above 170 O C, ammonium nitrate dissociates in the following reversible endothermic reaction:

# 1. NH4NO3 ↔ NH3+ HNO3 (absorbs heat at 834 BTU/LB)

Between 170 O C and 299 O C ammonium nitrate decomposes in the following irreversible
exothermic reaction:

# 2. NH4NO3 → N2O + 2H2O (generates heat at 316 BTU/LB)

If the vapours produced by the decomposition reaction (reaction # 2) are free to leave the surface,
( i.e. are not confined) and they are saturated with the vapours from the reversible dissociation
reaction (reaction # 1) products, then the exothermic heat of reaction and the endothermic heat of
dissociation will partially or fully balance each other and the temperature may remain essentially
constant. If not confined, it is even possible to heat pure ammonium nitrate to complete
decomposition and evaporation without an explosion - if the pressure is maintained at normal
atmospheric.
Although the above reactions may cancel each other to maintain a consistent temperature the
decomposition products or vapours released contain oxides of Nitrogen referred to as NOx gases and
are considered to be pollutants and harmful to human life and the environment.

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 Detonation Hazards of AN
Under certain conditions ammonium nitrate can detonate with a reaction front proceeding through
the explosive material at a speed greater than the speed of sound in the following exothermic
reaction:

# 3. NH4NO3 → N2 + 2H2O (as vapour) + 1/2 O2 (generates heat at 316 BTU/LB).

As reaction # 3 demonstrates, AN can explode during decomposition because it produces rapidly

expanding gases. However, the likelihood of an explosion is dependent on several other factors as
explained in the following section “Detailed Discussion Of Factors That Effect AN Safety “.

TEXAS CITY, APRIL 1947

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 DETAILED DISCUSSION OF FACTORS THAT EFFECT AN SAFETY
The following factors are important in considering the potential hazards of Ammonium Nitrate and
AN-containing solutions:

1. Contamination.
2. Confinement.
3. High Temperature.
4. Fire
5. High Acidity.
6. Concentration.
7. Sensitivity and Self-Detonation
8. Pumps Detonation Hazards for AN and UAN Solutions
9. Combinations of Hazards.
10. Plant Start-Up, Shutdown, Upset And Off-Line Situations

These factors are discussed in detail in the following sections, with emphasis on the “Engineering and
Design” and “Operational and Maintenance” considerations that are significant for each to Terra’s
manufacturing operations.

1. CONTAMINATION
The main hazards of ammonium nitrate (AN), namely fire, decomposition and explosion, are all
adversely affected by the presence of various contaminants. A large number of materials have a
strong, catalytic effect on the thermal decomposition of AN; these include acids, chlorides, organic
materials, chromates, dichromates, manganese salts, copper, nickel, zinc, lead and aluminium.
This list is by no means exhaustive and extreme care should be taken when selecting materials for
AN use. All these contaminants also increase the potential for explosion. It is also worth noting
that sources of contamination can be varied and are not always obvious – for example in raw
materials and as products of corrosion.

Three kinds of contamination can contribute to the initiation of an AN runaway reaction which
proceeds to detonation.

Contaminants That Act As A Fuel:

AN is used to make explosives because it is an excellent oxidizer. By adding fuel and an initiating
agent such as dynamite, AN will oxidize the fuel so rapidly that the material explodes in rapidly
expanding gases. A number of materials act as a fuel for ammonium nitrate, including paper, cloth,
oil, grease, wood and asphalt. Urea will also fuel AN in the absence of water.
Flammable (oxidizable) metals such as aluminum and titanium are also fuels.
All these contaminants can be commonly found within the AN production area. Great care must be
taken to maintain good housekeeping practices around an AN unit and at no time should AN and
organic fuels and solvents as well as general everyday debris come into contact with each other.
In addition care should be taken when maintenance is performed to ensure that the materials used
do not contain the above oxidizable metals.

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Contaminants That Act As A Catalyst:

Certain contaminants can act as catalysts that reduce the time and temperature required for
decomposition to gases. This is similar to the role nickel catalyst plays in a natural gas reformer
where natural gas is "decomposed" to carbon oxides and hydrogen. The nickel helps the reaction
take place at lower temperatures and more rapid rates than it would by itself. Some common
metals can act as a catalyst for AN decomposition, including copper, zinc, and metal corrosion
products: these items are more effective as filings, dust, or corrosion products because of their
increased surface area. Other substances which catalyze the AN decomposition include chloride,
free acid (i.e. low pH), salts of cobalt and nickel, chromates etc.

Contaminants That Increase Shock Sensitivity:

Some contaminants in AN actually produce compounds that are even more shock sensitive than
the AN. These include titanium that can form titanium nitrate, copper that can form
cupric nitrate and urea that can make urea nitrate (in the presence of nitric acid).

Design and Engineering Considerations

Design and engineering issues range from the obvious like materials of construction to operability
issues and the positioning of equipment. It is important that the Hazard and Operability process is
rigorously applied and that team members are experienced in ammonium nitrate production and
handling. As in operating and maintenance considerations, it is impossible to produce a
comprehensive guide but the following points represent good if not best practice.

- Ensure all “wetted” equipment is in stainless steel or other material at least as good.
- Avoid items commonly used in construction or manufacturing that can destabilize AN, such as
soluble chromium, copper, or zinc (contained in galvanized surfaces).
- As far as practical make recycle systems closed
- Provide a clean water supply for flushing and quenching
- Pay particular attention to pump seal flushes
- Ensure adequate oil removal from the ammonia supply
- Provide dedicated delivery systems with unique couplings so that alternative vehicles cannot
be used
- Look closely at vehicle logistics and movement to remove the need for vehicles on plant and
in stores
- Do not place oil containing equipment (e.g. gearboxes) above AN on conveyors or in store
- Consider how spillage is to be handled.
- Provide smoke detectors in dry AN storage areas alarming to a monitored location. Treat as a
safety system.
- Store flammable materials completely separately from AN areas.
- Provide an area for trucks to be cleaned prior to loading
- Ensure that pump seals are free from reactive materials. Although some sites still have carbon
in their pump seals, this should be reviewed for alternatives. (N.B. Graphite is often used and
is resistant to AN attack. It is carbon!)
- Ensure that there are no facilities for adding material to the AN system other than the designed
ones – e.g. shovelling spillage from the floor onto a conveyor
- Make up water to scrubbers must be from a safe source.
- Potable water connections should not be available on the plant as it contains chlorides

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- Combustible material such as wood and plastic should be avoided in the construction of plants
and transport vehicles.
- Good housekeeping standards should be maintained to prevent combustible materials from
- coming into contact with hot AN Solutions.
- The Make-up De-Mineralized Water (or Condensate) System to the Absorption Tower in the
Nitric Acid Plant should be equipped with an on-line conductivity meter to detect possible
contaminants.
- Sumps, and drains should go to a safe location and not be recycled.
- The quench water system source should be clean and without contaminants, and/or be directed
and handled in a safe manner without recycling to a higher strength.

Operational and Maintenance Considerations

Operationally speaking contamination can occur from a number of sources, for example in raw
materials, leaks, poor housekeeping, lack of control of recycle streams, incorrect materials leading
to corrosion, contaminated flushing water and rubbish left behind after maintenance. The
following points are by no means exhaustive but represent examples of good practice:

Ensure ammonia catch-pots are blown down once per shift to remove oil from the system.

- All traps and drains should be checked a least once per shift to ensure that there is no oil or
other organics and to clear the traps and drains of any contaminants.
- Use laboratory analysis to look for trends of contamination in raw materials and finished
product.
- When pump seals are provided with flushing lines, ensure that the flushing medium is not
allowed to become contaminated.
- When using additives such as magnesium nitrate, use a dedicated supplier and delivery system
so that personnel are fully trained and the equipment is not used for any other purpose.
- Have acceptance criteria clearly posted and understood. Make clear what action is to be taken
to take if criteria are not met.
- Ensure that recycle streams are closed so that recycled material cannot be contaminated
- Do not re-work spillage unless it can be clearly confirmed to be contaminant free.
- Make sure that flushing water is uncontaminated and is readily available so that alternatives
are not used “because it’s easier”.
- Keep motor vehicles and trucks away from plant areas and
stored material.
- Provide storage of pallets, bags, and other combustible
materials in an area separate from AN storage.
- Minimise presence of combustible materials in AN storage
areas.
- - For plant vehicles that are necessary for continued
operation (fork lift trucks, pay-loaders etc.), ensure that
there is a rigorous and auditable maintenance system and
that there is a procedure in place for dealing with fuel
and oil leaks.
- Ensure that the Management of Change process considers material compatibility with
ammonium nitrate.
- Identify an individual with suitable experience inside or outside the organisation as an “AN
expert” who can be used as a source of advice.
- Identify an individual in the plant management structure with responsibility for inspection of
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 AN systems following maintenance work to ensure they are clean and fit to go back into
service.
- Have in place a cleaning and flushing procedure for equipment that has been worked on.
- Ensure that start up and shutdown procedures exist and deal with the possibility of
contamination during these critical stages. Shutdown procedures should include the need to
flush the nitric acid sparger and then ammoniate the AN to reduce its sensitivity.
- Ensure that all operations and maintenance personnel are trained in the specific hazards of
ammonium nitrate.
- Create a procedure for dealing with ammonium nitrate that is left in equipment that has been
taken off line.
- Remember that where there is a recycle stream there is the possibility for an insignificant
amount of contamination to build up to an unacceptable level due to the “concentration effect”.
- Apply the management of change procedure to personnel changes so that expertise is not lost
- When maintenance is performed, or new equipment is installed in the Nitrates area, an
inspection of the materials used must be made to ensure that copper or titanium is not present.
- Following major overhauls in the plant it must be ensured that maintenance have not left
foreign materials such as wood planks, gloves, tools ladders etc. inside the vessel or piping.
This includes upstream plants.
- Incompatible organic material should never be used as gland packing material.
- Avoid cross-contamination from previous loads when transporting AN Solutions.
- The Nitric Acid Absorption Tower should be tested weekly for chlorides, and more
frequently if there is a known or suspected source of contamination.
- Ensure that adequate procedures exist for the reworking of off-spec product are developed and
followed.
- Clear equipment carefully before maintenance, and make sure that maintenance personnel are
aware that AN may be present so proper procedures can be used, such as cold cutting.
- Be careful with materials selection for nitric acid at elevated temperatures (>140 deg F) to
avoid corrosion and corrosion products.
- Flush out nitric acid sparger on shutdowns to avoid accelerated corrosion from heating the
nitric acid and sparger metal, and to reduce still ammonium nitrate in contact with nitric acid.

Blended and Compound Fertilizers

Ammonium nitrate is often blended or compounded with other materials to make products with a
range of plant nutrients. Common blend or compounding materials are potassium chloride,
phosphates, sodium nitrate and ammonium sulphate. Care should be exercised as the chloride is an
obvious contaminant which can promote decomposition and the ammonium nitrate should not be
allowed to become acidic. It should also be noted that with certain proportions of phosphate and
potassium chloride, the resultant material can become capable of self sustaining decomposition
(“cigar burning”) and need special care in drying and other hot working operations, storage and
transport.

2. CONFINEMENT
Pressure resulting from confinement will not initiate ammonium nitrate decomposition- But once
decomposition is underway, confinement pressure can greatly accelerate the reaction because it
acts to rapidly increase temperature. Under extreme conditions of pressure and temperature it can
permit the material to proceed to detonation in smaller quantities and confinement pressure is
usually the decisive factor in self-detonating AN. This is because without confinement, the force

Page 16 of 29
of rapidly expanding gases from hot, self-decomposing AN, will usually be dissipated through
venting without explosion.

Design and Engineering Considerations

Designing out the possibility of confinement of AN is not possible in the manufacturing process. It
is possible, however, to reduce the possibility of confinement through proper engineering. Even in
atmospheric pressure processes, neutralizers contain pressurized spargers and the resulting liquor
often must be pumped and the excess water taken off in evaporators. Plant designs using pipe
reactors instead of neutralizers significantly reduce the on-plant inventory of AN.

The first, most obvious, precaution at the design

stage is to ensure adequate relieving capacity is
built in. Relief devices have to be able to relieve
very large volumes of gas and vapour from
relatively low-pressure systems so it is common
to find systems that rely on water legs, such as
“goose-necks” or “lutes” and large bursting discs.
It must be remembered, though, that water legs
systems are only effective if the correct level of
liquid is present in it and the liquid is not frozen.
Water leg systems could also be subject to salt out
if dilute water flow is restricted. Low level and
temperature alarms can be fitted, or an overflow
and a constant supply of hot condensate will work, so long as condensate is available. Rupture
disks or relief valves must be kept clear of AN buildup.

Where possible, valves for AN Solutions should not have chambers that can trap AN. Drain
valves should be of a design that reduces the possibility of pluggage while the AN System is on
line (i.e. the valve seat should be as close to the process flow as possible, such as is available in
Strohman valves).

Steam tracing and jacketing on AN lines and vessels will heat up the (confined) contents. It is
imperative to use low pressure (and hence low temperature) steam for these systems in order to
minimize the temperature which the AN could reach. Such steam supplies are normally provided
by letting down steam from a higher pressure usually through a desuperheater. The desuperheater
should be fitted with a high temperature alarm and may include a trip on the downstream side that
would cut off the high-pressure steam supply. Hose connections into the high-pressure steam
system should not be provided.

Proper design of the jacketing system on AN lines and reliable preventative maintenance on the
steam traps and insulation can prevent crystallization of the AN in the lines.

AN pumps must be protected against “dead-heading”. This can be achieved in a number of ways,
perhaps the most common being to provide a recycle stream to ensure a minimum flow through
the pump. Recycle valves should have a mechanical minimum stop fitted and restriction orifice
plates should be traced or jacketed to ensure they do not freeze. It is also possible in multiple
pump installations to install mechanical interlocks (e.g. Castell keys) on the delivery valves so that
the valve on the running pump must always be open. In any event, pumps handling AN should
always be fitted with high temperature trips.
Page 17 of 29
 Other precautions, such as low Amp trips or flow alarms can also be added. Pump seals should be
designed so as to prevent the build-up of AN in chambers in the pump seal or the seal should be
provided with a flush (steam, for example) that will prevent freeze-ups but will not expose the AN
solution to a contaminant. AN pump design will be the subject of another design guide.

Pipe-work systems must be designed so that they can be easily drained and flushed, avoiding low
points and dead ends. Self-draining systems are preferred. Adequate hot condensate supplies
should be made convenient to these flushing points. Neutralizer spargers are another potential
confinement point unless they have drain holes drilled to allow proper flushing and draining as the
plant is emptied.

Storage tanks for AN liquor must be properly vented and hot concentrated solutions must be kept
alkaline, where necessary by provision for the addition of ammonia. A sample point or continuous
pH monitoring is also advisable. Heating systems for storage tanks must be designed to limit the
potential heat input.
Storage tanks should not be lined to prevent the confinement of AN between the line and the Tank
outer wall.

Mechanical handling equipment for dry product can also provide opportunities for confining AN.
AN dust can and will accumulate underneath bolts and rivets and between double skins on
hoppers. Hollow shafted screw conveyors are not advised and all equipment should be designed to
be easily and visibly cleaned. Hollow sections and double skins should be avoided: shafts should
be solid.

Operational and Maintenance Considerations

Operating and maintenance procedures and practices should ensure that AN which is confined is
not overheated, contaminated or acidic. It is important to remember that overheating can occur by
the application of work – e.g. deadheading a pump and continuing to allow it to run will rapidly
increase the temperature of the pump contents. There have been many examples of just such
incidents over the years leading to explosions. The manufacturing process inevitably means that
AN is contained in pipes, pumps and vessels and the potential for confinement and overheating is
always there, but is often engineered out at the design stage (see below). Therefore, strict
adherence to the modification procedure, hazard and operability studies, auditing and on-going
improvements are essential to ensure that inherently safe designs continue to be so.

Page 18 of 29
Operationally, good practices as described elsewhere in this document to ensure no contamination
and no acidic conditions are an essential part of controlling the risks associated with confinement.
Care must also be taken to ensure that running pumps are never deadheaded. This can include
physical interlocks to ensure that at least one delivery valve is always open. Particular attention
should be paid to clearing blockages in lines. Line plugs should always be washed out, never
melted by live steam or the application of heat. Even though the steam temperature might be
considered safe, the situation changes in the presence of contamination or low pH. Particular risk
areas are neutralizer spargers, drain lines, pipe-work low points and AN melt filters. Where AN
liquor is stored in heated tanks, procedures should be in place to monitor and control the Ph of the
liquor so that it remains alkaline. This is usually achieved by ammoniation.

- Goosenecks or lutes should be checked to ensure that they are not plugged and are free
flowing. This should be done pre-start-up, during normal operations, and during shutdowns.
Particular attention must be given to goosenecks/lutes in freezing weather!
- The high temperature monitors and trips on AN Solutions pumps should be checked regularly.
Spring contact thermocouples may fatigue—they should be checked for good contact regularly
or replaced. See Terra standard for high temperature pump trips.
- All equipment should be thoroughly flushed and drained when equipment is shutdown to
ensure that there are no traces of AN left anywhere in the system.
- Even with effective clearing for maintenance, maintenance personnel should be alerted that
AN -may be present, and plan their work accordingly (cold cutting, etc.).
- Steam supply to line jackets and the traps exiting these jackets should be monitored to ensure
that AN is not allowed to crystallize in the line.
- Steam jackets on lines should be monitored and or tested for leaks regularly to prevent AN
from entering the jacketed portion of the line, becoming confined and then being overheated
and decomposing.
- The Neutralizer should be equipped with a pressure sensing device and high-pressure alarm.
- If AN is trapped in a jacketed line, the steam should be shut off to the line jacket. The
pluggage should be cleared using condensate inside the line while ensuring that the line is not
over-pressured or overheated.

CAUTION:

It must be noted that under very unusual circumstances, the steam on a jacketed line containing
confined A.N. may actually be absorbing heat and preventing a runaway decomposition
reaction of the A.N. Caution must therefore be exercised when shutting steam off of a jacket
that is know to contain confined A.N and the temperature and pressure of the process side line
must be monitored very closely.

Maintenance personnel must also be aware of the possibility and consequences of confining AN.
Product can become trapped under bolt heads and rivets and between double skins. Steam jacketed
pipe-work should be treated with caution because of the possibility of AN leakage into the jacket.
Hollow shaft screw conveyors are a well-known hazard and should not be used as AN can get into
the shaft and create a potential “pipe bomb”. Vehicles that handle AN should also be considered,
particularly those that work with bulk product. When it comes time to carry out repairs to vehicles,
extreme caution must be exercised when burning or welding as there is usually oil and/or grease
present along with AN dust and all vehicles have many hidden “nooks and crannies” where a
mixture of AN and oil can build up.

Page 19 of 29
3. HIGH TEMPERATURE

Elevated temperatures above 170 O C can both cause and effect an A/N decomposition reaction.
When AN is in the presence of contaminants, decomposition temperatures can be drastically
reduced. Even temperatures associated with the production of AN can initiate a decomposition
reaction.
Heat also affects reaction time. At elevated temperatures A/N decomposes at an accelerated pace
into a runaway reaction. At reduced temperatures decomposition occurs much slower and can be
controlled.

Design and Engineering Considerations

- The use of steam heating coils should be avoided inside AN Neutralizers, as far as practical.
If a steam coil must be used, the steam supply to the coil should be at a reasonably low
pressure (steam temperature should be close to the saturation temperature of the AN solution).
An interlock should be provided that would shut off the steam supply to the coil any time the
nitric acid block valves to the Neutralizer are open.
- Consideration must be given to the steam pressure used to supply jacketed lines.(200 psig
steam (198 O C) should not be used as the temperature is above the decomposition
temperature of the AN.)
- An effective dilution or quench system shall be provided to the Neutralizer to control potential
excursions. Potential contaminants in the source of
water should be considered in the design, and in
dealing with quenched AN solutions.

- The maximum operating temperature in an AN Plant Neutralizer should be based on the

design of that specific Neutralizer and operating considerations specific to that design and site.
- The Neutralizer temperature probe should be located far enough below the overflow line to
ensure that the probe is always submerged in AN solution (even during shutdowns). A high
temperature alarm and trip should be included in the instrument loop.

- Good temperature monitoring should be designed

that includes consideration of start-up, shutdown,
and off-line situations. Good instrumentation will
require several probes monitoring different
locations in large vessels or large diameter vessels.
[If multiple temperature probes are to be installed,
they should be equally spaced around the vessel].

Page 20 of 29
 Operational and Maintenance Considerations

- The high temperature monitors and trips on AN Solutions pumps should be checked
regularly.
- Spring-loaded thermocouples tend to fatigue and must be checked for good contact or
replaced. See Terra standard for AN solution pump installations.
- External heat must not be applied to frozen AN lines, vessels or pumps to clear the same.
- Pump seals should be monitored for overheating and proper flow for flushes.
- Always take precautions against the sudden release of hot AN from lines, pumps or vessels.
- Live steam should not be injected into the Neutralizer as this can cause localized heating and
decomposition.
- Neutralizer temperatures must be closely monitored.
- Temperature probes should be calibrated regularly.
- Any temperature excursion above normal must be investigated by the operators. Action must
be taken immediately to bring the temperature back down to normal. The nitric acid supply
should also be shut off. If this cannot be done, the Quench system must be activated. The
Neutralizer should not be re-started until the cause for the temperature excursion is found and
corrected.
- Temperature measurements may not be representative on still neutralizers (no circulation, no
reaction). Dilution and/or circulation can be used to reduce a temperature hazard.

4. FIRE

Ammonium nitrate by itself is not combustible. AN is, however, an oxidizer and it can accelerate
the burning of fuels when it is involved in a fire. The AN may ignite combustibles such as wood,
paper, oil, clothing etc. The AN may also explode from heat or contamination given the right
conditions.
Do not attempt to put out an AN fire by smothering it as AN is an oxidizer.

NH4NO3 → N2 + 2H2O (as vapour) + 1/2 O2 (generates heat at 316 BTU/LB).

During this decomposition it also releases oxygen that can support its own combustion. The AN
fire “feeds on itself”. Because of this, fires involving AN cannot be extinguished by conventional
fire fighting techniques using oxygen-displacing fire fighting mediums or by containing it and
preventing oxygen from entering the confined area. Water only should be used to extinguish a fire
involving AN. (if the water is compatible with the burning product). Dry chemicals, CO2, halogen
or foam should not be used. Copious amounts of water should be used when fighting fires
involving AN and consideration must be given to the firewater run-off as regards possible
pollution. Electrical equipment, if involved, should be isolated before the application of water.
Wherever possible, fire involving AN should be fought from a maximum distance and/or
unmanned monitors should be used.
Several different AN decomposition reactions may be involved during an AN fire and one of the
products of the decomposition may be NOX fumes. These fumes are toxic. Therefore, positive
pressure self-contained breathing apparatus may be required when fighting AN fires

Design and Engineering Considerations

- Equipment containing oil or grease (such as gearboxes) should not be installed (or stored)
above AN conveyors

Page 21 of 29
- Conveying systems for solid AN fertilizer should have suitable protective systems to prevent
the spread of a fire to downstream equipment and/or bulk warehouses.

- Fire Detection Systems and Smoke Detectors should be installed on AN dry bulk conveying
equipment and in AN bulk warehouses. They should alarm locally and to a remote constantly
monitored area such as a Control Room or Security Building.
- Firewater monitors should be installed to allow bulk AN fires to be fought from a distance.
- Where necessary, provisions should be made to handle firewater run-off to prevent pollution.
- Ensure that MOC process considers material compatibility with AN.
- Storage areas for pallets, bags, and other combustible or possible contaminants should be
provided in an area separate from any AN bulk storage area.
- Hollow shafts and double-walled vessel should be avoided where possible in the design of
bulk AN handling equipment.
- Combustible materials (such as wood and plastic) and contaminants should be avoided
whenever possible in the construction of plants, warehouses, and any vehicles that handle or
transport AN.
- Conveying systems and warehouse design should be such that it will not permit the
introduction of foreign materials to AN. (i.e. spills, dissolving tanks, etc.) .

Operational and Maintenance Considerations

- Combustible and contaminants must not be stored in production or storage areas.

- Good housekeeping standards are necessary to prevent the potential exposure of hot AN liquid
to combustibles and contaminants.
- Proper signage should be in place prohibiting the storage of combustible materials and/or
contaminants and the entry of unauthorized vehicles in production or storage areas.
- All combustible and contaminants must be removed from within vessels, piping and the
operating area upon the completion of any maintenance work, especially during major
overhauls. The equipment and areas involved should be inspected by operations before
accepting the Work Permit as complete.
Production plants must not be restarted if combustible and contaminants are present!
- Customer return should not be accepted on UAN Solutions and Dry products (without the
express approval of supervision/management).
- Before issuing a Work Permit, maintenance should be made aware of the possibility of the

Page 22 of 29
 presence of AN, especially where hot work is involved. If the presence of AN cannot be ruled
out, cold-cutting may be required.
- Maintenance personnel must be made aware of the possibility of the presence of AN in any
areas way it may not be readily visible.
(See Item 6.7 in Section on “GOOD MAINTENANCE PRACTICES”).
- Combustible materials used during shutdowns and major overhauls in production and storage
area should be kept to a minimum.

5. HIGH ACIDITY
Nitric acid has a catalytic effect on the decomposition of ammonium nitrate. Even if the nitric acid
is not initially in the solution it is formed by the decomposition reaction. At locally high
concentrations the reaction is autocatalytic.
Ammonia will immediately neutralize any free nitric acid, thus inhibiting decomposition.
However, the ammonia does not dissolve well at elevated temperatures.

Design and Engineering Considerations

- Efficient and constant mixing of feedstock is required to avoid localized high nitric acid
concentrations.
- Design should prevent back-flow of ammonium nitrate solution into the ammonia or nitric
acid feed stock lines. Flush acid sparger with water on shutdown.
- Feed stream piping for the nitric acid and ammonia lines to the Neutralizer should have
double-block and-bleeds to assure positive block of feeds during shutdowns. The block valves
should installed as close as possible to the Neutralizer.
- Sample take-off points for the Neutralizer pH should be sufficiently below the Neutralizer
overflow to ensure that a sample is always available. The sample line and Ph probe should be
properly insulated to prevent salting out of the AN solution.
- Two nitric acid control valves (a large one and a small
one) should be used for the most efficient control of
nitric acid flow and pH. The larger valve handles the
basic acid flow requirement while the smaller valve is
sized to deliver app. 10% of the total flow required
and to control the pH in the Neutralizer within a
narrower range.
- Dilution water should be used to flush out the nitric
acid sparger on shutdowns.
- The Neutralizer shall be equipped with low pH
alarms.

Operational and Maintenance Considerations

- pH of the Neutralizer to be monitored and controlled closely.

- At least one pH probe and a backup would normally be in service.
- Free acid content in the solution exiting the Neutralizer should be promptly neutralized with
ammonia.
- Do not rely solely on pH probes for monitoring. Samples from the Neutralizer should be
tested for pH regularly as back up.
- The pH probes should be calibrated on a regular basis.

Page 23 of 29
 - AN solutions that are left in any vessel must be tested for pH
regularly. As the ammonia evaporates from the solution, the acidity
will increase correspondingly. The higher acidity increases the
sensitivity of the AN and the possibility of a runaway
decomposition reaction. The addition of ammonia may be
required.

6. CONCENTRATION
Detonability of aqueous ammonium nitrate solutions depends on a number of factors such as
concentration, temperature, pH, the presence of bubbles, etc.

Design and Engineering Considerations

- Consider steps that keep inventory of higher concentration, higher temperature solutions at
low or reduced levels in the plant.
- Avoid entrained bubbles in higher concentration solutions, particularly at higher
temperatures or pressures.
- Avoid remelting dry AN or seek advice from AN technical resources in developing sound
remelt procedures. Dry AN can cake in the remelting processes that result in localized
high concentrations. [Nitrochem incident]

Operational and Maintenance Considerations

- Air, nitrogen, or other non-condensable gasses should not be

injected into AN solution for learing, mixing, or other reasons,
including the Neutralizer sparger(s). Use dilution water for
clearing.
- Gasses can evaporate off the water thus increasing the
concentration while the same time cooling the solution increasing
the chance for salt-out. The air can also introduce contaminants to
the AN.
- Higher concentration ammonium nitrate solutions have higher melt
and boiling temperatures. Know the limits to avoid conditions that
represent salt out or decomposition.

Page 24 of 29
7. SENSITIVITY AND SELF-DETONATION
An important consideration for anyone handling ammonium nitrate is the difference between
ammonium nitrate that has been sensitized to more easily detonate if shocked, and ammonium
nitrate that self detonates. The presence of contaminants, high AN concentrations (≥ 90%), and
the presence of bubbles make AN more shock sensitive, (i.e. more likely to detonate when
shocked). Bubbles in AN can also greatly increase sensitivity. When liquid AN with bubbles is
shocked, the bubbles are compressed adiabatically, raising the temperature significantly. This
greatly increases the heat available to propagate the reaction. Bubbles are normally present in the
AN in a Neutralizer because:

1. Water is present in the nitric acid feedstock and the heat of reaction between the nitric acid and
ammonia boils some of the water out as steam.

And/Or

2. There is carbon dioxide and steam in the urea off gas feedstock to the Neutralizer.
(Where applicable).

AN heated in a confined area can self-detonate provided that the extreme conditions of pressure
and temperature are met.. This is true in any quantity but is especially dangerous in small
quantities of AN in isolated areas because:

1. It is easier to contaminate small quantities of AN with higher concentrations of contaminants.

2. 2. There are more of the small isolated areas than there are large storage tanks and the small
isolated areas are more difficult to monitor and control (e.g. trapped AN with heat applied).

Design and Engineering Considerations

- Minimize the volume of high concentration ammonium nitrate solution that contains entrained
bubbles.
- Select mixing operations that reduce or avoid bubble entrainment, such as pumping in tanks
with a minimum level.

Operational and Maintenance Considerations

- The injection of live steam into the Neutralizer should be avoided as the live steam can cause
localized heating which can lead to decomposition. The live steam can also introduce bubbles
into the solution.
- Air, nitrogen, or other non-condensable gasses should not be injected into AN solution--
including into the Neutralizer sparger(s)--for clearing, mixing, or other reasons. Use dilution
water for clearing.

8. PUMP DETONATION HAZARD FOR AN AND UAN SOLUTIONS

Explosion in AN solution pumps detonations are well known. UAN is generally very safe and easy
to handle, however the industry has experienced explosions of UAN when pumps were operated
with a blocked discharge.

Page 25 of 29
 While the mechanism is not well understood at this time, UAN is known to detonate due to the
temperature rise and extreme conditions that can occur within an operating pump with restricted or
blocked flow. AN solution is often at elevated temperatures to avoid salt-out: critical temperatures
can be quickly reached when flow is restricted.

Caution with any solution containing

ammonium nitrate is advised. Pumps with
higher horsepower and operating at higher
RPM may increase temperatures very quickly.
Tests have demonstrated that standard 3600-
RPM pumps can increase temperatures by 60
degrees F per minute or more with blocked
flow, leaving insufficient time to react without
an automatic safety system. The temperature
build up occurs rapidly at the high shear area of
the pump—which may not be well monitored
by thermocouples mounted at other locations.
Consult the Terra standard for AN/UAN
solution pumps for more detailed information.

Design and Engineering Considerations

Many UAN producers have put safeguards in place to prevent such detonations. The safeguards
include both mechanical safety systems and procedures designed to prevent pump operation with
blocked or restricted flow.
Some of those safeguards include:

- Minimum flow lines re-circulated to the feed tank. Caution must be taken to insure free flow in
the line, particularly in cold weather locations.
- Minimum flow and/or minimum amp trips.
- Properly installed temperature trips. Terra’s practice includes an evaluation of the pump type
and sensor installation to insure a temperature rise is detected quickly.
- Temperature trips should be checked on a regular frequency.
- Installations that prevent freeze-up or salt-out that could lead to a blocked discharge.
- Installations that prevent blocking in a pump discharge while the pump is running.
- Installations should be designed to provide easy operation while avoiding a blocked discharge.
- Organic gland packing material should not be used.
- There should be no unnecessary valves installed on the pump discharge or re-circulation line
that could inadvertently be closed thus leaving the pump dead-headed.
- Install temperature or flow alarms on flush lines to the pumps seals.
- Ammonia should not be injected into AN solution pump suction lines

Other factors may have to be considered dependent on the pump design and manufacturer.

Operational and Maintenance Considerations

- Operators should know the risks and understand safe operating practices.
- Procedures should avoid blocking in the pump discharge while the pump is running.
- Trips and procedures should be checked on a regular frequency.
Page 26 of 29
 - If an AN pump becomes overheated, it should be shut down immediately. The pump and its
piping system should then be cooled by flushing with condensate. Once the pump is flushed
and cooled down it can be blocked in and the drains and bleeds may be opened.
- - Inspect the flushing lines to the pump seals regularly to ensure that they do not fail thus
causing possible overheating or freezing (depending on design or application).
- Oil contamination from the pump gearbox must be avoided as must AN contamination of the
gearbox.
- If a pump impeller should become noisy, the pump should be taken off line immediately,
properly flushed and prepared for maintenance. The noise could be from a loose retaining
nut on the pump impeller that is allowing the impeller to run against the pump impeller
casing. This could result in localized heating and a possible detonation.

9. COMBINATIONS OF HAZARDS

Combinations of factors such as confinement, pressure, adequate time at elevated

temperature, and the presence of contamination make AN more susceptible to risk of
explosion

10. PLANT START-UP, SHUTDOWN, UPSET AND OFF-LINE SITUATIONS

- pH systems should be checked for proper operation
as a startup step.
- On shutdowns, the nitric acid sparger should be
flushed with water to dilute the acid and to ensure
that AN is not trapped with high concentration acid.
- The Neutralizer should be ”ammoniated slightly”
before shutting it down to avoid acidic conditions
- If this “slight ammoniation” cannot be done before
shutdown, it should be done after the shutdown or
dilute, drain and flush the Neutralizer. (The nitric
acid flow to the Neutralizer should be shut off first.
- Neutralizer should be re-circulated during short
shutdowns. If this is not possible, it should be diluted to a safe condition or diluted, drained
and flushed.
- For extended shutdowns, the Neutralizer should be diluted, drained and flushed.

Design and Engineering Considerations

- The Neutralizer product overflow should be equipped with a vent system to allow free product
flow and prevent vapor locking of the overflow line. Vent lines can be connected back into the
Neutralizer or scrubbing systems to avoid emissions.
- Set an appropriate maximum time limit for holding ammonium nitrate in the neutralizer before
flushing and draining. This limit should be considered a safety trip and treated with similar
procedures.
- When additional heating, tracing, steam-jackets are required for operation in cold climates,
Equipment and plant design should not create the need for unsafe operating practices. More
attention may be needed as regards design and location of drains on piping and vessels.
Page 27 of 29
- Neutralizers, tanks, and vessels should be designed to avoid trapping of AN. As an
example, internal structural supports made of piping materials must have holes to permit
flushing, clearing and draining.

Operational and Maintenance Considerations

- When a trip occurs or an unexplained excursion, the crew should work to establish control.
Before continuing on with normal operation or a restart, the crew should group and review the
situation to insure that plant is ready. Report the incident as a Level II.
- The nitric acid and urea off gas sparge(s)r must be properly flushed with condensate before
allowing maintenance inside the Neutralizer.
- If unusual noises or vibrations are coming from an operating Neutralizer it is most likely being
caused by a broken internal component. The Neutralizer should be shutdown immediately and
prepared for inspection and repair.
- Check for trapped AN points before any maintenance or hot work is performed. If the
Neutralizer internal structural supports are made of piping materials maintenance must ensure
that this piping is properly drained and flushed before commenting any hot work on it.
- Written procedures should be in place for all maintenance work inside the Neutralizer with
special attention being given to hot work, cutting, the hazards of confined AN and
incompatible materials.

Potentially hazardous conditions can develop either rapidly or over a period of time during
start-ups, shutdowns, process up-sets and off-line times in process vessels, pumps and lines
containing hot AN Solution or AN Solutions that is inadvertently being heated.

Some causes are as follows:

- Ammonia is evaporating out of the solution and the solution is becoming more
concentrated and more acidic.
- The temperature of the solution may drop, leading to the crystallization/freezing of the AN
and blockage of the lines.
- The liquid level in a vessel can drop resulting in a continuous sample not being taken and
the instrument thus reading incorrectly (possibly further exacerbating an existing unsafe
condition).
- Steam heating, either direct or indirect, can result in overheating of the AN solution.
- Solid AN may be depositing, sometimes in unknown locations.
- Continued recycling while “shutdown” could lead to an accumulation of contaminants
and/or change other process conditions.
- Pumps left running with no flow could overheat and explode.
- Dilution of the nitric acid sparger is necessary at shutdowns to avoid high concentrations
of acid in contact with AN and to avoid accelerated corrosion of the sparger which is no
longer being cooled by incoming acid during shutdowns.
- If circulation within the Neutralizer loop is stopped and the ammonium nitrate solution is
no longer being mixed, feedstocks should be tripped and over acidification at the nitric
acid injection point should be avoided. If re-circulation cannot be regained within 30
minutes, the Neutralizer should be drained and flushed.

Page 28 of 29
Exercise care at all times and review safety considerations, and maintenance
and operating procedures regularly. Never assume that operations or
maintenance personnel understand the dangers. Supervisors must make sure
they do. Operations and maintenance personnel must take it upon themselves
to understand as well. Continuous vigilance and periodic training will continue
to be required to ensure safe operation.

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