Nitrogen & Syngas 2018 Urea Clinic

SAFETY FIRST! …

BUT WHAT ARE THE SAFETY HAZARDS

IN UREA PLANTS?
Nitrogen & Syngas 2018 Urea Clinic
Hand Out

Part 1
• Introduction
• 100 Safety Hazards in a Urea Plant
• Safety Management
Part 2
• Workshop managing High Pressure flange leakages
Part 3
• Risk Registers
• Workshop Hydrogen Explosion risks in urea plants
Part 4
• Leak detection systems
• Closing remarks: How to behave in a urea plant ?
RISK REGISTERS &
ACTION TRACKING
SYSTEM
Have we taken all reasonable measures to reduce
our operational risks to minimum?

How can we prove that?

Organise knowledge and make it easily
accessible to operators and engineers
 Risk Register & Action Tracking
Safety Studies

HAZID
HAZOP
Risks Safeguards
Risk Registers
LOPA Identification Identification
CHAZOP
SMS HAZARDO
Constructability
Review
Corrective Responsible Action
SAFOP Actions Persons Tracking
3D Model Register
Review
SIMOPS
 Risk Register & Action Tracking
Safety Studies
Risk Register and Action Tracking Software
HAZID
HAZOP
Risks Safeguards
Risk Registers
LOPA Identification Identification
CHAZOP
SMS HAZARDO
Constructability
Review
Corrective Responsible Action
SAFOP Actions Persons Tracking
3D Model Register
Review
SIMOPS
Risk Register
 Risk Register

A cloud based centralized software documenting:

• Incidents,

• Lessons learnt,

• Near misses,

• Projects risks,

• Safety Studies findings.

 Risk Register
The system lists the following information:

• Cause of incident,

• Consequences,

• Identified safeguards,

• Prevention solutions

• Mitigation barriers,

• As Low As Reasonable Practicable (ALARP) demonstration

 Risk Register

List of process hazards

Prevention and mitigation barrier

Internal Risk assessment and evaluation

Risk Register
ALARP Demonstration support

Lessons Learned for operators

Risk Register
 Risk Register

• Description of incident

• Cause of incident

• Consequences
 Risk Register

• Description of incident

• Cause of incident

• Consequences
 Risk Register

• Identified safeguards

• Prevention solutions

• Mitigation barriers
 Risk Register

• Identified safeguards

• Prevention solutions

• Mitigation barriers
Action Tracking Register
 ALARP
As Low As Reasonably Practicable
 Risk Register
As Low As Reasonable Practicable (ALARP) demonstration
 Risk Register
As Low As Reasonable Practicable (ALARP) demonstration

Likelihood

Happened in the Happened at the

Happened more
Never heard of in Heard of in the organisation or facility or more
Category than once at the
the industry industry more than once in than once in the
facility
the industry organisation

Catastrophic 7 10 12 14 15
Consequence

Major 5 8 11 13 14

Moderate 3 6 9 11 12

Minor 2 4 6 8 10

Insignificant 1 2 3 5 7
Risk Register
Risk Register
Risk Register
Risk Register
Risk Register
Risk Register
Risk Register
Action Tracking Register
 Risk Register & Action Tracking
Safety Studies
Risk Register and Action Tracking Software
HAZID
HAZOP
Risks Safeguards
Risk Registers
LOPA Identification Identification
CHAZOP
SMS HAZARDO
Constructability
Review
Corrective Responsible Action
SAFOP Actions Persons Tracking
3D Model Register
Review
SIMOPS
 Action Tracking Register

Action tracking and collaboration

Action Tracking Technical Queries support

Register
Actions Close-Out verification
 Action Tracking Register
Traceability
allows managers and/or
supervisory personnel to
identify and track the statuses
of actions and close-out
records generated from Safety
Studies to be managed and
completed in a timely manner.
Advantages of using
ATR
Efficiency
action approval meeting minutes are
saved and stored. Records of
communication between various
parties (client, contractors, vendors)
during the action approval process
are kept for evidence, audit and
further information.
Simplicity
using one dedicated software solution
with web access for action tracking
management. Unlike Excel spreadsheet
implemented register, where a dedicated
team is required to support the register,
our software is maintained by us
ensuring all our clients have the most up-
to-date version. Web access to the
register ensures that authorized
personnel have unlimited access from
various OS platform.
Action Tracking Register
Action Tracking Register
Action Tracking Register
Multiple discipline Accessibility and
inputs Collaboration

ATR allows for action

assignment to responsible
Allows various options for
party including joint
controlled access by both
responsible party for multiple
COMPANY and non-
discipline inputs (e.g.
COMPANY users (e.g.
process and piping, or
vendors, consultants,
process and I&C), and
third party operators)
configurable number of
Approvers
Action Tracking Register
 Action Tracking Register

Advantages of using
ATR

Confidentiality Design Progress

Management
by allowing the third party
(vendors, consultants) access
only to their dedicated actions by using the ATR progress reporting
without visibility across project function, the Management team can
overall design. have a real time access at the rate of
actions closure, daily updates, focus on
levels of detail underlining those actions
that can impact the project schedule or
are critical for design safety.
Flexibility of configuration
such as the ability to change due dates
after the initial entry has been made,
reassignment of responsible people, or
Checkers and Approvers change based on
latest project inputs and decisions.
Action Tracking Register
Action Tracking Register
 Action Tracking Register

Advantages of using
ATR

In line with international

Compatibility
with major Operators and EPCM
safety studies actions close-out
procedures.
legislation
OHSAS 18001, UK HSE and EU
Seveso 3 when used in conjunction
with Risk Register in demonstrating
the ALARP principle.
Thank You
 Hydrogen Explosion Risks in Urea Plants

V4
Hydrogen explosions

1970’s:
Several
explosions in
HP scrubbers

But also in
other plants

Incident
Database:
74-001
00-002
Or Hydrogen flames
 Sources H2 and CH4

CO2 feed
Typical : 0.8 – 1.0 vol% H2

Max : 2 - 3 vol% H2

Causes for high H2 content in CO2:

1. Gas breakthrough from CO2 removal absorber in case of low
level in absorber. This is typically mitigated by ESD trip function
in ammonia plants - closes the XV for solution outlet absorber.
2. High hydrogen absorption rates due to foaming and high
circulation flow rates.
3. Tube leak in reboiler of CO2 reboiler (can give even higher H2
contents)
 Sources H2 and CH4

CO2 feed
Typical : 0.8 – 1.0 vol% H2

Preventive measures
- H2 converter
- Extra flash step in CO2 washing section in ammonia plant

Mitigation measures
- Expansion volume (hemisphere HP scrubber)
- Higher design pressure
 Sources H2 and CH4

NH3 feed
Typical : 0.01 wt% H2 and 0.09 wt% CH4
Max : Solubility

Prevention measures
- Take ammonia from atmospheric storage
- Ammonia de-gasification step

Mitigation measures
- Expansion volume (hemisphere HP scrubber)
- Higher design pressure
Mitigation measures

Prevention measures
 Stac guidelines

When oxygen is in the range of 0.6-0.8 vol% in CO2

ü CO2 feed max 300 vol-ppm
ü NH3 feed max 100 wt-ppm

ü Install a H2 converter
ü Install an expansion volume (sphere) for HP Scrubber
ü Use only normal air for passivation (no enriched or pure oxygen)
ü Proper grounding and protection against lightning
ü Pay attention to hot work / grinding

Source: Stamicarbon Y2K Update

H2 converter

CO2
 H2 converter

hydrogen

methanol

VOC’s
and Air
Toxics

CO
methane

93 204 540 degC

 Expansion volume

Expansion volume or 7X higher design pressure

 Enriched air

Type of explosions

Deflagration: P2/P1 about 7

Detonation: P2/P1 >> 7

Enriched air increases

Risks of Detonation !

Stamicarbon R&D
 Explosion diagram
Position of the point representing a gaseous mixture in the triangular
explosion diagram depends only upon the relative composition of the
three groups:
Flammables (H2, NH3, CH4)
Oxygen or Air
Inerts (N2, CO2, Ar)

while the extension of the explosion area depends only upon the
relative composition of the flammable components, like:
H2
NH3
CH4

Note: A higher pressure also increases the explosion area

 Explosion limits
N2
175 bar
90 10
150 degC
80 20

NH3-N2-Air 70 30

60 40

50 50

40 60

30 70

20 80

10 90

NH3 50 40 30 20 10
Air
90 80 70 60
% by mol
 Explosion limits

Some principles:
– LEL : Lower Explosion Limit
– UEL: Upper Explosion Limit

Note:
LEL and UEL are also sometimes called LFL and UFL
(lower and upper flammability limits)
 Explosion limits
N2
175 bar
90 10
150 degC
80 20

NH3-N2-Air 70 30

60 40

50 50

40 60

30
LEL
70

20 80

10 90

NH3 50 40 30 20 10
Air
90 80 70 60
% by mol
 Explosion limits
N2
175 bar
90 10
150 degC
80 20

NH3-N2-Air 70 30

60 40

50 50

40 60

30 70

20 UEL 80

10 90

NH3 50 40 30 20 10
Air
90 80 70 60
% by mol
 Explosion limits

NH3 or H2 as combustible:
A considerable difference
 Explosion limits
N2
175 bar
90 10
150 degC
80 20

NH3-N2-Air 70 30

60 40

50 50

40 60

30 70

20 80

10 90

NH3 50 40 30 20 10
Air
90 80 70 60
% by mol
 Explosion limits
N2
175 bar
90 10
150 degC
80 20

H2-N2-Air 70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2 50 40 30 20 10
Air
90 80 70 60
% by mol
 Explosion limits

Mixtures containing
NH3 and H2 as
combustible:
The flammable region
grows in size
Explosion range for mixture: LeChatelier’s rule
 Explosion limits

N2
90 10
175 bar
150 degC
80 20

NH3-N2-Air 70 30

60 40

50 50

40 60

30 70

20 80

10 90

NH3 90 80 70 60 50 40 30 20 10
Air
% by mol
 Explosion limits

N2
90 10
175 bar
150 degC
H2 -NH3 -N2-Air 80 20

70 30

H2/(H2+NH3) =0.1 60 40

10% 50 50

40 60

30 70

20 80

10 90

H2+NH3 50 40 30 20 10
Air
90 80 70 60
% by mol
 Explosion limits

N2
90 10
175 bar
150 degC
H2 -NH3 -N2-Air 80 20

70 30

H2/(H2+NH3) = 0.25 60 40

25 % 50 50

40 60

30 70

20 80

10 90

H2+NH3 50 40 30 20 10
Air
90 80 70 60
% by mol
 Explosion limits
N2
175 bar
90 10
150 degC
H2 -NH3 -N2-Air
80 20

70 30

H2/(H2+NH3) = 0.60 60 40

60 %
50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
 Explosion limits
N2
90 10
175 bar
150 degC
80 20

H2-N2-Air 70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2 90 80 70 60 50 40 30 20 10
Air
% by mol
 Explosion limits

N2
90 10
175 bar
80 20
150 degC
H2-NH3-N2-Air
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
90 80 70 60 50 40 30 20 10
% by mol
 Example

Inert vent composition

Question 1: is this vent explosive ?

Method:
Pinpoint in the explosion diagram the point of composition
And determine the explosion area
Check if point is inside or outside the explosion area
Assume following input data

AIT
degC

600

500

651
Answer 1 part 1: determine point in explosion diagram

vol% vol%
H2 31,2 N2 from air 29,3
N2 51,9
Ar 0,8
CH4 6,3
NH3 1,5 Air 37,1
O2 7,8 Inert 23,9 excluding N2 from air
H2O 0,5 Flammable 39,0
100,0 total 100,0 total
Answer 1 part 2: determine explosion area

vol% vol% flam

LEL UEL
H2 31,2 0,80 H2 4 74
NH3 1,5 0,04 NH3 15,5 27
CH4 6,3 0,16 CH4 5 15
mixture 4,6 63
totaal 39,0 1,00

Apply LeChatelier’s rule

Example:
UEL(mixture) = 0,80*74 + 0,04*27 + 0,16*15 = 63
 Explosion limits

Answer 1 part 3: Inerts

Draw explosion
90 10
diagram
80 20

70 30

60 40

50 50

40 60

30 70

20 80

10 90

Flam 50 40 30 20 10
Air
90 80 70 60
% by mol

Conclusion: vent is explosive

Question 2:
How one can avoid that the vent remains explosive ?
 Explosion limits

Answer 2: N2
Add CH4 and/or NH3
90 10
H2-N2-Air
NH3-N2-Air
80 20

70 30

60 40
CH4-N2-Air
50 50

40 60

30 70

20 80

H2 10 90

NH3 Air
CH4 90 80 70 60
50 40 30 20 10
% by mol

NH3 and CH4 are effective to reduce the explosion area

Question 3:
Why adding CH4 is a better choice than NH3 ?
Answer 3:

• CH4 is more effective in reducing UEL

(according LeChaterlier’s rule)
UEL CH4 = 15%
UEL NH3 = 27%

• CH4 is less expensive

Question 4:
Which assumptions one did make ?
Which notes one can make ?
Answer 4, part 1:
Note 1: LeChatelier’s rule needs experimental confirmation

Example:
H2/(H2+NH3)=0,1

LeChatelier’s rule
UEL= 50
(0,1*47+0,9*81)
Red line

Experimental
Green line
Answer 4, part 2:
Note 2: LEL and UEL depend on pressure (and temperature)
 Explosion limits
N2
175 bar, 150 oC
90 10

80 20
44 bar, 150 oC
70 30

60 40

50 50

40 60

30 70

20 80

10 90

NH3 Air
50 40 30 20 10
90 80 70 60
% by mol

A higher pressure increases the explosion area

 Stamicarbon

Walking through the plant

Gas compositions through the plant (falling

film carbamate condenser) and the distance
to the relevant explosion limits:
First without hydrogen removal technologies
Stamicarbon HPCC
 N2 Without
CO2 Compressor
90 10
Hydrogen
80 20
Removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
 N2
Stripper Off-gas Without
90 10 Hydrogen
80 20 Removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
90 80 70 60 50 40 30 20 10
% by mol
HPCC Off-gas N2 Without
90 10
Hydrogen
80 20
Removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
90 80 70 60 50 40 30 20 10
% by mol
 N2 Without
Reactor
Off-gas 90 10
Hydrogen
80 20
Removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
Watch the explosion area is
growing as we move further
through the plant.
HP Scrubber: N2 Without
Outlet 90 10
Hydrogen
Heat-exchanger 80 20
Removal
part 70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 50 40 30 20 10
Air
90 80 70 60
% by mol
 N2 Without
HP Scrubber:
Off-gas of 90 10 Hydrogen
Packed bed 80 20 Removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
 N2 Without
LP Absorber:
Off-gas 90 10 Hydrogen
80 20
Removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 50 40 30 20 10
Air
90 80 70 60
% by mol
And now we make the
same trip through the
plant; now with Hydrogen
removal.
In this example, for the sake of clarity,
complete removal of hydrogen both
from carbon dioxide as well as from
ammonia has been assumed.
 N2 With
CO2 Compressor
90 10 Hydrogen
80 20
Removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
 N2
Stripper With
Off-gas 90 10 Hydrogen
80 20 removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 50 40 30 20 10
Air
90 80 70 60
% by mol
 N2 With
HPCC
Off-gas 90 10 Hydrogen
80 20
removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
Reactor N2
With
Off-gas 90 10 Hydrogen
80 20 removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
So far, there seems to be little
difference with or without hydrogen
removal; however from here on
please note:
•The explosion area does not grow
•The totally different path of the gas
compositions through the diagram.
HP scrubber N2 With
Heat-exchanger 90 10 Hydrogen
Off-gas 80 20 removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
HP scrubber N2 With
Off-gas of 90 10
Hydrogen
Packed bed 80 20
removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
 N2
LP absorber With
Off-gas 90 10
Hydrogen
80 20
removal
70 30

60 40

50 50

40 60

30 70

20 80

10 90

H2+NH3 Air
50 40 30 20 10
90 80 70 60
% by mol
 Stamicarbon HPCC

Conclusion: HP scrubber and LP absorber may be in explosive range

 Saipem flowscheme

Conclusion: MP vent may be in explosive range

 Saipem
Inerts
90 10

80 20

70 30

60 40

50 50

40 60

30 70

20 80

10 90

Flam 50 40 30 20 10
Air
90 80 70 60
% by mol
 Inerts

90
80
70 10
60
Saipem

50
20
40
Flam

30
20 30
10
40
90
50
80
70 60
60
50 70
40
80
30
20 90
% 10
by
mol

Air
 rts
ne
I

90 10
80 20
30
70
40
60
m

50
50
a

60
Fl

40 70
i r

30 80
A

20 90
10 10
40 30 20 % by mol
60 50
90 80 70
Saipem

(AIR)
LEL
(AIR
UEL

)
UEL
(O2)

(O2)
LEL
 Saipem
N2
90 10 175 bar
80 20
150 degC
70 30
60 40

50 50
40 60

30 70

H2+ 20 80
10 90
NH3
90 80 70 60 50 40 30 20 10
% by mol
Air

NH3
H2
 Saipem

0.25 vol% O2 in CO2

A: Before water scrubbing

A1: After water scrubbing

 Saipem

0.8 vol% O2 in CO2

B: Before water scrubbing

B1: After water scrubbing

 Saipem

0.8 vol% O2 in CO2

B: Before water scrubbing

B2: After water scrubbing

+ 80 kg/hr CH4
Saipem
Saipem
Question 5:
Are there other area’s in a urea plant which could
be explosive ?
Answer 5, part 1:
Yes, atmospheric absorber as H2 and O2 (and other inerts)
are dissolved in solution outlet HP stripper
Answer 5, part 2:

Yes,

H2 can enter various sections of the urea plant when

interconnections are made with the NH3 plant
(drains, process water, nitrogen network)
Answer 5, part 3:

Yes,

When CO2 and/or NH3 feeds are connected to low pressure

sections in the urea plant to optimise N/C ratio’s or process
inert vents.
Answer 5, part 4:

Yes,

There are incidents reported of flames coming from the CO2

vent or drain of interstage separators of CO2 compressor.

Although max H2 content in CO2 is mostly 2-3% and this

below Lower Explosion Limit (LEL), we believe under
certain circumstances when icing of CO2 occurs, the H2
content could become higher than the LEL of 4 vol%.
Answer 5, part 5:

Yes,

Pay attention to stop, start, hold situations

For example:

• During maintenance, H2 could have accumulated in for

example the ammonia water tank

• During blocking in, H2 could have accumulated in the

synthesis

• During start up, H2 concentrations could increase due to

flushing with water