Professional Documents
Culture Documents
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and ProductionB.V.
Exploration
ShellInternational
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H2Sin Operations
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EP 95-0317
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HSE
MANUAL
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R e v i s i o n0 : 6 O c t o b e r 1 9 9 5
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EP HsE ManuarAmendment
Recordsheet
Section Number:Ep 95_0317
Section Tifle: H2S in Operations
Description of amendment
Contents
CONTENTS
Fluids
2.1 Process
(SRB)
Reducing
Bacteria
2.2 Sulphate
Assessment of Risks from HZS
5.1
Planning
Emergency
25
5 . 1 . 1 E m e r g e n ce
yquipment
25
25
zo
5.2.1 Hazards
28
5.2.2 Precautions
28
5.2.3 Generalprocedures/guidelines
28
rt
5.2
29
6.'l
29
6.2
30
6.3
Production Operations
30
The Framework
of Controlsfor Workingin
H2S Designated
Areas
6.3.1 Sampling
6.3.2 lsolation
a1
.21
J I
10
6.3.3 Depressurising
.r..)
10
5Z
10
6.3.5 Purging
32
11
H2S Detection
12
4.3.1 Fixedsystems
1a
4.3.2 Portablesensors
13
3 Personalmonitoringsystems
4.3.4 Testingand calibration
1 A
I T
WamingSigns
15
.5
AccessControls
4tr
.6
15
Respiratory
Protective
Equipment
4t 7t
17
18
18
19
Procedural
Controls
and Standing
Instructions
19
H2SCompetence
20
P 95-0317Revision0 5 October1995
6.4 Maintenance
Operations
33
34
Appendices
I
Formation
of H2S by SulphateReducing
Bacteria(SRB)
ll
PhysicalProperties
and Physiological
Effectsof H2S
37
lll
H2SCorrosion
41
lV
Pyrophoric
lronSulphide
45
H2SDispersion
47
Vl
H2S Detection
49
Vll
RespiratoryProtectiveEquipment
4 t
t $
.4
1'2
28
1.2 H2SAreaClassification
,B
4.9.5 Competencereview
25
ironsulphide
3.3.2 Pyrophoric
22
Recovery
'.3
4.9.4 Competencecertification
Firefighting
\,
t1
21
5.1.3 Rescueprocedures
Effectsof H2S
3.2 Erivironmental
4.9.2 Trarnrngprogramme
1.3 ..
20
Introduction
4.9.1 Competencerequirements
in operations
59
A2
Gfossary
65
References
67
ii
EP 95-0317Revision0 5 October1995
1 Introduction
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;::::*:::'il"fij;i1:il3fi:,T::."l:""xili:*il:3JH;SilHff
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It
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INTRODUCTION
of HoS exposure(Chapter'2)
of all sor-rrces
identification
' ! i r
' r
II
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It does not add.ressdetails on the protection of the general public or the seiectio
mabrials for HoS service.
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The Guideline provides the basis for the development of Opco specific procedure
Chapter 6 gives some specific guidance on the preparation of H"S procedures fo:
production, drilling and maintenance activities.
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I
the rnajor hazard of HoS is its ability to cause rapid darnage to heal
sudden death due to accidental exposure
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I
50 per cent of the people killed in H,S incidents were trying to resc
others.
'l
If the reader doesnot understand an)' part of this documentheishe must discussit wiih
.omeone who d.oes.
'
0 5 October1995
EP 95-0317Revtsron
of Sourcesof H2S
2 ldentification
OF HzS
OF SOURCES
IDENTIFIGATION
sufficient concentrations to
Liquid and gaseous hyd,rocarbons may contain HrS in
present a hazard to personnel, equipment and the environment'
pipelines, desulphurisation piant's'
HrS can be present in oil refineries, process plants,
swamps, or any area
oil/gas/water wells, during drilling or well workover, sewers,
(eg
utility shafts in offshore
where there is decayrng organic matter or stagnant water
platforms).
when acid is used to ciean
HrS can also result from acidicaustic reactions, for example
which has been used
caustic
equipment containing iron sulphide or to neutralise spent
flowed back after well
t* HrS scrubbing. HzS may also be present in spent acid
stimulation.
to resist the harmful effects of
All facilities potentially exposed.to HoS must be designecl
pressures'
HzS at the anticipated operating temperatures and
HrS in the upstream oil and gas industry comes from:
.
o
o
2.1
Process Fluids
entry, instrumentation
during normal maintenance operations, eg./sphering, vessel
or valve maintenance
2.2 SulphateReducingBacteria(SRB)
necessaryfor SRB
SRBs are the sourceof a range of hazard.sinclud.ingHgS. Cond:tions
of
means
(including H"S),
to exist an6 d.evelop,hazarclsassociatedwith SRBs
prevention, detectitn and control are ali describedin Appendix I'
EP 95-0317Revision0 5 October1995
l
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3.1
1i
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A S S E S S M E N TO F R I S K SF R O MH Z S
(ACGIH)
The current American Conferenceof Governmental Industrial Hygienists
(TWA)
and 15 ppm
8h
Threshold Limit Value (TL\ry is 10 ppm Time Weighted Average
Short-Term Exposure Limit (STEL).
or
The major hazard of HrS is its ability to cause rapid damage to health
sudden death due to accidental exposure'
Brief exposureto concentrationsabove500 ppm may result in rapid unconsciousness
without any warning symptoms.Exposule to HrS above500 ppm for any lenglh of time
is considered.as potentially lethal. Death due to stoppageof breathing may follow
within a few minutes unless the victim is removed to a safe atmosphere in time and
possible in
artificial respiration is applied..If the victim survives, complete recovery is
most cases.Exposuresover 30 minutes to HzS concentrationsof 200 ppm and above
may causer...,*r.lation of fluid in the iungs Oung oedema).At concentrationsabove
of the
l0 ppm, HrS can have an irritating effect on the eyes and the mucous membranes
In low
nose,throat an6 1ungs.The pr-imarysourceof exposureto HrS is by inhalation.
concentrationsHrS has the odour of rotten eggs'
at
It must be emphasised.that the unpleasant od.ourof HoS, which can even be detected
due
ppm
100
above
concentrationsof 0.02 ppm, may not be detectableat concentrations
to rapid loss of the senseof smell.
Odour cannot be relied upon to detect the presence of dangerous
concentrations of HrS.
The effect of H=S on the hoclyat clifferentconcentrationlevels and the occupational
exposurelimits are shown in Appendix II'
personnel at risk from exposureto H"S must be trained to know what to do if H"S is
person has to be rescued.Such training is vrtal since to
detected.or if an unconscior.rs
'conditioning'that might resuit in an
someextent it is necessaryto controi the
individual hur.r.vingimmecliatelyto the aiclof someoneovelcomeby H'S-
EP 95-0317Revrsion0 5 October1995
F
H S E M a n u a l E P 9 5 - 0 3 1 7 H y d r o g e nS u l p h i d e ( H z S ) i n O p e r a t i o n s
V
t)
3.2
G
EnvironmentalEffects of HzS
Emission controis should be set to protect people from toxic risks and avoid public
nuisance. There are no known health effects associated with long-term exposure to HrS
at concentrations at or below the point where short-term symptoms (for example eye or
respiratory irritation) are observed.
emission conditions
If under plessure then process fluids containing HoS could be released to the
atmosphele, for example, via a leak, weII services lubricator, maintenance or
maloperation of a sampie vaive. The release pressule, duration, rate (with time),
hole size, elevation and direction influence dispersion. Releases can also occur fi'om
vaporising liquid pools.
topography
Dispersion is accelerateclovel mole buiIt, np or rvoodeclland. Given stabie weather'
conditions a heaq;. gas rvill also tencl to accumulate in low lying areas thus the
contours of the land. and plesence of. for,'instance, buncied aleas can influence
dispersion.
ii
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b
E P 9 5 - 0 3 1 7R e v i s i o n0 5 O c t o b e r1 9 9 5
-. .
$t{ig,.-=*-i!..t-
samPlingttme
time
plym: fluctuate with time. A short sanrpling
ciisper..sing
a
in
concentrations
sampie
high exposureconcentrations,a longer
in the dispersionmocrei*uy o""
exposure'
time givesa more lealistic avelage
Raciiation'
using moclelswithin sIPNI's FRED 6ire'
estimated
be
can
rates
Dispersion
primariiy as a
moclels.FRED has been rleveloped
Exprosion.Dispersion)suite of
thus is weli
Assessmentstud.ies(seeEP 95-0352)
screeningtool for euantitative Risk
opco or
is not available for use within an
FRED
where
mod.elhng
of
type
suited to this
from
nu."r.ury, aclviceshould be sought
where specificcasestucliesu.J.or,riclered
SIEP'
t . , 2t l
^
r . - clictated
r r ^ + ^ + ^ . t 'by
the maxrmum co n c e n t r a t i o n o f
'HnS Riskt At'ea'
is
an
of
The classification
the Hzs to do harm is used
othe, *or,r. the potu.rtiul for
HrS in the process str.eam . In
of the dispersion is
that an accurate estimation
acknowledgecl
is
it
as
criteria
as the
difficult to Pledict'
10 ppm could occur
that Hrs in concentrations above
However. it may be possibre
perhaps public or
,Hrs Risk Ar;"
for example on a neighbouring,
outsicle the classified
necessitate the
Determination of this risk may
accommodation.
or.
faciiity
party,
thir.d
aggl'egate risk to
i.r.rrrairr* the calculation of the
use of more rigorous eRA t".irniq..u.
leak scenarios'
RiskA'La'clue to the cred'ible
the.I"rrifi"diHrs
outside
ind.ividuals
neghgible region' a
may be very low, perhaps in the
Arthough this aggregate risk
d'irection resulting in death
cond.itions with irr" *i"d in a
r.eleaseunder stable weather
yardstick would the'efore be
be feasible. A more suitable
nevertheless
could.
effects
or ill
the d-istance to neighbouring
d.istance oi irs r"^rT. to fix
the use of the maximum effect
in terms of effect
gives an i.nd.icati6n of the consequences
ar.easof concern. Table v. r
'worst case' dispersion scenarios'
of
distances of an arbitrary sel"ection
in a comm'unity
residents (eg infants, elderly)
It shourd be noted that sorrre
the working
than
Yrrore severely ;t lower levels
around a plant rnay react
population.
and is also
HZS is burnel i" the atmosPhere
when
formed
products
the
of
SOois one
often Present in combination
formed.whenpv'"pr'"ricironsulphicieoxidises.Itisalso
with HtS.
_-.rr^^^+.
gas (or liquid) with a strong suffocatrng
non-flammabre
Surphur d.ioxideis a colourless.
in sputum
and. causes coughing. an increase
odour. It is a respiratory irritant
at low concentrations.
production and b,o,,choconstr.iction
been set in order
rimits for sulphur dioxicle have
Recommend.edoccupational expos*re
of Governmental
The rggunggb American conference
to prevent these acute symptoms.
on an S-hour time
(ACGI}I) Thr.eshord.Limit Value based.
Ind.ustr.ial Hyelenists
Limit is 5 ppm'
15-minute short Term Exposr'r.e
weighted.average is 2 ppm.The
conversei5'rvhetr
be consicleleclto be nou-cor''.-osive'
can
watel'
fi'ee
of
absence
H,,S in the
such zr'sstalt-upishr'rtclurLngabnorrnal situzttions'
flJe rvater is plesent, especialiv
u'iIl most probabl]' take lliacel'
ottt a iircii' general con'osion
circr'riating
or
d.rilling
clown.
present' either'
ions ?l"nr"tttal sulphrtl' al'e
If calbon d'ioxide. o]:ygen' chior"ide
7
1995
E P 9 5 - 0 3 1 7R e v r s t o0n 5 O c t o b e r
H
S u l p h i d e( H z S )i n O p e r a t i o n s
H S EM a n u a lE P 9 5 - 0 3 1 7H y d r o g e n
inc iiy ic iua l l l ' o r to g e th e l th e n s e v e re col rosi on may take l tl ace w i thi n
per . iod. F u rth e r. d e ta i l s a re g i v e n i n A ppendi x III.
l)
iron sulPhide
3.3.2 PYroPhoric
pyrophoric iron sulphicle can be formeci on the internal surfaces of carbon steel
equipment containing HrS. h'on oxiclepresent on the internal sttrfaces will react u
the HoS ancl form p-r'rophoriciron sulphide which, on exposure to oxygen can autorgnitel This pr.ocessand the means to manage the hazard are detailed in Appendix
Although pyrophoric iron sulphicle can folm and collect on ali internal surfaces of
Lrl
ff:""
vessels
pigreceivers
\-
:::" .:T,T,:T:,:::
storage tanks.
\\[ei]st steps can be taken to reduce the formation of pyrophoric ilon sulphide it m
never be assumed that there can be an absolute prevention of the reactionTherefore any equiprnent constructed of carbon steel which is in contact
iron
sour hydrocarbons should be treated as if it contained pyrophoric
sulphide.
Great care must be taken on opening equipment likeiy to contain pyrophoric iron
sulphide, for its removal, d.isposal,etc. For further detaiis see Appendix IV.
ll
EP 95-0317Revtsion0 5 October1995
CONTROLAND SAFEWORKINGPRACTICES
points in turn:
by examining each of the following
derived
is
contrors
of
The framework
in what concentrations (Hzs Area
.
where is H2S likely to occur and
Classification)
(Hzs
the concentrations measured/monitored
how wilt H2s be detectecl ancl
Detection)
presence of H2S (warning signs)
what is needed to warn of potential
(Access controls)
to H2s d.esignated areas
what is need.edto control access
areas
work is carried out in H2S designated
what is needed.to control how
(Permit to Work)
must be carried/used- in H2s designated
what protective breathing equipment
Protective Bquiprnent)
areas (Respiratory
areas
for access/work in H2s designated
what procedural controls are required
.
'
r
r
r
\-
o
o
(Proceduralcoot"olsandStandinglnstructions)
in H2S
for personnel accessing/working
o
what competence levels are needed.
in HZS procedures)
designated areas (Competence
used:
on the type and extent of controls
The following factors have a bearing
entering
(eg sampling from H2s-containing equipment,
.
the tylpe of work activrty
vessels, etc)
(ie degree of exertion)
o
the level of human activity
reiative to potential H2S sources
'
the location of work personnel
rthenumbersofworkpersonnelinvolved(particularlylargenumbers)
release
.
the potential for an uncontrolled
or upsel
out (eg shutdown/start up, concurrent
.
the type of operations being carried.
oPerations)
effects of vibration'
of equi.pment (eg leaks, cracks,
the state of integrity of items
etc)
still
cond.itions (eg inversion, wind
the occurl.ence of abnormal atmospheric
etc)
conditions [often at night]' storm'
o
o
pelsonner'
I
EP 95-0317Revision0 5 October1995
H
HSE ManualEP 95-0317HydrogenSulphide(HzS)in operations
V
4.2
l)
HZSArea Classification
the release of heavier than air vapours (> 1.05 x d.ensity of air) from a liquid spill
an atmospheric vent at very low velocities.
ii
10
E P 9 5 - 0 3 1 7R e v i s r o 0n 5 O c t o b e ir9 g 5
H2S concentrations
and the effectson exposedvictims
H25
concentration
limit in gaseous
Derived maximum
H2S concentration
in air (ppm)
Effect on victim
Required action
for victim
>500
200 to 500
Maj orsymptomscausi ng
permanentphysiological
damageor death.R api dl ossof
senseof smel l .Lungoedema
afterabout 30 minutes'
exposureand may stilloccur
some time after rescue
Minor,reversiblesymptoms
such as irritationof eyes,nose,
throatand lungsfrom exposure
for maxi mumof 10 mi nutes.
A t 100 ppm senseof smel ll ost
w i thi n3 to 15 mi n. A t 200 ppm
senseof smell lost raoidlv.
Occupationalexposurelimit(for
8 hr exposure,ACGIH
documentationof TLVs).
Settinqon HzS alarm svstems
No svmptoms
Removalto safe
atmosphere.
Artificialrespiration
Removalto safe
atmosphere.
Artificialrespiration
Process
streams (ppm)
>500
<500
10to 200
10
<50
<10
Removalto safe
atmosohere
N one
None
E P 9 5 - 0 3 1 7 R e v r s r o n0 5 O c t c b e r 1 9 9 5
11
ldentifyH2S sources,
collectand analYse
praess/f acilitiesdata,
establishrelease
mechanisms
H2S-freezone
presencepcsible
duringnormaloPerating
conditions?
DerivedH2S
conccntrationin air
<200 PPm?
air may
As shown in Figure 4.1, all areas where the H'S concentration in
marked
be
be designated Hrs risk areas. They should
exceed 10 pp*in"u
minor or
upon a dejicated set of drawings together with the associated risk:
rnajor.
plesence is expected,
Note: During d.riiling or workover operations in areas where HrS
precautions as for the
the level of exposure cannot be accurately pred.icted.In that case'
highest level of accid.entalexposureshould be undertaken.
be pr:esent
For exploration driling in new areas it should ahvaysbe assumedH"S may
and precautionsestablishedaccordingly'
4.3 HZSDetection
personnel against
The objective in HoS detection is to provide early warning to caution
HSE precautions'
entry into a kno*ri hazardous area without taking the appropriate
Amongst the key points in defirung a detection system are the following:
.
ii
12
EP 95-0317Revision0 5 October1995
;i!''.!;.b-g-i"/.
'
.r-.ifi,.-__
Only equipment specifically developed for the detection of HrS will achieve the clegreeof
responsenecessary to alert personnel.
It is important to be aware that all detector systems have an in-built delay between HrS
release and its detection, due to the response time of the system and its components.
WHEN A}.I HzS ALARM IS SOUNDED THE GAS HAS ALREADY BEEN
PRESENT FOR SOME TIME AND I\{AY HA\M ALREADY REACHED
DANGEROUSCONCENTRATIONS!
4.3.1 Fixed systems
No matter how well designedthe facihty and how good the stand.ard.of operation an4
maintenance,the possibility of accidentalreleaseof HoS cannot be totaliy discounted..
For this reasonit is recommendedthat HrS detectionsystemsbe installed.in high HoS
risk areas,defi.nedas those where:
'
liquids with HrS contents which could glve rise to comparable H"S emissions with
the resultant possibility of a major hazard occurring outside the facility bound.ary.
4.3.2 Portablesensors
In addition to the fixed HzS detection systems, portable sensors are used.for alerting
the individual and should be availabie to designatedpersonnel.They may be used.in
locationswhere it is not practical to install fixed sensorsand can also pror.ideback-up
facilities in the event of a fixed system failure. These d.evicesusually glve an aud.ibie
and visual warning if a preset levei is exceededand pro'"ide the ability to have a
continuousread-outof the concentration.
EP 95-0317Revision0 5 October1995
13
sulphide(HzS)in operations
HSE ManualEP 95-0317Hydrogen
of the portabie
lnventories and the aliocation
foliowing:
.
OperatingManual
EmergencyProceduresManual
ContingencYPlans'
in the
d,etectorsshoulclbe clescribed
be robust in construction
and operated by one person
be capableof being easily hand.Ied
eight hours
rechargeabre,rasting at least
have a integral power source,
be easy to calibrate
alarm on failure'
'
.
4.3.3 Personalmonitoringsystems
is exceeded'
used to-wa.rn that a preset level
personarHrs monitoring systems are_only
as testers'
de*ri.". ,ro, should they be used
gases
They are not meant to be ,i""rrrring
diffusion characteristics of toxic
personal monitoring ,yrt"*, are based.on the
which generate-san electric current
Juctrochemi.ur-J"r"ctor
"r
and usually incorporate
an audible or visual
This current is converted into
as the toxic gas passes over it.
a personal H2S monitor
to be consideredin selecting
Th"
(or
both)
;"rnts
signal
dispray
ur" d."t.ribed in APPendix VI'
is made fully
d.escribedabove is that the operator
monitors
the
using
for
has to be
A prerequisite
the equipment and of what action
rimitationsof
and.
aware of the capabilities
sensing head should'never be
being tri#red
alarm
the
'poison' most
of
lt
event
the
in
taken
of HrS will quicklv
Higii*ar
"ti;;it"*..
or
clothing
by
shieided
personal monitors'
the manufacturer's
be tested.in accordancewith
shouid.
equipment
and
systems
AII
strict application of
,;;;1;$r, "rtuuii.h"d. tt"ough
maintenance
the
or
recommend.ations
depending on the particular
6cno ilethod'oiogy
the Reliability centred rvr^irrt"nance
The functioning
situation-BecauseHosdetectionsystemsarep'i*u'iif*u"'i"gd'evices'notonlythe
speed.of '..porr.e of the sensor'
the
also
urrt
verifiua
be
accur.acyshould
devrces'operator
as visual beacons.audible warning
such
parts
system-related.
the
of
at i'egttlat intervals and
and.arike should also be verified
."rrtre
controt
the
in
to
interfaces
shourd.be given to accessto detectors
consid.erurron
Due
,rr".
of
beforeeachperiod
'estrlts of rvhich should be
testing and calibration, til"
maintenance
frequent
enabre
recolded.
VI'
For further details seeAppendix
14
1995
EP 95-0317Revision0 5 October
fif,H:T::Tffi"ff,*H'$5;fttTilHffi::;*,:iT;:l;,m
'I
level of training should also be marked by appropriate signs and markers. Signr
pictorial content are preferred to text only.
Ij
\-
4.5 AccessControls
Procedures must be in place for access,escape and movement control of personnel in
HzS designated areas. These should include:
.
all personnel should sign in and out at a central control point, outside the area,
where competency certifi.cates are checked
special instructions concerning the work location, (normal access and escape
routes, wind direction)
radio communication
The procedures may vary for different tpes of iocation (eg onshore or offshore) but
should be prepared for the different activities which have to be performed.
EP 95-0317Revision0 5 October1995
15
HSEManua|EP95-03lTHydrogenSulphide(HzS)inoperations
job, together
pointecrout to personsdoing the
wind,sockstrategicalrysited and
instructions as to where to escaPe
with
positioned
adequatearea warning signs
osCCesscontrolrequirementasdescribedin4.5
tag board
o
us made of personaltags and central
for the type of environment encountered
r
acld.itionarprotective clothing provided
person and positioned correctly
o
safety equipment checkedby a competent
lines
BA; portable d.etector;belts and life
ie compressedairrine BA; self-contained
to a piece of equipment
required.;positive isolation of aII lines
8)
r
eotry into a confined space(seeRef'
waterwetting of any possible
For example: removar of pyrophoric sludge/debris_and no entry if H2S above
and 02 levels;
residues; gas testing ro, fl"*mable, to,.J
then lower HzS limits may be
L0 ppm (if escapeis particularly time consumin!
if possible'
consider"at' rr"th air flow to be established
o
frequency of testing for HoS and by whom
.retestingforHzSpriortorestartinganyworkperiod
greater degree of dilEculty where it cannot
.
for work of an increased.time scale or
wil remain below 10 ppm' The wearing
be guaranteed.that the averageHos level
shourd.be stipulated. (A11possible
of a compressedairline breathing upp^r"tus
of
be und.ertakenbefore the extensive usage
steps to gas free the equipment ,rrorrra
BA is accePted)'
full Hos protection):
NO ENTRY (exceptin emergency,with
not
even if flammable vapours or H2S are
o
if the confined spaceis being inerted,
Present
16
EP 95-0317Revision0 5 October1995
4.7
1t
I
protective
Respiratory
equipment
Typeof Apparatus
Description
Application
Compressedair cylinderscarriedon
wearer'sback supplyfull face mask
throughflexiblehose
'Positivepressure'
mode
recommendedfor H2S-
'Positivepressure'
mode minimises
pullingtoxicvapouraroundseal of
face mask
contaminatedenvironmentup to a
max. 20,000ppm (2%) H2S
Duration30 or 40 min dependingon
cylindercapacity
Suitablefor escape
Compressedairline breathing
apparatus with full fuce mask
'Positivepressure'
mode with
cylindersrecommendedfor H2Scontaminatedenvironmentup to a
max. 20,000ppm (2%) H2S
Directsupplyfrom a compressoris
less reliableand not recommended
Not suitablefor escaoe
Combination of self-contained
and airline breathing apparatus
(cascade system)
Self-contained
breathingapparatus
with compressedair cylinderand
provisionfor connectinginto
compressedair supply
Emergency escape BA sets with
full face mask
Type | - Smallcompressedair
cylindercanied in jacket pouch/
shoulderstrapsuppliesfull face
Duration10 or 15 minutes
dependingcylindercapacity
mask throughflexiblehose'Positive
pressure'mode prefened
Type ll - Clearplastichood sealedat
neck.Air suppliedfrom cylinder
throughflexiblehose
Chemical canister respirators
EP 95-0317Revision0 5 October1995
Duration5 to 15 minutes
Easy to put on
Only to be considered for use for
escape purposes subject strictly
to conditions descrlbed in
Appendix Vll
17
Protectionlevelclassification
Level of protection
Description of protection
Monitoronly
For work closeto a potential sourceof leakagethe mask should be hangrng from
the neck 'at the ready'.
'to hand'
For work further removed from a potential source of leakage having the mask
ready, nearby and in the line of escapeis sufficient.
'standby' should always
However, a potential rescuer and/or the buddy on
'at
the ready' and use a BA set.
have his mask hanging
In areas where HrS is normally present (refer to Figure 4.1), Ieve1F shall always apply.
In areas where HzS presenceis quite possible first entry shall always be made with
protection at level F. Only once the area has been made safe can the level of protection
be reduced,eg to level B.
A BA set may either be self-contained,or air hose supplied.Where an escapeBA set or
BA is to be 'to hand', reliance may be put on strategically placed communal sets.
Individual allocation of sets is, however,preferred to avoid the risk of confusionin an
emergency.If appropriate,safety belts with lifelines to permit easy rescuemay need to
be worn.
Refer to Appendix VII and Table VII.1 for a summary of the main work scenariosand
the recommendedlevel of personalprotection.
4.7 .3 Protection in event of accidental release scenarios
The following guidelinesmay be used to determine personalprotection for escapefrom,
or rescuein aleas where HoS is not normaliy present but only after an acciclental
release.
200 ppm (< 500 ppm in
Where the maximum HrS concentrationin air wiII not exceed.
process),where escaperoutes are sholt and the need for rescueis unlikely, it is
sufficient to use a monitol QevelA). This might apply to visitors to site, operators
carrying out routine checks,or maintenancepelsonnel cioinglight work. eg painting.
18
EP 95-0317Revision0 5 October1995
Consideration should be given to how personnel will be alerted when they are not
actually breathing from their BA sets. Reliance on a warning from personal or frxed
monitors can provide adequatewarning for a distant sourceof H2S when concentrations
cannot build up too quickly. For closer sourcesthe sound or sight of a leak will provide
much earlier warning. However, the employeeat risk may not be alert to these
'standby' in such
warnings if engrossedin work. Hence, the importance of a buddy on
HrS work situations. The 'standby'shall be positioned out of the danger area and shall
have no work responsibility other than that of obsennrngthe workers within the danger
area and giving the alarm.
I
I
-t
tI
t
The proximity to the source of a possible release and the time it takes to reach a
dangerousH2S concentration are thus important in deciding the state of read.inessfor
the donning of a BA set.
.t
4.8
'1995
EP 95-0317Revision0 5 October
19
4.9
HZS Competence
4.9.1 Competencerequirements
Sites with HtS classifiedareas should.have a three ievel competence
schemein place.A
medical assessmentshould be required for personnel at levels
2 and.B to id.entify any
factors which may preclude a person from wearing breathing
apparatus. Local
reguiations may require more specific med.ical"rr"rr*ents. personnel
with known
physiological or psychologicalcond.itionsthat impair
their normal respiration shall not
be assignedto work involving potential exposure to HoS or
sulphur dioxide
environments if use of breathing equipment o, exposure itself
is likely to complicate
their respiratory problems.
Level 1 - Familiarisation
AII staff and visitors to the site should.be aware that the
site contains HrS classified
areas' and of the hazards and risks of HoS. They should.also
be aware of the emergency
-should
proceduresin the event of a releaseand
be informed.and where necessary
instructed in the following:
o
o
.
systems
ll
20
EP 95-0317Revision0 5 October1995
.t
I
r \-1
I
Staff with special duties with respect to contlol of HrS or to emergency response during
a release will require specialist competence in those aspects of their duties in addition
to competence at Level 2. Such staff includes emergency response teams, medics,
production site supervisors, drillers and toolpushers, and safety officers.
-'l
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I
4.g.2 Trainingprogramme
The training programme should be commensuratewith the level of competencerequired
and may be on an individual basis or as a training course.Where the training cr
run externally, or is not specific to the worksite, further training on the procedt
detailed.arrangements for the particular worksite should be given.
Competenceat Level 1 can normally be achievedas part of the general site
introduction. the essentialpoints that must be covereclas a minimum at this le'
given above.
For staff required to be cornpetent at Levels 2 or 3, a comprehensive tr:
prograrnne for designated personnel should contain the following aspects
plus any additional local requirernents:
I
H2Sintroduction
I
J
what is HrS
characteristics
physical properties
rrrasurement of atmospheric
.oncentrattons
CIL\D
I
sources
effects on health
effects on environment
effects on equipment
colour coding
ldentification
o
safety signs
access to worksite
prsonnel movements
wind direction/indication
self protection
buddy system
l'escueprocedure
transportation
evacuation
contingency plans
prmit-to-work system
EP 95-0317Revision0 5 October1995
21
HSEManualEPg5.O3lTHydrogenSulphide(HzS)inoperations
Detectors
servicin g recluirements
fixed
portable
personal
alarm settings
positioning
Iimitations
sensitivitY
calibration
ResPiratoryProtectiveequiPment
aratus
self- contained breathing app
cascade sYstem
escaPesets
servicing of BA
First aid
o
fesuscitation
artificial resPiration
programme
4.g.3 Specific elementsof the training
be adhered to in
fotlowing guiderines should
the
training
providing
when
r".r.l of .otttpetence is achieved':
order to ensure the "ppropti"a"
.
breathing aPParatus(BA)
and participate in
require all pe'sonnel to wear it
should
BA
of
use
the
in
any
Training
be of a duration sufficient to highlight
shourd
This
,"rri*.
work
a simulated.
in a search and rescue situation'
constraints which could.be d.etrimentar
.
detectors
The use of Portable a n d o t h e r t y p e s o f H " S d ' e t e c t o r s w h i c h a r e p r o v i d e d o n t h e
b-vall participants'
instaliation should be practised
first aid
with actrve
practical sessionson resuscitation'
Training in first aid should include gurr. first aicl should'also be explained if this
participarion by ail course memberr.
of injury'
this co,rld be beneficial in the case
is not separ.atelytrained for as
22
EP 95-0317Revisron0 5 October1995
,l
Competencycertificate
Opco
l
, l, '
l
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HrS Competency
Certificate
4.9.5 Competencereview
Proper recordsshould be kept for each person assignedto installations, indicatinp
instruction and training were received..Competenceshould be reviewed regularly
carrying out drills at the worksite. Experience has demonstrated that drills are
extremelv effective.
E P 9 5 - 0 3 1 7R e v i s i o n0 5 O c t o b e r ' 1 9 9 5
23
1I
J
5 Recovery
RECOVERY
5.1
E m e r g e n c yP l a n n i n g
I-i
5.1.1 Emergencyequipment
-l
I
Locations where HrS can be present in the air above the TLV-TWA of 10 ppm s
6ave the following equipment in addition to that provided for normal operation
,j
1I
.t
II
.l
spare self-contained BA sets + spare bottles (two additional sets against number
being used)
spare escape sets (two additional sets against number being used)
interpretation
rescue operations
I
;
I
"i
EP 95-0317Revision0 5 October1995
25
for protecting
Emergency Response Procedures for HrS reiief should include controls
people outside facility boundaries.
5.1.3 RescueProcedures
and practised
For every site defined as an HrS area, a rescue pian should be developed
plocedures and of the
as a regular check of the effecii reness of the emergency
together with the
practice
competence of the personnel involved.. The frequency of
in the HSB Case'
,..q,rirud performance criteria for the drills should be established
part in a rescue
Where local medical facilities may be called upon to treat or play a
for the
procedu'e it shoulcl be confirmecl that personnei are awale of the requirements
treatment of HrS Poisoning.
part of the person
The rescue proced.uresshould be based.on minimum action on the
action of the
sighting the victim, ie to raise the specific alarm. In other words a single
The details of
witness should. be sufficient to set the rescue proced.ures in actionto the
information
medevac,
organising med.ical assistance, manpower assistance,
point'
,"Jporrribie Supervisor should be left to be organised by a central
spot provided they
This will allow the witness to take immed.iate rescue action on the
are equipped and trained to do so.
Rescue procedures should contain the follorving:
.
rporting code
witness actions
is permanently
The central reporting point should. be situated in a location which
alternatives.
manned. and alJay. safe. ti ttti. is not possible. procedures shouid indicate
points, a
This point should be contactabie from the field r.ra dedicated manual call
point
reporting
central
d.ed.icatedemergency phone or a dedicated lacl.iochannel. This
should be the focal point for cailing in resources, ie medical assistance, experienced
manpowel, transport, nr.edevac,etc.
be vested with
This central reporting point should. have the requisite expertise level and
higher'leveisto
the authority to call in such l'esoLu'cesrvithout, having to refer
of the
The reporting code shouicl be sholt ancl precise, it shouid contain the location '
eg HoS
caller..his name and a single catchwolcl to ind.icate the nature of the incident,
\riCTIM' and possibly the number of pelsons involved'
Witness actions: Before an)'resclle attempt tire witness should raise the alarm.
is
Thereafter. the witness could tr'-va linritecl fesctre attempt provided heishe
26
EP 95-0317Revision0 5 October1995
l
l
5 Recovery
equipped to do so, ie when he is wearing a BA set the witness could try to isolate the
source of the leak.
.t
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_t
I
J
I
'J
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'
The witness should evacuateto a safe area (eg upwrnd of the HoS source)and ,
sets when possible.Provided one BA set is available and the witness has given the
alarm and is familiar with the use of the BA set, the witness should try to carr
victim to an HoS-freearea and try to resuscitatehim. A single person attempti
rescueneedsto be aware of the risks. If unable to remove the person and a secondBA
set were available the witness couid.try to put this set on the vrctim.
-l
I
I
on HoS
Other points
Harmful exposures only occur by inhalation. Intake via other routes is of no medical
significance.
The use of 4-dimethyl amino phenol as an antidote for the systemic toxic effects of
HrS is not recommended. Experience has shown that, following successful
resuscitation. recovery will usualiy be rapid and complete without the use of an
antidote.
The reporting point should take all the necessaryactions as iaid down in the
emelgencyprocedure,thereby relieving the personson site of ail organisational
reporting matrers such that thet'can dedicatetheir efforts to rescuingthe endangered
hfe.
E P 9 5 - 0 3 1 7R e v i s i o n0 5 O c t o b e r1 9 9 5
27
5.2
operations
Firefighting
5.2.1 Hazards
Pure HtS is a flammable gas. If burnt in the atmosphere
it forms sulphur dioxide (refer
to 3'2'3) and water. In concentrationsof 4.3 to 46.0 per
cent by volume in the
atmosphereit will readily burn upon ignition. In
most situations Ho
with other saseswhich mav be light oJh"u'oy.pure
Hrs;;;h;#t
which could be
releasedfrom a rich surfinor soruiion is slighiry
h;;;;
than air.
5.2.2 Precautions
In the event of a fire of HrS-containing material, it
is usually better to let it burn under
control until the sourcehas been isolaied rather
than releasl Hrs to the atmosphere.
@xposureto the resultant sor, should be avoided.)The;;ffi;
equipment should
be cooledand wherever possibieattempts mad.e
to d.ispersethe sulphur dioxjde product
of combustionby water sprays.
The decision to allow a fire to continue will d.epend.
on the circumstances.If the escape
is small in volume and can be isolated easily then
extinguishment could be the
preferred course of action. A11approaches
must be from an upwind direction by
personnelwearing a self-contained.
breathing apparatus.
5.2.3 Generalprocedures/guidelines
The responsibilities for salvage/clean up
and the proceduresfor breathing apparatus
for
firefighters are described in Ep g5-0ssi
Fire Control and
Recoverv.
28
EP 95-0317Revision0 5 October1995
I
6 Guidelinesfor the Preparationof H2s procedures
,I
_l
I
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I
GUIDELINES
FORTHEPREPARATION
OF HzS
PROCEDURES
;ilT#::;'ffi";::::::ffi*:l';""J.:ffi";.,"uu,.bedef
;m:ilt'Ji" ##Ti?$:'1fffitff;'Te
'
'
equipment
than
isreasonabrv
h'"3tumil3;i:;:;ff;n?T##ff;::ffi-":ffi"'ffiJlilff
.-
: ::;"j;il:ff';:H:i:,":n::."
o
6.1
The procedures should be based on the health risk assessment. The following elements
related to personnel protection should be covered as a minimum. The requirements
need to be defined for:
.
work method
breathing apparatus
detection/monitoring
wind indication
escape routes
rescue plan
equipment
Depending on the work scenario and HrS concentrations involved, the wearing of
personal monitors, BA sets, escape sets, portable detectors the use of the buddy system,
etc should be determined for the different stages of the job.
It should be made clear and known who is authorised to conduct the general site
introduction.
A s1'sten should be set ttp to ensure that all site personnel have a valid HrS certificate.
Numbers of staff on site at any given time shouid be kept to a minimum.
EP 95-0317Revision0 5 Octobertgg5
29
isolation
depressurising
boxing up
spading/Olinding)
flushing
drying
opening up
vessel entrv
line up
prssure testing
draining
recommissioning
puf glng
despading/(deblinding)
6.2
'
'
'
'
6.3
Production Operations
30
EP 95-0317RevisionO 5 October1995
!tK--ffiirurun***,.o'l
_t,
:t
_t
:l
6.3.1Sampling
Whereverpossiblestreamsshould be sampieddownstreamof the HrS removalpr.ocess.
Sour stream samplingshould be minimised.
Sampling should only be carried out by following approveclproceduresancl uncler a
permit to work system.
All sampling to be carried out by a minimum of two peopleof which one is always an
observer.
Samplepoints should be designedto minimise the volume of gas or liquid releasecl
during the operations.A.ty releasesshould be remote from the person taking the
sample,ensure that the concentrationof HrS in the atmosphereis below 15 ppm (the
15-minuteexposurelimit) and be directed to a restricted area. If this cannot be
achieveda BA set should be worn.
Samplepoints should be assessedindividually, based on the volume of HrS that coulcl
be releasedwhen the sample is taken and the degreeof dispersion".rr-,*irrg worst
conditions.In any casea BA set should be worn for sampling sour LPG where the purge
is releasedcloseto the sample point. Even with all these precautionsthe operator
should always remain upwind of the sample point.
'1
I
,
I
6.3.2 lsolation
Equipment should be isolated in accordancewith 'the minimum mand.atorvisolation
requirements'as iaid down in EP 95-0230Design and Engrneering.
A doubleblock and bleed consistingof two separatebiock valves with or without a
spectacieblind is recommendedfor all systems containing toxic fluids und.erpressure.
Isoiation, depressurisationand purging of the main system followed.by iocal isolation is
always preferred.This reducesthe number of isolations against high pr.essur-e
or toxic
material and the amount of valving needed.
EP 95-0317Revision0 5 October1995
31
S u l p h i d e( H z S )i n O p e r a t i o n s
H S E M a n u a l E P 9 5 - 0 3 1 7H y d r o g e n
6.3.3 Depressurising
Depressurisingof equipmentand processlines should be clonethrough the process
vent/relief system to the flare. When this is not possibleand equipment has to be
aII sourcesof ignition should be eliminated from the area where
clepressurised,
flammabie vapours may accumulate.
Roacisshouldbe closedoff and signspostedto keep vehiclesand other potential sources
of ignition away from the area.
Attention should be paid to the wind direction in defining the extent of the possible
hazard, in particular with the location of living quarters, workshops, control room or
other areas where a number of peopleare continuouslypresent.
Concentrationsof HoS vapours should be measuredcontinuously and the rate at which
depressurisationtakes place is to be limited to ensure dispersionof the H2S vapours at
safe concentrations(ie no risk of personalexposuresin excessof 10 ppm). Such an
operation should not be carried out in calm wind conditions.
6.3.5 Purging
Irrespectiveof whether HOT work is planned on equipment or process lines it is always
goodpractice to purge the systemsto be isolated u'ith nitrogen gas or other suitable
inert medium.
Any of the following methodscan be used:
fill the process lines and equipment with watel', aftel which the water is drained
and replaced by nitrogen
Not recommended for corlosion-sensitive or cryogenic systems.
32
EP 95-0317Revision0 5 October1995
o
,rl
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I
I
I
Venting the system during the purging operations must be done from various vent
points in the system to ensure all sections of the system have been sufficiently purged"
Repeatedlypressurising the entire system with nitrogen gas should ensure that the
dead legs in the system get sufficiently diluted with nitrogen gas.
For HOT work to take place on processlines the hydrocarboncontent should be less
than 0.1 per cent by volume.
'l
l
a
pressurisethe entire system with nitrogen gas and vent to flare or atmospherea
number of times (test as above).
Specialcare should be exercisedwhen declaring a system safe for HOT work when
lower explosivelimit levels are being determined d.uring the relative cool hours of the
night or morning. Processlines always contain minute amounts of hydrocarbon
productswhich will releaseflammable vapours when heated up due to the ambient
temperature rise or direct sun radiation.
For further referencesee SSHC Guideline Gas Freeing and Cleaning of Oil Storage
Tanks @ef. 9) and EP 95-0270 GeneralWorkplacePractices.
6.3.6 Vesselentry
For full procedural guidelines on vessel or tank entry see EP 95-0270 General
WorkplacePracticesand HSC Guideiinesfor Entry into Confined Spaces1992 (Ref.8).
Further to the above guidelines the following precautions should also be taken:
.
the first opening of any vessel should always be carried out by persons wearing full
air supplied breathing apparatus with at least one person watching from a safe
distance, ready to raise the alarm and don BA in the event of difficulty
Once the first manhole is removed a check should be made of the internals for
debris and H"S.
if debris is present then steps shouid be taken to keep air from it, usually by
damping down
Air supplied breathing apparatus should be worn until such time as the HoS is
below 10 ppm and all of the debris is removed.Care should be exercisedas the HtS
ppm level may rise whilst debris removal is taking place.
EP 95-0317Revision0 5 October1995
33
H S E M a n u a l E P 9 5 - 0 3 1 7H y d r o g e nS u l p h i d e( H z S )i n O p e r a t i o n s
6.4
MaintenanceOperations
details of any other work taking place or planned in the vicinity, which might
affect or be affectedby the planned work schedule.
Oncethe basic planning has been established,the supervisorshould carry out a site
inspection with the personnel involved.
This inspection should include:
o
a check of any work taking place in the vicinity of the equipment being
decommissioned
The working team assignedto the job should then be properiy informed as to the
specificcircumstancesand requirements and be instructed and trained in the use of the
necessaryequipment.
34
EP 95-0317Revision0 5 October1995
I
APPENDIX
BACTERIA
OF HZSBY SULPHATEREDUGING
FORMATION
(sRB)
When the oxygen consumed by bacteria or by chemical interactions is greater than the
oxygen input into the water, a iowering of the dissolved oxygen content will occur. In
,l"ili"l:'JJ:ii;l11;:litTtr;:i;r"'"TH?i:::
:iffi::,i'*TJlffi
their metabolicprocessesleading to the formation of HrS and other bacterial products.
:H:ffi::'#:1ff"::::l,T.""uitions
wi'onry
becreate,
rorsRB
.
i
.-
a carbon enerry source,ie organicmatter such as oil or lower fatty acids (abundant
in formation water)
The temperature is another important factor which regulates SRB activity: growth
rates are optimal within a temperature range of 20 to 30"C. At lower temperatu
growth is reduced but is still evident at 5 to 10"C.
Hazards associatedwith SRB activity are:
Fornaation of HzS
HzS is sparingly solublein water and will, therefore, move into the atmosphere.This
could lead to lethal concentrationsof HoS directly abovethe water column and,
consequently,to unsafe situations particularly in areas which have restricted
ventilation.
Forr''ation
of acid compounds
Anaerobic growth of bacteria in water results both in the production of HrS and acidic
compounds.A drop in pH often occurs(a lowering of pH from 8.2 to 6.0 in a period of 15
hours is not unusual). The acid conditions created can contribute greatly to the rate of
corrosionof metals and the disintegration of any concretethat comesinto contactwith
the water.
E P 9 5 - 0 3 1 7R e v i s i o n0 5 O c t o b e r1 9 9 5
35
the difficultf in achieving a homogeneous mix between the biocide and the
stagnant water'
To overcome the resistance build up, dosing of alternative chemicals at intervals could
be tried. For example a weekly switch between two or more compounds or shock doses
every few weeks can be used.
Chlorination is also a possibility but there are doubts about its suitability
readily dissipates in stagnant water conditions.
as chlorine
A preferred alternative to the use of biocides or chlorine for controlling the activity of
SRBs is aeration of the water. This method is particularly attractive in the offshore
storage and separation of oil and water. Aeration of water volume in storage cells can be
achieved by introducing (compressed) air into the stagnant water, thereby severely
iimiting the growth of the anaerobic bacteria. A second method is by continuously
changing the water thereby maintaining an appreciable level of dissolved oxygen in the
water. If aeration of the water i's applied corrosion rates will probably be higher and
this will have to be taken into account during the design stage (material selection) or in
operation (corrosion inhibition).
The use of germicidal ultraviolet light in the treatment of the water may be another
option, but may not be fully effective if solid particles ale present.
If SRBs are suspected or confirmed, a testing programme should be set up at the
earliest practicable opportunity to evaluate the best control method.
36
EP 95-0317Revisron0 5 October1995
".e
..:Jnl.ria;,&.ba
r..--....
APPENDIX
II
PHYSICAL
PROPERTIES
AND PHYSIOLOGICAL
EFFECTS
oF HzS
ll.1
PhysicalProperties
Table ll.1
'\-
Physicalpropertiesof HrS
Property
V al u e
Auto-ignition
temperature
260"C
Boilingpoint
-60.2'C
Meltingpoint
-82.9"C
Criticaldensity
0.349g/ml
Criticalpressure
9 0 . 2 3b a r a b s .
Criticaltemperature
100.4'c
1.5392gll
Density:liquidat boilingpoint
0 . 9 9 3g / m l
Flammablelimitsin air
Freezingpointat 1 atm.
-85.5'C
Molecular
weight
34.08
Solubility
in water0"C, 1 atm.
0.6729/100ml water
1. 18 9 5
Vapourpressure-20"C
1 8 . 1b a ra b s .
ll.2 Characteristics
l" IH#*i:::rab1e
byitscharacteristic
rotten.egg
odour
At
soluble in both water and hydrocarbon liquids. Pools of water or sludge at the
bottom of a tank may thus contain concentrations of H"S and if ag:tated or heated
will release the gas
pure HrS is heavier than air and can collect in los' iying areas. especialiy pits
and sumps rvhich are closed-in and have poor ventilation. Horvever'. potentiall-"*
fatal concentrations of H,,S (ie 500 to 1.000 ppm) in ail do not act like a heavrerthan-air gas
'1995
37
is available
it can burn when mixed with air and when an ignitiou sottrcer
it burns with a biue flame anclgives off sulphur dioxide (SOu),which aiso provides
a health hazard (see3.2.3)
it can form pyrophoric iron sulphide on the internal surfacesof carbon steel
equipment containingHrS. Pyrophoriciron sulphide can auto-ignite when coming
into contact with air.
ll.3
PhysiologicalEffects
Table ll.2
effectof H2S
Physiological
Concentrationin air
1 ppm
Effect
Odourof rotteneggs can be clearlydetected
1 0p p m
15ppm
20 ppm
50 ppm
1 0 0p p m
200 ppm
The senseof smellwill be lost rapidly,and it will irritatethe eyes and throat.
Prolongedexposure(>20 to 30 minutes)may cause irreversiblepulmonary
of fl ui di n the l ungs.
o e d e m a ,i e accumul ati on
300ppm
Markedconjunctivitis
and respiratorytract irritation.Concentration
considered
to l i fe or heal th.
i mme d i a te ldangerous
y
500 ppm
700ppm
> 1 0 0 0p p m
U n c o n s c i o usness
at once.P ermanentbrai ndamageor deathmay resul t.
Rescuepromptlyand applyartificialventilationand/orcardiopulmonary
(C P R ).
re s u s c i ta ti on
38
EP 95-0317Revision0 5 October1995
.r?L"'
uiiliii*;!;;.*r*-.-,"
Effectsof H2S
Appendixll PhysicalPropertiesand Physiological
ll.4 OccupationalExposureLimits
The occupationalexposurelimits referred to below are thosepubiishedby ACGIH -1994
anclthis document is updated and published annually. Threshold Limit Values (TLVs)
are guidelines used when referring to the airborne concentrationsof substances.They
are called:
Threshold Limit Value - Tirne Weighted Averages (TLV-TWA)
The time-weighted averageconcentrationfor a nolmal eight-houl workday and a 40hour workweek, to which nearly all workers may be repeatedlyexposed,day after day,
without adverse effect.
Threshold Li-'it
E P 9 5 - 0 3 1 7R e v t s t o n0 5 O c t o b e r1 9 9 5
39
Ac u te e ffe c ts o f e x p o sure to H 2S
minor
irritation
o
o
lt nv
c,
;
I
I
I
II
I
I
i
t
10
<nn
IUU
" P o t e n t i a l l yl e t h a l f o r t h e m o s t v u l n e r a b l e p a r t o f t h e p o p u l a t t o n( 5 % )
R e m r n d e r : l h e s h a d e d a r e a s a r e o n l y a p p r o x r m a t i o n sa n d t h e g r a p h s h o u l d b e u s e d a s a g e n e r a l g u i d e h n eo n l y
40
EP 95-0317Revision0 5 October1995
*L
;;&b*b;.;..
.*q!&.-.
:.
I
I
Appendixlll H2SCorrosion
III
APPENDIX
HrSCORROSION
il
Generalcorrosion
The formation of iron sulphide, a corrosionproduct under the right conditionscan slow
down further corrosion.If iron sulphide scalesare adherent, tight and dense,the
generalcorrosionrate is expectedto be low.
Pitting corrosion
\-.
If the iron sulphide scales break dcwn locally the exposed fresh metal areas may
actively corrode leading to a severe form of corrosion pitting. High concentrations o
chloride ions, elemental sulphur, settled solids and oxygen are among the known cz
of iron sulphide scale breakdown. Carbon dioxide can also severely increase both
general and pitting corrosion.
lll.1.2Hydrogendamage
Sulphidestress cracking (SSC)
The hydrogenatoms embrittle the steel. At locationswith high stress and a susceptible
microstructure this leads to cracking of the steel and sudden failure.
Hydrogeninduced cracking(HlC)
The hvdrogen atoms diffuse to inclusions in the steel, mostly MnS, and AloO, where
they combineto form gaseous(molecular)hydrogen.The resulting pressule results in
the formation of cracks.mainly palallcl to the steel'swall. One or more surfacesof the
'blister' formation. HIC can occur in the absenceof applied
steel may bulge outwards in
stress.
EP 95-0317Revision0 5 October1995
41
lll.2 Protection
Protection of the equipment should be consiciered.
cluring engineering design and from
the outset of production operations ancl not
left until corrosion is d.etected..
Various
design and operational steps can be unciertaken
to limit (or at best eliminate) sulphide
corrosion and the ensuing hydrogen embrittlement,
namely:
Pitting corrosion
Traces of air should' be kept out, d.amage of
sulphide layer avoided. Inhibition with
oiVinhibitor system when corrosion monitoring
shows the corrosion rate to be
unacceptably high' The use of so-called HrS
,u-ri.trrrt steel refers to resistance to
cracking (see III'4) and has nothing to do with
resistance to pitting corrosion. some
stainless steels and, at high tempei'atures,
some nickel alloys can be used.to hand1e
very corrosive sour conditions. copper base
alloys may und.ergo accelerated.weight loss
corrosion in soul oilfield environment, particular.ly
*h"ru oxygen is present.
SSC
Plant should be constructed. fi'om steel which
complies with NACE guid.eline MR-0 1-75
(Ref' 11)' Main requirement is control
of the steei.s hard.ness to 22Rockwell C max.
There is no established protection for a piant
which d.oesnot comply with NACE and
which handles sour streams. such a situation
rvould constitute a clefinite safety hazard.
Htc
All .olled steel p'oducts lihe p'esstr'e 'essels
and seam-rveld.ed.
pipe sho'ld comply with
DEP 31'40'20'31-Gen @ef. 12), rvhich limits
the suiphur concentration in the steel to
0'003 per cent and requires the steel to pass
a qualificatron test. Forg:ngs ancl seamless
pipe are normally less susceptible to III-C
than eq.ripment made from plate, however.,
there have been occurrences of HIC in seamless
pipl within the gr.oup.For seamless
linepipe it is normal to specifi' IIIC testing.
Fo'. seamiess piping in p'ocess plant, where
monitoring of HIc damage is possibie. it is
normai to specif-v" Lu*iroum sulphur
content of 0.01 rvt pel cent in the steel.
In contr"astwith SSC, HIC can be monito'ecl
with trlr,'.asonicinspection techniques
because it develops mol.e slowi1'. horve'er'. suclclen
failure fi.om HIC has occurr.ed.,
Exposure of eqtripment to conciitions ri-hich
could possibll' cause HIC is oniy allowed
in
exceptional cases' and onlv rvhen stirtable
monitoring ancl inspection progl.ammes
are
implemented.
42
E P 9 5 - 0 3 1 7R e v i s r o 0
n 5 O c t o b e r1 9 9 5
Appendixlll H2SCorrosion
\\Tren conditions permit. an internal organic coating ls an acceptable defence (Ibr I
not for SSC). Inhibitors ale not accepted as an established defence againstHIC. In
general. drying is the best defence agarnst all risks stated above. Removal of the H
solve materials problems by chemical scavenging or absorption is not a practical
method.
'
\-
'\-
References:
NACE Standard MR-01-75 Gef. 11)
DEP 31.40.20.31-GenLine Pipe fol use in oil and gas operations under sour conditions.
(Ref. 12)
P i p i n g C l a s s e sD E P 3 1 . 3 8 . 0 1 . 1 5 - G e n( R e f . 1 3 )
lll.5 Maintenance
SparePartsSour ServiceEquipment
Use of spare palts and replacement mateliais must be subiect Loextra plecautions. A
control system must be in folce. ensur'rng that spare palts and materjals for repail and
maintenance of sour system al'e n-rantifacttrredto the NACE specified materials
specification.
T h i s o f t e n r e q u i r e s a d e d i c a t e c lm a t e l i a l s i n v e n t o r y c o n t l o l s v s t e m . N , i a i n t c n a n c ea n c l
materiais supply,'staff must be rnaciefulh- awal'e of the special r:eqtrilements fol sour'
selr..iceequipment.
0 5 O c t o b e r1 9 9 5
E P 9 5 - 0 3 1 7R e v i s r o n
43
AppendixlV Pyrophoric
lron Sulphide
IV
APPENDIX
R O NS U L P H I D E
PYROPHORIC
lV.1 Formation
'
Iron .sulphide is formed when st,eelcomes into contact,with HrS in the absence of
oxygen. When formed as a corrosion product in this way it is usualiy very finely divrder
and oxidises rapidly on exposure to the oxygen in air. This generates a lot of heat and
pyrophoric iron sulphide can auto-ignite. This can cause an explosion or fire if
hydrocarbons together with air are present. The chemical reactions are complex but ca
be simplified to (chemically unbalancecl):
FeO+HrS)Fe*S*+H2O
FeS + Oz J
\--
Even if hydrocarbons are not present, the exothermic oxidation of pyrophoric iron
sulphicle can generate enough heat to clamage the equipment.
Pyrophoric iron sulphide can form even at vely low H"S concentrations (<0.1 ppm) as
long as the partial pressure of HoS exceeds the partial pressure of oxygen in the
environment. The amounts formed will of course be reduced if the internal surfaces are
cleaned regularly and kept relatively free of iron oxide by remoting the water produced
during the reaction. Iron sulphides formed at high temperatures are more reactive
(oxidatively) than iron sulphides formed at low temperatures.
\*
Great care should be taken when opening up equipment to the atmosphere. Oxygen wi
react w-ith the pyrophoric debris in an envilonment which is not yet hydrocarbon-free
and thereby cause an explosion and file but even when hydrocarbons are removed the
pyrophoric debris can stalt burning spontaneousiy.
One should rernernber that in pyrophoric matter, combustible material and ignition
source are combined and will react in the plesence of oxygen.
Removal of hydrocarbons by. eg nitrogen pulgrng of gas systems rvili remove the dange
of explosion but not necessarily the dangel of file.
Dampening down n'ith water will retard the reaction and allow safe removal of the
debris. This mai'be the only practical method in large installations. eg storage tanks. I
certain applications however the introduction of water is not permissible, in sour
systems from a corrosion point of view. and in cryogenic sy'stems due to the risk of
process freezing.
The best way to deactivate the clepositsrs to follow the nitlogen purge with a mixtnle c
5 per cent oxygen in nitlogen rvhich allorvs controlled oxiclation.
E P 9 5 - 0 3 1 7 R e v i s i o n0 5 O c t o b e r 1 9 9 5
45
l V. 2 . 2 R e m o v al / c o n t ai n m e n t
E a c h c a s es h o u l d b e j u d g e d o n i t s o r v n r n e r i t s . b u t m o s t i m l r o l t a p t i s t h a t n g i g n i t i o n
takes piace.
Although the intt'oduction of watel fol clampening clown may be prohibitect in view of
possible corrosion. this may stiii be a feasible option in certain par.ts of a plant.
The trse of water may be prohibited in a launcher because of its inclination but it is
possible to dampen down a receiver (whele after all any clebris is received) because of
its declination. Special attention should in this case be paid to wetting of collection
trays.
Vent and flares in sour service should be pulged at all times cluring normal operations
to prevent introduction of oxygen and special measures shotrld be taken wherever this
purge is interrupted ol discontinued.
When a plant is shutdown for a longer period the vent ancl flare lines shoulcl be purged.
and blinded off. Vent and flale iines rvhich had been nitrogen pulged ancl spaded off
have been observed to glow cherry red after a spoot had been removed. for modifications.
Special care should be taken while opening up fixed or floating loof oil storage tanks.
Mixing of siudge with the crude oil and flushing q'ith water will at least avoid. a
hydrocalbon air mixtur.e rvith the pyrophoric debris.
For equipment temporarily out of operation (centrifugal compressor) a continuous pur.ge
under slight overyressure may. grve adequate protection.
lV.2.3Transportation,storageand disposal
it is important that any pyrophoric debris remains wet, preferably submerged. in water,
throughout the period of storage and tlansportation fi'om the worksite to the designated.
safe area for its disposal.
Transportation should be in a watertight metal container. The container used.for
tlansporting the pyrophoric debris should be cleariy identified ancl must never be
transported together with flammabie materials. It is also good practice to pack
equipment, such as filter elements rvhich may contain pyropholic clebris in plastic bags
to keep oxygen away.
One way of disposal is to durnp the pyrophoric debris in a dedicated safe
location exposing it to the atmosphere and oxid.ising it.
Note: One of the products of this oxidation is SOo which also pr.ovides a health hazar.d..
refer to 3.2.3.
46
E P 9 5 - 0 3 1 7 R e v r s r o n0 5 O c t o b e r 1 9 9 5
AppendixV H2SDispersion
A P P E N D I XV
H Z SD I S P E R S I O N
'TRC
Table V.1 gives the results of clispersioncaictriations performed using the
Dispersion'model within the FRED Version ?.1suite of pt'ograms.
The TRC Dispersion moclelis in fact an integrated suite of models. The program takes
the initial release conditions ancl,if necessary, atrtomatically makes the transitron fi'om
jet dispersion to Gaussian (btroyzrnt)ol hear,l gas dispersion.
Table V.1 indicates the clistancesfi'om source to H,S concentlations of 200 ppm and
10 ppm for leaks from three hoie sizes and two containment pressul'es.other
assumptions are:
1.
2.
Reiease height is 3m
3.
4.
Neutral conditions
5.
6.
7.
8.
Sample time of 10 min FRED calculates using 10 min, the results are simiiar fol a
15-minute sample time used in II.4, Occupationai Exposure Limits)
These conditions have been albitlariiy chosen. The table is an exarnple only, each
specific case must be modelled separately. The results may then be used to assess the
feasibility of HrS in concentrations of 10 ppm, 200 ppm, etc reaching aleas of conceln
beyond the ciassified 'HoS Risk Alea'.
Table V.1
Pressure 50 barq
H o l e d i a m e t e r( m m )
200ppmH2S
1' O
nrn
" n
YF'
F - ^l Q
A 6 A
JOU
' A
ZIU
. r. l i s t , o f s r . r i r s l q L i e nvte r s i o n s o f
T h e s e c a l c t t l a t l o n si r a v e l r e e n l ' r i n o n I l n E l ) r , e ' r ' s i c )" r. 1
I r R , E D .o t ' o t h e t ' n r o c 1 , ' i sr.l r a v g ' l r c l a t ec l i f l ' c l e n tr e r s t r l t sl.r o w e \ - e rt h e o l c i e l ' o f m a g n r . t u c i e
shotrldbe similar'.
Rr)vrsror
17
&.. ^
U.i..---AppendixVl H2SDetection
VI
APPENDIX
HrS DETECTION
systems
vl.1 FixedDetection/Monitoring
V|.1.1General
of sensors permanently installed at fixed
Hrs detection is achieved by havrng a system
to the atmosphere or accumulate. Portable
locations where HrS is most likely io exit
is
They mal.be used in locations where it
sensors are used for alerting the ind.ivrdual.
facilities
back-up
can also provicle the required
not practical to install fixed"sensors, and
in the event of fixed system failure'
of
possible leak sources in an HoS-containing section
It is very d.ifficutt to define all the
that
in practice to position Hrs detectors such
a process, and therefore it is not possibie
the
include
.o.,r.". Further complications
they will detect leaks from each iossibie
of the
speed's,plant geometry and the density
range of possible wind. direction, and
outdoor'
provrde aclequate reliability, especially in an
rereased.carrier gas. Moreover, to
testing' calibration and maintenance'
situation, such systems require r"gt'lar
ground level
systems shoulcl be instalied above
sensors for the detection and monitoring
-containing
pipeline
such as Hos
(ie a minimum of 1.2 m) except in special situations
and
HrS ulg loi necessariJy:heavier than air
trenches. Hazard.ous concenti'atior* of
They
concentration'
ihe Hrs b'eathing zone
sensor.sat ground. rever may not incricate
etc'
can also be easily contaminated by splashing,
flow
it may be practical to install pressure or
In some cases, for example a pipeline'
due to a rupture.
trips to give warning of a serious release
detection systems make an important
Despite the foregoing limitations, HrS
an Hos-containing plant' DEP 32'80'10'10
contribution to the safety measu'es on
(Refl 14) provides a methodology to select the
(Instrumentation protective Functions)
are trvo appl'oaches which are normally
appr.opr.iatelevel of safeguarcling- There
10)'
"ppft"a. Refer to API Guide RP 55 G'ef'
source
v1.1.2Sensorsof leak detectionfrom single
from a single source where the HoS concentration
A sensor is installed to detect,ieakage
trign probabihc.v of a leak' It is generaliy
in the fluid is high and./or there is a relatively
design measure to minimise the
appired on equipment for which an alternative
to d.irect it to a safe location, is not readily
probablity and/or quantity of a rerease, o-rbe wired into a shutdown logic'
availabie. A detection system may also
V1.1.3H2Sarea monitoringsystems
1995
E P 9 5 - 0 3 1 7R e v r s i o 0n 5 O c t o b e r
49
Vl.2 PersonalH2SMonitors
In selecting a personal HoS monitor the foliowing points should be considerecl:
Intrinsic safety
The equipment must be certified safe to use in potentialty flammable atmospheres,
including hydrogen/air mixtules. where appropriate.
Operability
The equipment should be light, easy to handle and straightforward to operate by one
pelson. Robust construction should ensure continuous operabiiity and intrinsic safety.
Measuring range
This should cover 0 to 50 ppm and instruments are availabie with a continuous readout.
Alarm level
This is normally preset by the manufacturer at either one or two different levels
(warning and evacuation levels). It is recommendecl that units are purchased which
alarm at 10 ppm.
Alarm signal
Monitors g:vrng an audible aiarm. \trhele high noise levels may mask the aud.ible signal
an extension ear plug is recommendecl.
Accuracy
The accuracy of H,S personal monitor.'-"i-qtypicaliy +l- LS per. cent.
Humidity
The monitor shor,rldbe capable of functioning within the limits of its accuracy in
humidities ranging from 10 to g5 pel cent. It should function at gleater than g5 per. cent
humiclity if watel is kept off the sensol heacl ancl rviil tenci to lesilond at lower H"S
levels. ie the 10 ppm alarm could be activateci at lorvel ievel-q.The unit shoulcl r..i.,rr, ,o
no|mal readings fot'H:'-q when retttlneci to lorver'humiditl,' conditiops. The const].ncrion
of the housing shoulci not allorv slrlash rvater. fol examl-rleririn rvater. to penetr.ate the
sensol'.
Tem peratu re
Tire monitol shortld normally be calrable of'f uncttonnlg o\/el'a I'ange of 0 ro 50'C. \\:6er.e
the eqtripment i-" r'eqtrit'edfor ttse in sub-zelo tempelatules. the mantifacttrr.er./sr.rppliel
50
F P 9 5 - 0 3 1 7 R e v i s r o n0 5 O c t o b e r 1 9 9 5
AppendixVl H2SDetection
should be contacted because trnits porvered by special lithium batteries are available
50"C. It sbould be noted that lorn'temperatut'es
which function ovel' a range of -40'C t,r.r
seriously impede the speed of response. The effects of temperatttre should be confirmecl
with the equipment manufactuler.
Batterycheck
The monitor should be fitted rvith a check device to indicate the power level in the
battery. The battery should be capable of operating fol a minimum of 10h.
Alarm response time
The monitor should be capable of aialming at the 10 ppm level within 15 secondsof the
sensor being exposed to that levei and within 3 secondsat the 50 ppm level.
Interfering compounds
Substances such as hydrocarbons, mercaptans and SOo shor.ridnot advelsely influence
the detector system within the range of 0 to 50 ppm of H"S.
V l . 3 H r S D e t e c t o rT u b e s ( M a n u a lS a m p l i n g )
The detector should be acculate in pelfolmance for the range of concentration requiled
and simple to operate. The detectol usuali1,-incorporates a hancl-opelated aspilating
pump, with a colour metric detectol tube that plovides an integral scale reading
gladuated in ppm HrS. A type of cletectol that leqniles lefelence to glaphs or charts is
n o t r e c o m m e n d e da n c l s h o u l d n o t b e u s e c l .
Vl.4Testingand Calibration
Electronicsystems (fixed)
shall be veriiied fol acclllacl'.speeclof
Ali H-S detectionsvstelr-qancleqtrrpn'rent
l ' e s i ) o n s ea n d o p e l a t i o n r j e f f i c l e n c vn s l l c l ' n l a n u f a c t u i ' e r " sr ' ' c o m m e n c l a t r oInn. a c l c h t r o n .
s e n r i c o n d t t c t o it'r ' p e o f s c n s o l s s i - r a l l r e e x i l o s e c lt o a r - rH , S t e s t m i x t t r l e a t i r f i ' e q u e n r ' 1o' f
at least once evel'\' tu.o ntonths.
Revisron
0 5 O c t o b e r1 9 9 5
EP 95-C317
51
lI
I
52
E P 9 5 - 0 3 1 7R e v i s i o n0 5 O c t o b e r1 9 9 5
AppendixVll RespiratoryProtectiveEquipment
VII
APPENDIX
RESPIRATORY
PROTECTIVE
EQUIPMENT
Vll.1 General
It should be noted that full face masks do not seal ploperly on beards or with the
wearing of spectacles, with the result that positive pl:essure can be lost, thus permit,ting
ingress of contaminated air from the surroundings. For breathing apparatus @A) it
should be checked that every bottle is full prior to use. The contents, especially for a
iarge non-portable bottle, may not be what is written on it. Confirmatoly air quality
check-sshould be applied to bottles which are not filled and transported under full
company control.
Both pl'essure/demandand positive plessure systems ale avaiiabie. For use in an HoS
atmosphere oniy a positive plessure system is recommended. The main types of
respirator are described below. More detaiis can be found in the SSC guide 'Hydrogen
Sulphide', Section 7 (Ref. 1).
Vll.z Self-Contained
BreathingApparatus(BA)
This self-contained breathing apparatus consists of compressed air cylinder/cylinders
calried on the wearer's back. Air is supplied to the fuli face mask via a flexible hose
through a plessure reduction and demand valve. The system can be obtained either in
the 'demand' or'positive pressure' mode. In the positive pressure mode the possibility of
pulling in toxic vapour alound the seal of the face mask is minimised. Cylinders of
1200, 1800 and 2400 litres are readily available from the manufacturers. The amount of
ail remaining in the cyiinder(s) is easily checked by the wearer by means of a pressure
gauge fitted to an extension tube attached to the front harness and by an audible low
pressure alarm. This type of equipment in the 'positive pressule' mode is recommended
for use in H"S contaminated environments up to a maximum of 2 per cent (20,000 ppm)
Hrs'
Vll.3 GompressedAirline BreathingApparatus
These sets consist of a full face mask attached to either a remote set of cylinders
containing compressed air or to a compressor. The bank of remote cylinders or the
compressor should never be left unattended whilst users ale connected. The face mask
is connected to the bank of compresseclail cylinders or the compressor via a flexible
hose and pressure regulator. The hose should be of a construction capabie of
withstanding chemical attack and ki.nking under pressur-e.In the case of the
compressor it may be necessary to include a filter downstream of the compressor to
remove any contaminants. The compressed air hose breathing apparatus with a remote
set of cylinders is recommended for use in an l{'S contaminated envilonment up to a
m a x i m u m o f 2 p e r c e n t ( 2 0 . 0 0 0p p m ) H r S .
The supply dilectly from a compressor is less reliable and thelefore not recommended.
E P 9 5 - 0 3 1 7R e v i s i o n
0 5 O c t o b e r1 9 9 5
53
V l l . 4 C a s c a d eA i r B r e a t h i n gS y s t e m
This equipment. used typically on drilling rigs. combines the complessed airline system
of VII.3 with the self-contained breathing apparatus of'WI.2 by providing with the
latter a possibil:ty of connecting into a compresseclarrline supply.
The self-contained bleathing appalatus set ailows the pelson to leave the hazard area
when necessarv.
Vll.6 ChemicalCanisterRespirators
These respirators consist of a full face mask connected to a canister by means of a
flexible tube. The canister contains an adsolbent material selected for the specific toxic
gas, in this case HoS, which it removes from the inhaled air'. The canister of adsorbent
is for one time use only and must be discarded after use, regardless of how short the
usage was. While breathing in, a negative pressure is developed inside the face mask
and, if a poor face seal exists, HrS could enter the mask. As these respirators have no
independent air supply they must not be used in atmospheres where the oxygen content
is less than 21 per cent vol. The nominal protection factor of this type of equipment is
from 50 to 400 (eg with a 500 ppm HrS atmosphere, protection factor 50, wearer
breathes l0 ppm HzS). The length of time of adequate protection varies according to the
exposure time and the concentration of HrS. There is no indication of remaining
adsorbent capacity or point of saturation. There is also a limited shelf life for chemical
canisters. Because of the problems outlined above, the use of chemical canister
respirators is not recomnrended for service in HrS environrnents and due to
their low protection factor these chernical canister respirators should not be
used in drilling or workover operations.
It is important to distinguish between the various types of such chemical adsorbent
respirators which are on the market as some offer insufficient margin of safety. The key
points are:
'
Although air-supplied escape sets ale lecommended, chemical cartridge respirator-s may
be considered, on a lirnited, carefulll' selected basis, for emergency escape pur?oses,
providing the following are observed:
.
use only in H"S concentrations of less than 200 ppm
.
r'eliably establish that cluantit5' and cairacitv of aclsorbent is sufficient fol purpose
54
EP 95-0317Revisron0 5 October1995
AppendixVll RespiratoryProtectiveEquipment
set tlp a tl'alntng pr.'ograntmeto ensule proper use and maintenance of the
respirators
set up administration to ensure canisters/cartriciges are discarcleclwhen the exnir.v
date on them is reached or if they have been usecl (ie seal broken).
V l l . 7 C a r ea n d M a i n t e n a n c eo f B A E q u i p m e n t
Breathing apparatus in its entilety shouid be checkeclat least monthly ancl details of
the inspection and any maintenance recorded. A11work on bleathing apparatus rn,hich
includes maintenance, inspection and cylinder refilling shoulci only be carrieci out by
technicians competent in such work.
The competencies should be clear'ly defined and checkecl.The responsibiiities for
carrl"ing out the work should also be clearly defined. The quaiity of breathing air shoulcl
be regularly checked.
Problems of poor visibility and freezing of exhaiation valves may be encounterecl when
using self contained breathing apparattts in sub-zero temperatures. Fult face pieces
shouid be designed so that the incoming fresh air sweeps over the inside of the
eyepiecesto reduce misting. Anti-misting compounds may be used.to coat the insicie of
the eyepieces to reduce misting at room temperatures ancl d.own to temperatures
approaching 0oC.
Full face pieces are available rvith inner masks that clirect exhaied air through
exhalation valves and, when properly fitted. are more likely to provide adequate
visibility at low temperatures.
At very low temperatures the exhalation valve may collect moisture and either freeze
open, allowing the wearer to breathe contaminated air, or freeze closed.thereby
preventing normal exhalation. Dry ail suitabie for respiration should. be used.with selfcontained and compressed ail line breathing apparatus. The clew point of the breathed.
gas should be appropriate to the ambient temperatures (preferably not exceeding -b0 oC
at atmospheric pressure).
High plessure connections on self-contained breathing apparatus may leak because of
metal contraction at low temperatules but the only penalty is likely to be outwar.cl
leakage.
For further details see:
'
E P 9 5 - 0 3 1 7 R e v r s i o n0 5 O c t o b e r 1 9 9 5
- American
British
BS 4275.Sect.5.6.3.
1,I974 (Ref.17)
Australian
Gelman
DIN 318E(Ref.19)
} F
33
s u l p h i d e( H z S )i n o p e r a t i o n s
H S E M a n u a l E P 9 5 - 0 3 1 7H y d r o g e n
for personnelin H2Sareas
levelsof protection
Table vll.1 Recommended
R ecommendedP rotecti on
l evel - w here H 2S
concentrationis known not
to exceed200 P P m
R ecommendedprote ct ion
level - where H2S
concentration is known to
exceed 200 pPm
Type of
s i tu a ti o n
E x a mp l e s
V is i ts ,
ins p e c ti o n s
Ou ts rd ev i s i to rs ,
ma n a g e me nat u d i ts,
engineers,draftsmen
on fieldvisit.
M a i n te n a n c e
supervisorinsPecting
worksite
Moni tor
Moni tor.
Escapeset carried
or cl oseto hand
B*
Norm a l
operations
Operatorchecking
i n s tru m e nre
t a d i n gs,
stoppingistarting
p u m p s ,b u t e x c l u di ng
any livework such as
s a mp l i n go r ta n k
dipping
Moni tor
Moni tor.
Escapeset carried
or cl oseto hand
B.
Work out of
rangeof
' H2 S -l i v e '
Moni tor
P a i n ti n gw e l d e dl i n es
in pipe track,road
re p a i rstre
, n c hd i g gi ng,
repairinglightfittings
Moni tor.
Escapeset carried
or close to hand
B'
No.
equ i p m e n t,
pip i n g e
, tc
4
W o rk sn e a r
'H2S-live'
equ i p me n t,
pip i n g ,e tc
but u n l i k e l y
to disturb
them
W o rk l i k e l y
to disturb
' H2 S -l i v e '
equrpment,
p i p i n ge, t c
56
B'
Moni tor.
Escapeset with
mask at readY
c*
Moni tor.
TestingnewlY
c o mmi s s i o n ero
d tati ng E scapeset carri edor
M o d i fY i ng c l o s et o h a n d
e q u i p me n t.
pipingwhere stresses
could be transmittedto
. d j u s t i ng
l i v ep i p i n g A
a n dc a l i b r a t i n g ' w e t '
of
c o m p o n e n ts
i n s tru m e n ts
B'
Moni tor.
Escapeset with
mask at ready.
C+E
A t l eastone
standbyw i th B .A .
SET
E P 9 5 - 0 3 1 7R e v i s i o n0 5 O c t o b e r1 9 9 5
AppendixVil RespiratoryprotectiveEquipment
Table vlt'1 Recommendedlevelsof protection
for personnelin H2s areas(continued)
No.
fa
Type of
situation
S am plin ga n d
dipping
Ex a m p l e s
T a k i n gg a s o r l i q u i ds ampl es
D i p p i n ga ta n k
Recommendedprotection level
(for all H2S concentrations)
Moni tor
B.A.set - mask fitted
At leastone standbywith B.A. set
F+E'
Openinglive
equipm e n t
Leaking
equipm en t
O p e ra ti o n ai nl v e s ti g a ti on
of l eak.
Op e ra to irs o l a ti n gl e a k i ng
e q u i p me n t
Entryintolow
lyingarea
IU
'1 4
t l
Note:
Moni tor
B.A. set - mask fitted
At leasttwo standbywith B.A. set
Wo rk o n ta n k b u n d so r in pi pe
trenchesand culverts
Moni tor
Escapeset if gas test shows H2S
free
Mask fittedif not gas tested
Accessto tanksvia bundledarea At leastone
standbywith B.A. set
rntry
into
trntryIntovessels,tanks,
I
I Monitor
I vesselor other b u i l d i n g so r c o mp a rtments
Escapesetpermissible
onlyonce
space c o n ta i n i n gp ro c e s se q u i pment I isolated,gas
I confined
freed and air flow
w h i c hm a y c o n ta i nH 2 S i n the
establ i shed.
atmosphere
B.A. set - mask fitted
At leasttwo standbywith B.A. set
(at l eastone i f i sol atedand gas
i
freed)
|
Entryinto
Arrivalat unmannedplatformor
Monitor
suspected
productionfacilitywhere integrity B.A. set mask fitted
unmonitored
of H2S detectionsvstemsis in
At leasttwo standbywith B.A.set
area
doubt
F+ 2E .
B+E*
OR
F+ E
B+E*
OR
F+ E
F+ 2E *
'H2S
concentration'
refersto concentration
of hydrogensulphidein the atmosphere.
For liquidstreamstake concentration
in equilibriumgas at atmosphericpressure.
Escapesets to be used only if the enduranceis sufficient
for the lengthof the escaperoute.
' F or
ex plan a ti o n
o f p ro te c ti o n
l e v e lc l a s s i f i catton,
see Tabl e4.3.
57
AppendixVlll TypicalProcedures
APPENDIX
VIII
TYPICALPROCEDURES
V l l l . 1S p h e r eR e m o v a l
A sphele removal exercise in an H"S risk area lequiles three persons as a minimum.
Two actually carrying out the job and the third observing from a safe position away
from the launcher. As a minimum, four sets of self-contained breathing apparatus mus
be prepared, function tested and declaled fit for usage. One for each of the two persons
carrying out the loading, one for the observer anci one spare kept with the observer in r
safe area. Portable continuous H,S monitols must be checked priol to commencement r
work as must the personal HtS detector worn b1'the observer.
\-
1.
2.
The portable continuous H,,S monitors are positioned around the receiver and
turned on.
3.
4.
5.
The observer takes up his upwind position, ensuring unobstructed watch of the
two carryrng out the work.
6.
7.
8.
Open the line to vent betrveen the double block valves on the sphere receiver
incoming line.
9.
Commence the gradual depressurising of the sphere receiver via the depressuring
line to flare or vent. Check pressure on the gauges on the sphere receiver.
11. The two persons carrying out the work should now put on their breathing
apparatus face masks havrng first opened the supply from the cylinder and then
tested the face seal.
12. Open the drain valve and flush with r,vaterfrom a separate top connection.
Alternatively purge rvith nitrogen to flare or vent.
13. Stop flushing, open door'. remove debris with a (non-meta1lic) rake and transport
wetted debris in the dedicated container. Be aware of the effect of pyrophoric iron
suiphide.
14. Remove sphere.
15. Close the receir-et'door'.ciose the dlar.n vall'e and ciose the flush connection.
16. Ciose the iine to vent between the cloublebiock valves on sphele receiver inlet line.
lT.
1E. SlowiStrel)r'essttt'isethe lecervel' anci ciri';e out vu'atervapour with gas to the vent or
flat'e -qvstent.Leali checks on the ciool seal must be made thloughout the
r e l ) r ' e s s lui s n t i o n .
E P 9 5 - 0 3 1 7R e v r s i o 0
n 5 O c t o b e r1 9 9 5
59
Vlll.2ProcessStreamSampling
Vlll.2.1Introduction
This guideline deals with the sampling of sour product:
'
AII accessways to the sampling point should have HrS warning notices posted..
'
'
If pressurised sample cyiinders ale to be used, the cylinder must have a valid.
pressure test certificate and be stowed/transported in a purpose-built secure
container with ventilation holes. Prior to the sampiing taking place the control
room supentsor must be informed.
'
'
'
The sampler must work from an upwind position even if he has a self-contained
breathing apparatus on.
'
60
EP 95-0317Revrsion
0 5 October1995
AppendixVlll TypicalProcedures
1.
Priol to conltecting the pressure cy-lindel to the sampling pipework the quick
coupiing seal rings should be inspected. If any signs of deteriolation are er,rclent
then a replacement seal shoulcl be fitted.
2.
Connect the cylinder to the sampiing pipervork by tightening the quick coupiings.
Oor iiquid samples the disk T must be at the top of the veltically mounted
cylinder).
3.
4.
Fully open valves D, E, A and H slorvl)'. (If liquicl, valve H remains closecl).
5.
Slowly open valve B. Check the cluick unions for leaks. Fuliy open valve B. The
cylinder is now under sampie conditions.
Slowly open valve G allowing flow through the cyiinder. (The return line
downstream of valve H returns to a palt of the process which is at a lower pressure
than the sampling point). Once a suitable through flow has been alloweci (for
purging, etc).
7.
8.
Slowly open valve F, thereby venting the pipework between valves E and G.
9.
Slowly open valve C, thereby venting the pipework between valves D and B.
The cylinder quick couplings can now be undone and the cylincler prepared for
transportation.
Both sides of all quick couplings should be closed off.
\/alve F should be slowly opened and as soon as a small amount of liquid passes,
valve F is closed.
7.
8.
9.
The cyltnder couplings can be undone and the cyiinder plepared fol transportation.
l..iote: It is essential that the cylindel is in a vertical position with the disc T at the
top. Disc T indrcates which end of the cyiinder has the internal ullage tube. The
space above the tube allows fol expansion of the hquid.
Prior to using a pressure cyiindel for liquid sampling, rock the cyiinder gentiy to ancl
flo. If a rattling sound comes from within the cylinder reject it, thi-s noise most probably'
indicates that the ullage tube has detached fr,'omthe cyiinder top. It could be
extremely dangerous to use a cylinder rvithout the ullage tube. Expansion of the
enciosedliquid could cause the cvlinder ro burst.
E P 9 5 - 0 3 1 7 R e v i s r o n0 5 O c t o b e r 1 9 9 5
61
HSEManua|EP95-03lTHydrogenSulphide(HzS)inoperations
Fol fulthel
details see:
.AnalysisofoilFielciWater.sAPIRPa5CRef.2l).
(schematic)
arrangement
FigureVlll.1 Typicalgassampling
To Process
To ClosedDrain
62
EP 95-0317Revrston0 5 October1995
AppendixlX Exampres
of H2s Area cfassification
Systemsin Use
APPENDIXIX
EXAMPLESOF HZSAREA CLASSIFICATION
SYSTEMSIN
USE
lX.1 ShellExpro
shell Expro have established five ciiffer.ent ar.eas
as far as Hos hazar.ds ar.econce'necr,
reference Hydrogen sulphide Gtriclance by UESE/14
@"f. ;;;.
'
H2S-0 areas - he.e HoS will be encounte'ecl during
normal oper.ations.
'
H2S-1 areas - hele thele Itlay be a
Presenceof HoS uncler.normal oper.atrng
conditions' II,S'1 area-scan be macle safe fo. r,oor'fing
by the application of iaicl
down procedures: this cannot be achieveclfor..H.'S-O
areas.
'
H2S-2 areas - these ar.enolmall-r'HrS-free but
may be contamrnateclby a -svstem
malfunction, leakage ol olrening of enclosecllines
or equipment.
There ale two types of H"S-2 aleas. Majol
and IVIinor. In an H2S-2 Major area a
release would carry a risk of serior,s, irrle.rersible
effects, which in practice means an
Hts concentration in air exceeciing 200 ppm. i1
an H2s-2 Minor u."" the potentiaj Hos
concentration would never exceed 200 ppm
ancl the "i=. therefore only carries tir. '.irf"
of minor (reversible) effects.
Non-H2S areas - these are always fi'ee of
H"S rvhich in practice means that the
concentlation in air cannot exceecl5 ppm by
iny reasonable mechanism.
lx.z PDO
PDo distinguishes,as far as accidentalreleases
a'e concerned(which excluciesplannecl
exposule)'between three diffelent categoriesof onshole
pr.oductionfacilities: Sweet,
Low Risk Sour and' High Risk So...?"cilities,
refelencereport TR/00 yg4by TSE/11
Gef' 23)' The basis for the classificationis that no person should
intentionally be
expo-ced
to a concentrationof HrS of 10 ppm in air or more u,ithout ppE
being worn.
Facilitl'specificreleasescenarioshave been cleveiopecl
but in all casesassessedto date
the dominant factor in detelmining H=s concentratron
in air ^isL the
U ^ r vu
concentration
\ - ' r r u s r r r ' r c t L r u ru
r l H.,s
of
in the procgss str.eam.
.
Sweet area
An area is ciassified a.ssrveet rvhen no process
stream in that a'ea has an H"S
concentration that exceed-q50 ppm. This is commensurate
rvith ";;;.;;'"
potential concentration in ail of ies.sthan
10 ppm based on estimatecl clilution
following a release.
E P 9 5 - 0 3 1 7 R e v i s i o nO 5 O c t o b e r 1 9 9 5
63
.-
-.
-:---
-.--*,-!4..J-
S u l p h i d e( H z S )i n O p e r a t i o n s
H S EM a n u a t E p 9 5 - 0 3 1 7H y d r o g e n
.
64
E P 9 5 - 0 3 1 7R e v i s i o n0 5 O c t o b e r ' 1 9 9 5
Glossary
GLOSSARY
A g l o s s a r y o f c o m m o n i y u s e d t e r r r r si n H S E i s g i v e n i n b o t h E P g S - 0 1 0 0H S E
Management Systems and EP 9i)-i)300C)vervie',vHazarcis anci Effects Management
Process.
E P 9 5 - 0 3 1 7 R e v i s r o n0 5 O c t o b e r 1 9 9 5
65
References
REFERENCES
1
2
3
4
5
6
1 7 BS 4275:1974,
Recornmenclations for the selection. use and maintenance
of
respiratory protective equiprnent. BSI.
18
LT\.
2 3 TP'/001194.
Sweet. Low Risk Sour and High Rish sour by TStr/11,pDO.
E P 9 5 - 0 3 1 7R e v i s r o0n 5 O c t o b e r1 9 9 5
67
HydrogenSulphideSafetyTraining Course
Duration:
Intended for:
Aim:
Objectives:
(scBA).
7. Understand and explain an Air Loop (Cascade)system.
8. Passa wriften test
Contenfi
S::iffi:"lffiu*o orHzs
and
soz
E.
F.
G.
H.
I.
ii 3:ffiffi# fff#:.1h"s
anAirLoop
sysrem.
L. Written Test
Approvals:
As English is the predominant language used during emergencies, the attendees must be
able to understand spoken English. It is the responsibility fhe sponsoring company fo
ensure that the attendee is physically fit