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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

Originalhard copy and CD_ROilf-G

Contents

CONTENTS

ldentificationof Sources of HZS

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

5.1.2 Procedurefor majorH2S release

25
zo

concernsfor H2S emission


3.2.1 Environmental
and air qualitystandards

5.2.1 Hazards

28

3.2.2 Dispersionin the surroundingatmosphere

5.2.2 Precautions

28

3.2.3 Productionof sulphurdioxide

5.2.3 Generalprocedures/guidelines

28

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5.2

fety Effects of H2S

Guidelinesfor the Preparationof


HZS Procedures

29

6.'l

Formulation of Work Procedures

29

6.2

Drillingand Well Operations

30

6.3

Production Operations

30

Control and Safe Working


Practices

The Framework
of Controlsfor Workingin
H2S Designated
Areas

6.3.1 Sampling
6.3.2 lsolation

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6.3.3 Depressurising

.r..)

4.2.1 The basisof classification

10

6.3.4 Flushingand draining

5Z

4.2.2 The effectsof dispersion

10

6.3.5 Purging

32

4.2.3 The classificationprocess

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

Permitto Work (PTW)

15

Respiratory
Protective
Equipment

4t 7t

4.7.1 The typesof RPE

17

4.7.2 Protectionfor normalooerations

18

4.7.3 Protectionin event of accidentalrelease


scenanos

18

4.7 4 Protectionin areas subjectto sulphatereducingbacteria(SRB)

19

Procedural
Controls
and Standing
Instructions

19

H2SCompetence

20

P 95-0317Revision0 5 October1995

6.3.6 Vessel entry

6.4 Maintenance
Operations

33
34

Appendices
I

Formation
of H2S by SulphateReducing
Bacteria(SRB)

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PhysicalProperties
and Physiological
Effectsof H2S

37

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H2SCorrosion

41

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Pyrophoric
lronSulphide

45

H2SDispersion

47

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H2S Detection

49

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RespiratoryProtectiveEquipment

4 t
t $

.4

1'2

28

1.2 H2SAreaClassification

,B

4.9.5 Competencereview

25

ironsulphide
3.3.2 Pyrophoric

22

Recovery

3.3.1 Effectson metals

'.3

4.9.4 Competencecertification

Firefighting

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5.1.3 Rescueprocedures

Effectsof H2S
3.2 Erivironmental

4.9.2 Trarnrngprogramme

3.1 HealthEffectsof H2S

1.3 ..

20

4.9.3 Specificelementsof the trainingprogramme 22

Introduction

4.9.1 Competencerequirements

HSE Manual Ep gs-O317Hydrogensurphide(Hzs)


Vlll Typicalprocedures
lX

Examplesof H2S AreaClassification


Systemsin Use

in operations

59
A2

Gfossary

65

References

67

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EP 95-0317Revision0 5 October1995

1 Introduction

ffydrogenSulphideGIgS)is an extremely ciangeroussubstance,causingfataiiti


,".r. H.S occursfrequently in EP operations,it is consiclerednecessaryto cleclit

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;::::*:::'il"fij;i1:il3fi:,T::."l:""xili:*il:3JH;SilHff

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The apploach is in line with the hazirds and effects


supersedesEP S-SOOO-32.
managementprocessdescribedin the HSE ManagementSystemEP 95-0300.

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fhe report describesfour steps:

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INTRODUCTION

of HoS exposure(Chapter'2)
of all sor-rrces

identification

assessment of the risk to personnel(Chapter 3)

controls and safe working practices (Chapter 4)

recovery method.sin the event of loss of control (Chapter 5)

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Recoveryshould include contingencyplanning for all H"S-related situations (eg H:S


leakage,evacuationprocedures,etc)
\-

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It is of vital importance that these four steps are completedbeforeany work is r


undertaken.
The report is intended for use by field personnel in drilling, production and
maintenance operations and does not cover design requirements for new plant.

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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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Reference is made to Shel1 Safety Committee guide Hydrogen Sulphide, Hazard


Precautions G,ef. 1).
The reader's attention is drawn to the following:

the rnajor hazard of HoS is its ability to cause rapid darnage to heal
sudden death due to accidental exposure

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odour cannot be relied upon to detect the presence of dangerous


.oncentrations of HoS

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50 per cent of the people killed in H,S incidents were trying to resc
others.

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If the reader doesnot understand an)' part of this documentheishe must discussit wiih
.omeone who d.oes.

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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:
.

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2.1

material and the


the original reservoir, as a result of the hydrocarbon source
gas. If this is the case then H'S
cond.itions under which it was converted to oil ancl
will be produced with the fluids
bacteria (SRB)
stagnant seawater systems, by the action of sulphate reducing
(seawater, brackish,
the reservoir after proionged. injection of water with oxygen
'souring'
it due to the
within
fluids
the
of
formation water) which *ut result in
will
be
HrS
process. Any
action of SRB introduced during the injection
subsequentiy produced with fluids'

Process Fluids

in the process fluids arises :


The risk to personnel on a facility where HrS is present
o

during an accidental release

entry, instrumentation
during normal maintenance operations, eg./sphering, vessel
or valve maintenance

during venting from tanks'

upon the concentration of HzS


The level to which personnel could be subjected d.epend.s
local conditions. refer to 3'2'2,
in the process fluidand the d.ispersion and d.ilution under
d.ispersion in sur-roundin g atmosphere'

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

3 Assessmentof Risksfrom H2S

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basedon broad basedconsequence


This documentprovidesa set of recommendations
analysisand operationalexperience.
A full risk analysis may proviclea better insight into the potential frequency and
of specificHoS related events and point to possiblerisk reduction
consequences
measures.Howe!'er, perioJs of highest risk may not always be predictable and 'HrS
Risk
recognisedand.it is advrseclto acloptthe recommendationsfor classificationof
use
the
Areas,containedin this document.By doing so, procedures,including those for
of protective equipment, will ensure the appropriate state of workforce awarenessand
preparedness.
'HrS Risk
Risks associatedwith incidents that may effect areas beyondthe classified
Area, should always be assessedand this may even be a legislative requirement. Such
parties
risks may be to persons,for instance,in Opcofacilities or accommodation,third
or the public (refer to 3.2.2).
The threats presentedby HrS in a processand non-process,eg seweragethroughout the
Iifetime of that facility or pi-pelinewill be recorded in the HSE Case together with the
control measures.

3.1

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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

Health Effects of HrS

(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

REMEMBER:50 PER CENTOF THB PEOPLEKILLED IN H.,S


INCIDENTS\AIERETRITNGTO RESCUEOTHERS.

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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.

3.2.1 Environmentalconcernsfor HzSemissionand air qualitystandards


The air quality in respect of allowable concentrations of HoS varies considerably from
country to countrS'.
Alowable emission concentrations can be as low as 1 (one) ppm HrS with a
corresponding air quality of 0.02 ppm HrS over a 30- (thirty-) minute period. These
levels do not present a toxic risk although they can result in a pungent odour. The
odour threshoid for HrS depends upon the individual and can be as iow as 0.02 ppm.
Higher concentrations will most certainly cause odour ploblems.

3.2.2 Dispersionin the surroundingatmosphere


Dispersion of gas containing H2S in the surrounding atmosphere depends on a number
of factors:
.

nature of the source of the HrS


HzS in EP process operations will rareiy be present in pure form which is heavier
than air, it will usually be a constituent of a process fluid such as produced gas,
condensate or crude oil. (Simiiariy HrS encountered in non-process situations, such
as sewerage systems will also be a constituent of a composite gas). Dispersion
depends on both the nature of the process fluid (for instance a light gas will behave
differently fi'om a dense gas) and the initial concentration of HoS in the plocess
fluid.

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.

atmospheric conditions, wind speed and dilection


A high pressule gas release rviil initially be diluted by air due to the turbulence of
the jet, thereafter the ambient temperature and atmospheric stability become
influencing factors. !\;ind speecl and dilection affect both the jet behaviout' and
subsequent diiution.

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.

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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-

3 Assessment of Risks from H2S

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.

3.2.3 Productionof sulphur dioxide

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

3.3 SafetYEffects of HzS


3.3.1 Effectson metals

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)

a vel ' y shol t

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

carbon steel equipment, likely places of accumulacions ale:


Iubricatols (retrieval of wireline fishes, mill-scale from tubing)
:

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.

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EP 95-0317Revtsion0 5 October1995

4 Controland Safe Working Practices

CONTROLAND SAFEWORKINGPRACTICES

working in H2s Designated


4.1 The Frameworkof controrsfor
Areas

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
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(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

the timing of wor-k (eg at night)

(eg where personnel have to work in


the workplace and access cond.itions
o' with poor access)'
crampedicongested cond'itions
the necessaly controls are that:
The key requirements in devising
taken into account
.
all the factors are recognised and

rhe risk is assessed

the appropriatecontlols are specified

and carried out by competent

pelsonner'

I
EP 95-0317Revision0 5 October1995

H
HSE ManualEP 95-0317HydrogenSulphide(HzS)in operations
V

4.2

l)

HZSArea Classification

4.2.1 The basis of classification


The classification of HrS areas should be based on rhe likelihood of HrS presencein
the area and the rnaxirnum concentration of HrS that can be present.

Likelihood of H"S presence is defined according to a range of possibilities between


impossible (ie always below the Occupational Exposure Limit (OEL), of l0 ppm) ancl
expected uncler expected operating conditions. The two leveis of significa"." i"
determining how concentration
contributes to alea classrfication are 10 ppm (the 1evel
below which there ale no health symptoms - the OEL) ancl 200 ppm (the approximate
dividing iine below which the effects of HrS cause minor/reversible symptoms and above
which major/permanent physiological damage is causecl).

4.2.2 The effects of dispersion


In all work situations (except those involving confinecl spaces and entry into equipment)
some dispersion will occur when HoS-containing fluids are released..Gas leaks-from
equipment under pressure can be considerably cliluted in a short d.istance by jet
entrainment of the surrounding air (even when pressures are very low, say 0.1 kpa).
The probability of inhaling undiluted process B&s, if an accidental leak occurs, is
extremely low and in principle a d'ilution of e0 to 30 times can be assumed within 100
diameters of the outflow. However the consequences of an accid.entcausing exposure
to
high levels of HrS are extremeiy serious and it is not acceptable to ignore this small
but
significant risk. For example, an exposure, to 1000 ppm HrS in air, ho*"17"r brief,
is
Iikely to be fatal unless rescue and resuscitation are immed.iate.
For this reason the maximum level in a gaseous process stream, for which the health
risk can be truly considered minor in the event of an accidental leak, is 500 ppm.
Even
this level needs to be qualified because there are types of gaseous release in which
no
dilution occurs:
'
.

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.

Light sour condensate is probably the worst in this respect.


00 nqm HrS in the process (or 200 ppm if significant hearry vapour release is possibie)
f
is the limit above which the HoS concentrations in air are likely to ,"rult
in *"io,
symptoms, causing permanent physiologicat damage. At the iower end
of the scale
50 ppm in a plocess stleam is recommended as the levei below which an accid.enrai
leak
is unlikely to cause any noticeable toxic effects of health hazard significance.
Accurate estimation of the dispersion to detelmine HnS concentration at particular
a
location remains difficult. For this reason it i.s lecomrrjrendedto base the
use of
protective equipment on the maximum concentlation of H"-s in
the process stream
rather than in air'. Table 4.l summarises HrS concentrations i.rproless gas
streams,
derived maxima in air. the effect on expo.ud vicrims ancl the required. action
in the
event of exposure.

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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

4 Controland Safe Working Practices


Table 4.1

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

R api dunconsci ousness.


Deathoccurswithin minutes

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

'Hydrogen Sulphide' 1986)


@eferenceShell Safety Committeepublication
G,ef. 1).
See also Appendix V.

4.2.3 The classificationprocess


The sequenceto be followedin determining HrS area classificationis shown in
Figure 4.1.

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

HSE Manual EP 95-0317HydrogenSulphide(HzS)in operations


Figure 4.1 HrS area classification

ldentifyH2S sources,
collectand analYse
praess/f acilitiesdata,
establishrelease
mechanisms

H2S-freezone

concentrationin air <10


ppm under all

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:
.

it should exhibit fail-safe design

it should be specific for HrS

ii

12

EP 95-0317Revision0 5 October1995

;i!''.!;.b-g-i"/.

'
.r-.ifi,.-__

4 Controland Safe Working Practices


.

it should have detectors close to all potential sources of leakage.

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:
'

the processcontains gaseswith HrS concentrafionsin excessof 1.0 per cent


volume (10,000ppm) or

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.

However, considerationshould also be given to installitrg HrS detection systems where


such concentrationsexceed0.1per cent volume (1,000ppm), particularly where
dispersionof leaked gas could be hindered or where escapeis difficult, as for example
offshore.
A fixed system does not in itself provide protection for personnel. It shouid.not therefore
be considereda substitute for normal entry precautions to a high risk area, where tests
using portable equipment and carrying of breathing apparatus should be part of
procedurefor entry.
The basic requirement is a system of sensorslocatedwhere HrS is most iikely to be
releasedto the atmosphere or accumulate. For further details on the design of fixed.
detection systems, refer to Appendix VI where relevant sections of SSC guid.eline
'Hydrogen
Sulphide,December1986' (Ref. 1) have been included for easy reference.
Refer also to DEP 32.3I.20.11-Genffi,ef.2) for further detail concerning the selection,
location, installation and calibration of fixed HrS detection systems.
It should be noted that high concentrationsof H,S in small volumes mav be insufficient
to trigger the HrS detectionsystem.

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

operation and suitable


continuous and automatic in
be
should.
provided
The instrument
audible (and'
instrument should give " tl"ut
The
p"r.orrrer.
for use by non-technicar
UrS at the pre-selectedconcentration'
visual) alarm in the pr"r.rr.. "i
In add-itionthe instrument should:
.besuitableforuseinhazardousal.eas(mandatory)

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,

have test function caPabilitY

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'

4.3.4 Testingand calibration

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

4 Controland Safe Working practices

4.4 Warning Signs


It is important that all equipment containing H"S is clearly marked, with vesselsand
pipelines individually identified. This is in addition to area warning notices which
should be in all working languages.In some countries a national standard is available
and in somelegislation clearly definesthe colour coding for processequipment and
pipework containing HrS in hazardousconcentrations.

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

The following may be used as references:


ISO 3864 Safety Signs and Colours equivalent to BS 5378 @efs. 3 and 4)
BS 1553 Specificationof graphical symbols for general engineering @ef. 5)
SSC Safety Signs and Colour Coding September 1981 G,ef. 6)
API RP 49 RecommendedPractice for Safe Drilling of Wells containing HoS G,ef. 7)

\-

4.5 AccessControls
Procedures must be in place for access,escape and movement control of personnel in
HzS designated areas. These should include:
.

inform the person in charge of the nature of your activities

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)

use of calibrated portable HrS detection equipment

use of escape or BA sets

working singly or in pails

radio communication

special production supervision for non-HrS trained personnel as required, eg


construction workers. dr-ivers, etc.

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.

4.6 Permitto Work (PTW)


A PTW should be issued fol any work to be carried out in H,S plant areas. As with any
requilement for hazardous rvork. it is necessary-to establish the level of risk to the
persons involved before defirung the necessary contlols and should address:
o

satisfactory communication for al'ea or confined space entry

personal HrS monitors ro be worn

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

10 ppm or more of H2S vapours'


if the confined.spaceis known to contain
ventilation should be applied'
In both these circumstancesfurther
d'escribedin EP 95-0315'
Permit to Work generic guidelines are

16

EP 95-0317Revision0 5 October1995

4 Controland Safe Working Practices

4.7

Respiratory Protective Equipment

4.7.1 The types of RPE


Table 4.2 summarisesrespiratory protective equipment and its application. Seealso
Table\TI.1.
Table4.2

1t
I

protective
Respiratory
equipment

Typeof Apparatus

Description

Application

Self*onta ined breathi ng


apparatus wlth full face mask

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

Compressedair from remote


cylindersupplyor compressorfed to
full face mask throughflexiblehose

'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

As for compressedairlineabove but


also suitablefor escaoe

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

Full face mask or mouth/nose


assemblyconnectedto canister
(containingH2S absorbent
chemical)by flexibletubing

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

HSE Manual EP 95-0317HydrogenSulphide(HzS)in Operations

4.7.2 Protectionfor normaloperations


Depending on the H"S at'ea classification and the circumstances that influence the
extent and level of controls (see 4.1 and 4.2), the foilowing levels of personal protection
are recommended:
Table 4.3

Protectionlevelclassification

Level of protection

Description of protection

Monitoronly

Monitorand escapeBA set to hand

Monitorand escapeBA set mask at the ready

Monitorand BA set to hand

Monitorand BA set mask at the readY

Monitorand BA set with mask fitted

Definitions of the terms 'at the ready' and


'at the ready'
.

'to hand' are as follows:

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

4 Controland Safe WorkingPractices


If a rescuesituation might arise ol escaperoutes are }ong,then a BA set (essentialfor a
rescue,Ievel D) or an escapeset (endurancepermitting, level B) shouldbe 'to hand'.
This might apply during maintenancework where an injury could occurpreventing
escapeor where work is underway several levels from the ground.
In areas where the H2S concentrationcould exceed200 ppm (> 500 ppm in process),
compressedair full-face mask breathing apparatus with adequateenduranceis
necessary.
.1

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

4.7.4 Protectionin areas subject to sulphate-reducingbacteria(SRB)


In all areas where SRB activity takes place, the presenceof H2S shall be consideredas
Iikely but not normal and warning notices and area identification shall be applied
accordingly.Accessshould be permit controlled. First entry shall always be made by
someonewearing BA and carrying a portable gas detector (protection level F). Gas tests
should include measurement of flammable gds, toxic gas and oxygen levels. When the
HrS concentrationis found to be below 10 ppm and instantaneous release can be
discounted, entry is permitted without BA being worn (protection level B or D). Single
person accessshould be prohibited. If the alarm of any monitor is set off all staff within
the area must don the self-rescueequipment and evacuatethe area without delay. If
escapeis particularly time consuming an ('early') alarm setting of 5 ppm may be
adopted

4.8

ProceduralControls and Standing lnstructions

Local levels of exposureand the appropriate level of protection of personneland other


precautions,should be documentedas standing instructions. For all normal activities
these standing instructions should lay down in unambiguousterms:
o

which areas are hazardous due to HtS

which jobs are/are not coveredby the instruction

rvhat precautions are mandator-vin the different situations

who may authorise permits for thesejobs.

Detailed guidelines on plepaling proceduresfol HoS are given in Chapter 6.

'1995
EP 95-0317Revision0 5 October

19

HSE Manual EP 95-0317Hydrogensulphide(HzS)in operations

4.9

HZS Competence

All personnelwho visit, work or carry out special (emergency)


duties in an ar.eawhere
HzS is a potentiai hazard neeclto have a levei of com;retencecompatible
with the task-s
they are expectedto carry out and must be trained..In line with
basicprocedures
developedas part of HSE managementsystems(seeHSE Manua]
Ep 95_0100and Ep
95-0r20),competenceassurancerequires the competenciesto
be identifiecl,training to
be provided and performanceagainst requirements to be reviewed
at regular intervals.
only personnel who are trained. and certified to the required
level of competenceshould.
be allowed entry
HrS d.esignated.
area.
Training
record.san6 competence
11 3"
certification should be containedin an HSE personaip"r.port
or similar document.
Accessby personnel to an Hzs area without an H2s entry permit
should be prohibited.,
unless they are under direct control and surveill"-n." of "
itoperly authorised an6
trained HrS permit holder who is accountablefor the personnel
for the time of exposure.

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

use of personal monitor and awareness/operationof detection

o
.

meaning of and actionsin the event of warning signais (visual


and.audible)
what to do in caseof HoS release.

use ofan escapeset.

systems

Level 2 - Classified area competence


AI1 staff who ale required to enter an HoS classified area
as part of their normal work
should understand and have demonstraied.the ability to respond
to the following
requirements:
o

to recognisethe potential hazard

to be fully conversant with and capable of using all types


of breathi.rg apparatus
@A) as supplied at the location

to be fully' conversantwith use of pelsonal and.portable


monitoring equipment

to understand emergencyrequirements should the presence


of H"S be detected.
to understand emel'genc)'requilements
shoulcla casualtysituation occur.

ll

20

EP 95-0317Revision0 5 October1995

4 Controland Safe WorkingPractices

.t

I
r \-1
I

to be able to carry out first-aid for victims of H'S exposure.

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

I
J

to be capable of undertaking their roie in ener.'gencyplans and if necessary take


control of contingency and evacuation procedttres

Level 3 - Staff with special duties

l
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

occupational exposure limit for HoS

comparison with other gases

CIL\D
I

sources

effects on health

effects on environment

effects on equipment

pyrophoric iron sulphide

colour coding

ldentification
o

area and risk classification

safety signs

Safe working practices


.

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

air hose breathing apparat'us

aratus
self- contained breathing app

cascade sYstem

escaPesets

limitations of breathing apparatus

Iocation of breathing apparatus

wearing of breathing aPParatus

mask to face seal checking

working with breathing aPparatus


donned

servicing of BA

First aid
o

fesuscitation

artificial resPiration

emergency response and


who are required' to carry out
staff
above,
the
to
In addition
specialist
will .u"d to be trained' in their
*"d,i.., drillers and HSE officers
competencies-

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

4.g.4 ComPetence certification


with the 'equired
training program*:r.o*mensu'ate
on satisfactory compretionof the
level' a per*sonalH"S
passing a test as appropriateto the
on
and.
competence,
of
validity
Ievel
i. *ir." t, Fislr'e 4.2. The maximum
"**pI"
entry permit .^r, u, issued,.er,
coltrses
refr-esher
year..on expiry of the permit.
or r.r.i ^ permit should,be one
per-iod.
prio' to issttinga
in 4.i.: ana 4.7.3shoulclbe attended
describecr
s*biects
the
covering
tl

22

EP 95-0317Revisron0 5 October1995

,l

4 Controland Safe Working practices


new permit. Relaxation to a two-year validity is acceptable in areas of low risk or for
those staff involved daily in H,S operations.
Figure 4.2

Competencycertificate

Opco

l
, l, '
l
I \-I

HrS Competency Certificate Level.....


This is to certifv that

HrS Competency
Certificate

has successfullycompleted training for


entry into hydrogen sulphide designated
areas
Signed
Date
Expiry Date

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)

portable HrS monitor u'ith continuous read out and alarm

prsonal HrS monitor

portable HrS detector suitable for sample aspiration

portable notices warning of H'S areas and portable barriers

mechanical resuscitation equipment

diagram in control room showing location of emergency equipment.

5.1.2 Procedurefor major HrS release


Locations where HrS can be present above the TLV-TWA of 10 ppm should have a
written action pian in case of HoS release. It should be based on and include the
following information:
.

site of H2S risk areas

siting of HrS emergency equipment

interpretation

rescue operations

procedures and controls as necessary for people outside facility boundary

first aid treatment for HrS poisoning

action on hearing Ar'ea HrS Gas A]arm covering, eg:

of the fu'ea HtS Gas Alarm

I
;
I

"i

separate action for permanent staff and rnsitors/ contractors


use of escape respirators
assembly points and escape gates
roll calI. accounting for visitorsicontractors
search and reseue operation. wearing BA and using HrS detection equipment
road closures dou'nwind/stanclby boat actions
stopping of hot or cold work
checks on builcling ventilation
informing local conlrnunitl' emergency services r,vhereappropriate

EP 95-0317Revision0 5 October1995

25

HSE ManuatEP 95-0317Hydrogensulphide(Hzs)in operations


action in case of fires in H"S areas

action on hearing other plant gas alal'ms


o

methods for iocating a leak source

methods of isolating the leak

methods of clispersing the leak

procedure for all clear and return to work.

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:
.

central reporting point

rporting code

witness actions

rPorting Point 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
I

-l

Becausepersonstend to rescueinstinctively they shoulcibe trained not to do s


not properly equipped.Figure 5.1 beloq' lists first-aid actionsand provides further
medical advice on rescueof an H"S vrctim.

_t

IF A WITNESS HAS NO BA SET AVAILABLE


ATTEMPT TO ENTBR THE RISK AREA

I
J
I
'J
I

'

THE WITNESS SHOULD NOT

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

Figure 5.1 Medicaladvice

First Aid and Medical Advice


HrS poisoning is a life threatening condition characterised by loss of consciousness
and associated respiratory faiiure. Treatment must therefore be rapid to be
effective.
Remove the affected person to an HrS free area.
If breathing has stopped apply artificial respiration and continue until a mechanicai
resuscitator is available to support respiration or until the victim resumes breathing.

I
I

Obtain medical attention immediately.


If eye contamination is suspected flush the eyes with clean water for up to 10
minutes.
Subsequent to the resuscitation procedures described, keep the victim under
observation and treat symptomatically as indicated by the patient's condition. The
possibility of delayed pulmonary oedema up to 24 honrs after exposure should not be
overlooked..
If the victinc is moved to a medical facility,
poisoning is supplied to the rnedical staff.

ensure that inforrnation

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

HSE ManualEP g5-0317Hydrogensurphide(HzS)in

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

Chapter 6 gives somespecificguidanceon the preparation of H"S procedur.esfor typical


production, drilling and maintenanceactivities.

I
-l
I

GUIDELINES
FORTHEPREPARATION
OF HzS
PROCEDURES

Proced.uresfor operationsinvolting HrS shoulclbe written for a specificlocatior


conditions prevailing locally.
The immediate health effects for people exposedto HrS depend primarily on tht
concentrationof the HrS in the air. Precautionsand proceduresshould be basedon

;ilT#::;'ffi";::::::ffi*:l';""J.:ffi";.,"uu,.bedef

all facilities where HrS may be encountered.While no risks shall be taken it is

;m:ilt'Ji" ##Ti?$:'1fffitff;'Te

'

'

equipment
than
isreasonabrv

h'"3tumil3;i:;:;ff;n?T##ff;::ffi-":ffi"'ffiJlilff

.-

three main elements:

: ::;"j;il:ff';:H:i:,":n::."
o

6.1

developing standing instructions for all normal activities.

Formulation of Work Procedures

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

H:S warning signs.

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

HSE Manual EP 95-0312HydrogenSurphide(Hzs)in operations


A "r'ork programme should be agreecl and signecl by all parties
involved., ie production,
maintenance, drilling, contractot's, etc. The programme shoulcl
include the for.mulation
of special procedures in respect of Hrs hazar.dsdrring,

isolation

depressurising

boxing up

spading/Olinding)

flushing

drying

opening up

vessel entrv

line up

prssure testing

draining

recommissioning

puf glng

despading/(deblinding)

All procedureswhich cover multifunctional departments should


be authorised.by that
authority which heads all those d.epartments,ie OperationsManager
or Technical
Manager or by all parties concerned.

6.2

Drilling and Well Operations

Specific HrS procedures covering Driliing Operations in


aleas where HrS is likely to be
encountered are documented in EP 95-0210 Driliing (sub-chapter
6.b) and ApI Rp 49
7)' It must be ensured. that such procedures tie-in well
@@ef'
with the existing local
Emergency Contingency plans.
Considering the danger and. the consequencesof exposure,
when operating in an HrS
environment, it is important to take note of the fotlowing
key operational precautions
which are adequately covered in the above d.ocument
and inlne general sections of this
manuat:
I

all personnel on a driJling location where HrS is anticipated.


shall have available to
them a certified breathing apparatus
r t

all BoP equipment and tubulars to be used in wells where


HrS is expected.to be
encountered, must compiy with metallurgical specifications
suitable for sour
service

'

effective fixed detection systems that activate audible


and visual warning alarms
must be installed at strategic locations on the well location
only personnel trained. to work in an HoS environment
may be deployed to work on
well locations where HrS is expected.

'
'
'

there must be an ag:'eed.HrS 'd.r'i11'plocedurewhich


shali be carried out once a
week or more frequently until personnel on site are
conver.sant with it
drills should be monitored. against known and agreed performance
criteria.

The effectiveness of any H:S contingency pian can only


be assured if all staff involved. in
the operations are fully "*tu
of the consequences of exposure to HrS. They must
be
familiar with the right steps to control a hazard.ous
",r".rt *ili " o"tJ"tial release of
HrS and to recovel from the hazardou-ssituation should.
the release actually occur.
Effective training ancl competence assessment ale of vrtal
importance to achieve this.

6.3

Production Operations

in Appendix VIII examplesof typical srep-b],-srepprocedules


al.egiven (sphere
removal,sampling).

30

EP 95-0317RevisionO 5 October1995

!tK--ffiirurun***,.o'l

_t,

:t
_t
:l

6 Guidelinesfor the Preparationof H2s procedures

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

Samplepoints should be colour-codedand plugged if not in regular use. They should be


clearly identified with a notice which aiso specifiesif applicable that a BA set is
compulsory.
If it is not possible to have a short stub between the line and the sample point then the
system should be vented or drained to a closedsystem.
Samples should be analysedin a laboratory fume cupboard. To avoid atmospheric
pollution, waste gas samples should be bubbied through 20 per cent MEA solution to
absorbthe HoS (mono-ethanolamineMEA or di-ethanolamineDEA).
AII samplesshould have a label marked 'DAITGERHoS', and should be transported in
the back of an open vehicle or boat. In the laboratoriesthe samplesshould.be kept in a
fume cupboard,with the extractor fan switched on if there for a short period.ancl
outside the laboratory in a secure area if kept for an extended period..
Collectionvesselsmade of material resistant to HoS should be employedwhen sampling
sour gas screams.

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.

6.3.4 Flushingand draining


Flushing can be done by circulating water or other suitable medium through the process
Iines. Equipment can then be drained at the various low points to a safe place.
With HrS bearing productsall personnelinvolved in the operation should use BA sets.
Warning signs should be placed at various strategic locations around the working site to
warn other personnelthat HrS products are being drained.
When draining operationstake place through a closeddrain system, check that all
drain points on other equipment have been closed and blinded before draining starts.
This will ensure that the medium being drained cannot enter previously declared safe
equipment or areas where peopleare at workWhen dr.aining operations have to take place into open gutters warning signs should be
placedat the drain outlets and along the open gutters and HoS concentrations
measured.
The drained product should be diluted with large amounts of cold water.
Check at various locationsalong the gutter that no HOT work takes place during the
draining operations.
Always work in teams of at least two men with the secondperson watching from a safe
location.

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

6 Guidelinesfor the Preparationof H2SProcedures


r

purge eachsectionof line rvith nitrogen gasuntil the hydrocarbongas is


sufficientiy diluted
Test to below 10 per cent Lower ExplosiveLimit (LEL) and"ior10 ppm H"S but
remember some detectorsrely on cataiytic combustionand do not work in nitrogen
atmosphere.

o
,rl
J
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.

If pyrophoriciron is a possibility further precautionsas describedin 3.3.2shouid be


taken.

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.

the initial entry into a confinedspaceshould aiways be made by a pelson attached


by a safety line to the outside and wearing fuli air line supplied breathing
apparatus

personalHrS detectorsshoulclbe worn at all times


In the event of alarm the causeshould be identified and the level of H"S
determined.Suitable action shouid then be taken to reducethe level below 10 ppm
beforework resumes.

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

The following are essentialelementswhen planning and executingmaintenancework


in an HrS environment.A competentsupervisor shouid be placed in charge of the whole
operation.He will liaise closelywith the Operating, Engineering or Maintenance
department at all times. Detailed discussionsbetweendepartments are essential in the
early planning stagesof the work.
Such discussionsshould include:
o

a clear definition of action parties and areas of responsibility

an appreciationof any operational constraints which can affect the plan


eg Iive processlines or equipment in operation adjacentto the actual worksite,
time constraints, the availability of flushing lines/equipment to a safe standard.

details of the product carried in the lines or equipment to be decommissioned


eg HoS,pyrophoriciron, toxic hazards.

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

restrictions and any


a survey of the surrounding area to establish access/egress
sourcesofhazards

a check of any work taking place in the vicinity of the equipment being
decommissioned

a check on the location of existing fire equipment and respiratory protection


equipment and an assessmentof any additional equipment that may be required.

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

AppendixI Formationof H2Sby SulphateReducingBacteria(SRB)

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

following nutrients are present in the water:

.
i

.-

a carbon enerry source,ie organicmatter such as oil or lower fatty acids (abundant
in formation water)

sulphate (SOa,abund.antin seawater).

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.

1.1 Monitoringof SRB Activity


The early onset of SRB activrty can be detected by measuring the HoS content of water
from the suspect source. This is normaliy done in a iaboratory but a simpie qualitative
test kit using lead acetate paper is available from HACH for use in the field.

1.2 ControlMethodsfor LimitingSRB Activity


Several methods have been used to control SRB activity. One approach to reducing the
activitl- of SRBs is by the use of biocides, chemicals rvhich porson the bacteria.

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

HSE Manual EP 95-0317HydrogenSulphide(HzS)in Operations


The effectiveness of conventional biocides fol tire control of SRB activity is reduced in
many situations, due tci:
.

the difficultf in achieving a homogeneous mix between the biocide and the
stagnant water'

the environmental/ecological constraints


As the use of biocides could lead to the discharge of unacceptably large volumes of
toxic materials

the generally high cost of biocides

SRBs building up a resistance to individual biocides.

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.

1.3 Safetyin PotentialSRB Activity Areas


Safety precautions must be taken in all aleas where SRB activity takes place and where
the build .,p in H"S concentrations (above TLV 10 ppm) couid be potentially harmful to
personnel. The same precautions should be taken as for normal H"S releases.

36

EP 95-0317Revisron0 5 October1995

".e

..:Jnl.ria;,&.ba

r..--....

Appendixll PhysicalPropertiesand Physiological


Effectsof H2S

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

Density:gas 0'C 1 atm.

1.5392gll

Density:liquidat boilingpoint

0 . 9 9 3g / m l

Flammablelimitsin air

4.3 to 46% (by vol)

Freezingpointat 1 atm.

-85.5'C

Molecular
weight

34.08

Solubility
in water0"C, 1 atm.

0.6729/100ml water

Specificgravity15'C, 1 atm. (air= 1 )

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

(above100ppm),H:S rapidly par:aiyses


higherconcentrations
the senseof smell.
ODOIJRS}L{LL NOT THEREFOREBE USED AS A WARMNG MEASTIRE
o

normaUy present as a gas and not as a liquid

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

EP 95-0317 Revision 0 5 October

'1995

37

HSE Manual EP 95-0317HydrogenSulphide(HzS)in Operations


.

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.

it is corrosive in the presenceof water

it causescracking and embrittlernent of metals under certain conditionsbut


steelsof the correctquality which are resistant to these forms of attack can be
used.

ll.3

PhysiologicalEffects

Table ll.2

effectof H2S
Physiological

Concentrationin air
1 ppm

Effect
Odourof rotteneggs can be clearlydetected

1 0p p m

Unpleasantodour.Possibleeye irritation.ACGIH recommendedThresholdLimit


ValueTLV - TWA see 11.4.

15ppm

A C GIHT L V S TE Laveraqedover 15 mi nutessee 11.4.

20 ppm

Burningsensationin eyes and irritationof the respiratorytract afterone houror


moreexposure.

50 ppm

Lossof senseof smellafter about 15 or more minutesexposure.Exposureover


one hour may leadto headache,dizziness,and/orstaggering.Pulmonary
oedemareportedfollowingextendedexposureto greaterthan 50 ppm. Exposure
at 50 ppm or greatercan cause seriouseye irritationor damage.

1 0 0p p m

Coughing,eye irritation,loss of sense of smellafter 3 to 15 minutes.Altered


pain in eyes,and drowsinessafter 15 to 20 minutes,followedby
respiration,
throatirritationafter one hour.Prolongedexposureresultsin a gradualincrease
in the severityof these symptoms.

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

after shortexposure,breathingwill stop if not treatedquickly.


Unconsciousness
Dizziness,loss of sense of reasoningand balance.Victimsneed promptartificial
(C P R )techni ques.
resusci tati on
v e n ti l a ti oann d /or cardi opul monary

700ppm

quickly.Breathingwill stop and deathwill resultif not rescued


Unconscious
promptly.Artificialventilationandiorcardiopulmonary
(CPR)is
resuscitation
n e e d e di mmedi atel v.

> 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

For fulthel details seeAPI RP 55 [Ref. 10).

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

Value - Short Terrn Exposure Lirnit (TLV-STEL)

The concentration to which workers can be exposedcontinuousiyfor a short peliod of


time'r'ithout suffering from 1) irritation, 2) chronic or irreversible tissue damage,or 3)
narcosisof sufficient degleeto increasethe likelihood of accidentalinjury, impair selfrescueor materially reduce work efficiency, and provided that the daily TLV-TWA is
not exceeded.It is not a separateindependentexposurelimit, rather it supplementsthe
time-weighted average (TWA) limit where there are recognisedacute effects from a
substancewhose toxic effectsare primarily of a chronic nature. STELs are
recommendedonly where toxic effectshave been reported from high sholt-term
exposuresin either humans or animals.
A STEL is defi.nedas a 15-minute time-weighted averageexposulewhich should not be
exceededat any time during a workday even if the eight-hour time-weightedaverageis
within the TLV. Exposures at the STEL should not be longer than 15 minutes and
should not be repeated more than four times per day. There should be at least 60
minutes between successiveexposuresat the STEL.
The current TLV-TWA is 10 pprn (L4 rnglrn3) and the TLV-STEL is L5 pprn (21
6g/mg) for L5 rninutes. These lirnits are based largely on the irritant
properties of HrS.
The graph overleaf Figure II.l gives an indication of the acute effectsof exposureto
HrS. Exposure should be kept strictiy to levels belorvthese limits. Be aware that rvhere
the sourceis rich in HoS, gas or liquid, the transition from lou' to very high exposure
may be instantaneous.

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

HSE Manual EP 95-0317HydrogenSulphide(HzS)in Operations


F igur e l l .1

Ac u te e ffe c ts o f e x p o sure to H 2S

minor
irritation
o
o

lt nv

c,

' '- ----T- I

;
I

I
I

II
I
I

i
t

10

<nn
IUU

H2S Concentration ppm (volume)

" 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

lll.1 Types of Corrosion Damage


When d.issolvedin water H"S forms a weak acid which is corrosiveto steel. In the
reactionbetweensteel and H"S:
Fe + HzS -) FeS + 2H
atoms. Normally these atoms react to
iron sulphide is formed, together with h5'clrogen
form hydrogen gas:
2H)H2
but this reaction is sloweddown in the presenceof HoS, and the resulting hydrogen
atoms migrate into the metal.
Two types of corrosiondamageoccur.These are loss of wall thickness and hydrogen
damage.

lll.1.1Loss of wall thickness


a

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

HSE Manual EP g5-0317 HydrogenSurphide(HzS)


in operations
stress-orientatedhydrogeninduced cracking (SoHtc)
The presenceof a t'ensiiestressin the u'all oi'a
vesselor'lripehnemaclefi.omsusceptible
steei may result in throughrvalltinking of incliviciuai
HIC cr.acksthr.oughan
embrittlement mechanismtermed soHiC. The
incliviclualcr.aclisofren appear.asa
stackedarray through the vesseror.pipelinewail.
Corrosion resistant alloys
stainless steels,nickel-baseclalloys ancl titanium
alloys are used to a limited extent in
production operations'Thesematerials are
also susceptibleto weight loss corrosionin
the forms of general and localisedcorrosion( pitting
ancicrevicecorrosion)as well as
stress corrosioncracking (scc) anclhycrrogeoembrittlement.

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.

lll.3 Definitionof Sour Serice

'

\-

The definition of sour service(of equipment) is historically linked to the amount of


which can causeSSC.The NACE guidelineMR-0I-75 states that SSC is considerec
possiblewhen the partial H"S gas pressure (= mol% x total pressure)exceeds0.05
(0.0034bar). Liquids in equilibrium with such gas are also consideredto be sour.
Systemswith a total pressule less than 65 psi for gas systems or 265 psi for oil sys
are thereforeconsideredoutside the scopeof this document.For tubing and casing,
more susceptiblegradesof steel are allowed for temperatures above80"C.
For HIC there is no international standard. The present SIPM policy is that HiC cr
occurin water-containingliquids in equilibrium with partial HrS gas plessures
exceeding0.05 psi, as above,but without any exemptionsfor lower pressuresor hig
temperature becauseof lack of evidenceto this effect.

lll.4 Common Pitfallswith Materials in Sour Service


The name'HoS-resistant steel' refers to resistance to sulphicle stress cracking (SSC)
only and the use of such steel gives no protection at all against pitting corrosion.
The NACE guideline does not address the risk of HIC and compliance with MR-0I-75
gives no protection against HIC. MR-O7-75 addresses SSC only. It gives no guidance on
synergistic chloride ion/sulphide ion stress corrosion cracking of stainless steels and
some nickel-based alloys.
'magic
There are no
bullets' (why can't we add an inhibitor'?) to save equipment in sour'
service which was not designed for it.
Monitoring and inspection plogrammes cannot reduce the risk of SSC in equipment
which does not comply with NACE. Cracking can develop too fast for this.
I

'\-

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

\--

Fe*O* + SO2 + Heat

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.

lV.2 Handling Pyrophoric lron Sulphide


!V.2.1Openingup to atmosphere

\*

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

HSE Manual EP 95-0317HydrogenSulphide(HzS)in operations

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.

Release is continuous, holizontal and in the clirection of the wind.

2.

Reiease height is 3m

3.

Wind speed is 3m/s (at 10m stanclalcl meteolological herght)

4.

Neutral conditions

5.

Surface roughness is 0.03m (fair'ly level grass plains or deselt)

6.

70 per cent humiciity. ambient temperatule 15"C

7.

Parent medium is methane. 99 per cent methane. 1 per cent HrS

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

Examplesof 1 per cent HrS in methane,dispersion


distances
Pressure 5 barg

Pressure 50 barq

H o l e d i a m e t e r( m m )

Dis t anc e( m e tre s )rn


dir ec t ionof j e t to
dis oer s et o .

200ppmH2S

1' O
nrn
" n
YF'

F - ^l Q

A 6 A

JOU

' A

ZIU

Note Basedon one per cent H.S in methane


T h i s t a b l e i s a n e x a m p l e o n l y . e a c h s p e c i f i cc a s e m u s t b e m o d e l l e ds e p a r a t e l v

. 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

into plant a.eas from any source and


Detectors ar.einstalied to detect H"s d.ispersecl
in
N'lonitoring systems a'e generaliy applied
thus also covers the less likely .or,i."..
u,here the installation of individual detectors
enclosed process builcl.ingsand in areas
jr.rstifiecl.eg sightgiasses. control valves, d'ain
for each potentiar sour.cecannot be
points. etc.

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

HSE Manual EP 95-0317HydrogenSulphide(HzS)in Operations


Upon cietectionof H2S at a concentration of 10 ppm or grczrler'.thc sJ/sLemsshould
sound a unique alarm and register a visrrzrlalarm in the main conLlc.rl
room. The
monitoling system should also be capable of displaying an alarm fi'om any of the
inclividual sensor'locations and indicate the alea affected. Consicleration should aiso be
given to providrng both an audio and visual alalm in the building or' location wher.e the
HrS is detected. Guidance on the location of sensors in open areas is provided in EP 950230 Design and Engineering. For further infolmation on design and selection of fixecl
HrS detection s-r'stemsfor driliing locations refel to EP 95-0210 Drilling.

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.

Monitor calibrationand functionalcapability


A reliable field calibration kit and function test capability shouid be provided by the
equipment manufacturer. This should be used to verify the monitor at least onceper
day or shift.
Fail-safefeatures
Care should be used when selectingspecificHoS monitoring units to determine whether'
the system is equipped with internal fail-safe checksthat will sound the alarm or
trigger a warning light if there is a defectin the monitor.
Service
The availability of service and spare parts should be of plimary considerationwhen
selectinga palticular system.
Product information on commerciall5'available detectionand monitoring equipment can
be obtainedfrom SIEP on reouest.

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

HSE Manual EP 95-0317HydrogenSulphide(HzS)in Operations


Portable systems
A 1'eliablefield caiibration kit shor"rldbe provicled by the eclttipment manufacturer. This
should be used to verify the monitors at least once a da1'ol shift and always before
initial use.
Detector tubes
The pump used with the detector tubes should be checked for leakage before use
according to the manufacturer's instructions. A stock control system should be in place
to ensule that adequate supplies are maintained and that the tubes are in date.
Procedural coverage
All velification and maintenance activities on the detection equipment shall be carried
out and recolded throughout its life time as per manufactttreL's instructions. Procedural
coverage must be transparent to all parties invoived. Fol exampie it would include the
initiation of maintenance if equipment fails verification.
The records must be traceable and auCitable and should form the basis of the
performance indicators to be deveioped for each individual element of the gas detection
system as well as for condition based maintenance.
The periodic evaluation of equipment perfolmance wilI serve to raise awareness of its
reliability, availabiiity, performance and maintainability. A maintenance management
system plovides a convenient environment to achieve all of the above.

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

HSE Manual EP 95-0317HydrogenSulphide(HzS)in Operations

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.s EscapeBA Sets


An auxiliary self contained air supply as desclibed in VII.2 but rated fol less than 15
minutes is suitable only for escape or self rescue use. Gas mask canister type breathing
and demand type (negative pressule) equipment as described below are not
recommended for use for the l'easons grven in VII.6.

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:
'

they must have a full face mask

the canistel must contain sufficient adsorbenf


The canisters which strap to the beit are generally large enough. Cartridges which
fit directll' to the mask usually contain rnuch less adsorbent.

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
.

use only full face mask designs

r'eliably establish that cluantit5' and cairacitv of aclsorbent is sufficient fol purpose

set up a r.'egularmaintenance pl'ogramme to ensLu'ethe integlity of the masks

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:
'

SSHC Guidelines 1989 - Personal Plotection Equipment Guicle G,ef. 15)

standards for breathing air qtrality

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

ANSI CGA G-7.1 i11ef. i6)

British

BS 4275.Sect.5.6.3.
1,I974 (Ref.17)

Australian

AS 1716App.E 19S4@ef. 18)

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

Any work nearflanged Moni tor.


Escapeset carriedor
p i p i n gp, u m p s ,
vessels,comPressors, cl oseto hand
etc in which H2Scontainingfluidscan
escapethrough
flanges,seals,vents
or breathervalvesinto
th e i mme d i a te
atmosphere

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

T u rn i n ga s p a d e ,re m o vi ngbl ank Moni tor


F+2E*
to allowgas test
B.A. set - mask fitted
M a k i n ga g a s te s t
At leasttwo standbywith B.A. set
(at leastone if fully depressurised)

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.

EP 95-0317 Revision 0 5 October 1995

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.

The previously checked self-contained breathing apparatus is donned by the three


persons. Face masks left off.

2.

The portable continuous H,,S monitors are positioned around the receiver and
turned on.

3.

HrS accessrestriction notices a1'eplaced at all necessary points.

4.

A11downwind work is halted and personnel cleared.

5.

The observer takes up his upwind position, ensuring unobstructed watch of the
two carryrng out the work.

6.

Close the upstleam valves of the sphere receiver in-coming line.

7.

Close the downstream valves of the sphere receiver in-coming line.

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.

10. Once fully depressurised close off the depressurising valve.


\!,

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.

Open the clorvnstream valves on the inle.t to the sphele leceiver.

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

HSE Manual EP 95-0317HydrogenSulphide(HzS)in operations


19. Two pelsons carrying or-rt,
the work move to a szr{'eulea ancl may then r.emoveface
m asks.
20. The sphere receiver should be ieft r'eacll'fol the next sirhering operation ciepenclent
o n l o c a l O p c o ' sp r o c e d u r e s .
21. Remove all equipment usecl on the iob and clispc.rsc,
of cleblis in accord.ancewith
waste mana gement procedur.es.

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..

'

AII equipment necessary for the sampling mtrst be thoroughiy checked.and


positioned ready for the samphng to take place.

'

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.

'

AII safety equipment being used must be function-tested prior to usage.

'

The sampler should be equipped with a self-contained breathing apparaLus.

'

An observer positions himself upwind in a safe unobstructed area from which he


has a clear r-iew of the sampler at all times.

Work in the downwind locations is stopped immediately prior to samplittg taking


place.

The sampler must work from an upwind position even if he has a self-contained
breathing apparatus on.

'

On completion of sampling, the sample containers must be clearly identified and


should have an HoS warning label attacheci.
The container with the sample should not be tlansporred in an enciosedvehicle.
A carrier must be given warning for the transportation of samples containing HrS.

Vlll.z.zGuidelinesfor takinga pressurisedsample


The schematic in Figure VIII.l shows a typical layout for pressurised. sample taking.
The pipework eithel side of the quick couphng trni.onsis ieft in situ rvhen permanent
sampling points ale established. The pressule cylindel containing the sample is
transported to and from the labor.atorl'.
The sampli.ng cylinder (or sampie bomb) may arrive at the sampling location either.
pressurised (inert gas, ie N2) or under a slight vacuum. When a liquid sample is taken
and vapour break or,rtis to be kept to a minirnum then the pressurised (inert gas)
methocl can be used. The paltially evactrated cylindel can be usecl for gas samples.

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.

Close valves C and F

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.

Vlll.2.3For a gas sample


6.

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.

Close valves H, G, E, D, A and B.

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.

Vlll.z.4For a liquid sample


For liquid sample points valve F shouid be routed to a part of the process with a lower
pressure than the sample point. Valve C should also route the same way.
6.

\/alve F should be slowly opened and as soon as a small amount of liquid passes,
valve F is closed.

7.

Close valves D. E. B and A.

8.

Slowly open valve F and depressurise between valves E and G.

9.

Likervise slowly open valve C and deplessurise betrveen valves D and B.

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:

API RP 44' (Ret' 20)'


sarnpiing Petloleum Reservoit'Fir-rrcls

.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

To iilustlate how opcos have actuaiiy implementecl


the guiclelines given in chalrter.(i
two examples are briefly descr.ibeclbelow.

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
.

Lovv Risli Sour


if a concentration above 50 ppm but below
A faciiiry is classifiectas Low Risk Soul
which could give rise to a maximum
500 ppm HrS is present in the process stream.
concentratj.onin air of 200 PPm'

High Risk Sour


500 ppm HrS'which could
A facility with process stream containing above
the vicinity of the leak, requires a
potentially expose a person to above 2Ooppm in
potential leaks. If the results show that
cletaileclassessment of the clispersion fro.r,
200 ppm in air at a point two metres
there is a creclible risk of exposure to above
classified as High Risk Sour'
from the release sour.ce,the facihry wili be

specifu detection systems (fixed or


Based.on these area classifications, both Opcos
pro."dttres ancl warning notices along the
portable), PPE, entry, work and emergun.y
guidelines provided in this document'

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

Hydrogen Sulphide, SSC.December1936.


DEP 32'31'20'1l-Gen,
The instrumentation of fire and gas cletection
s1'stems,SIPM.
ISo 3864,safetl' colours and Safety Signs, ISo, 1gE4.
BS 5378.Safetl'signs and colours, BSI.
BS 1553,Specification for graphical sl,mbols for general
engineering, BSI.
safety signs and colour cocling, ssc, september19g1.

RP 49 Recommended Practices for Safe Drilling of Wells


Containing
Hydrogen Sulphide, ApI. April 19g7.

Guidelines for Entry into Confinecl Spaces, SSHC.ApriJ


1gg2.

Gas-freeing and cleaning of oil storage Tanks, ssHC,


April lggg (anci
AddendumApril 1992).

10 RP 55. Recomrnended Practices for Conclucting Oil


and Gas producing ancl
Gas Processing Plant Operations Involving H,vdrogen
Sulphide, ApI,
Febr.uary1995.
11 MR-01-75,Material Requirements for SSC resistant
metallic materials for
oilfield equipment, NACE, 19g4.
L2 DEP 37'40.20.31-Gen,
Line Pipe for use in oil and gas operations under
sour
conditions. SIPM.
13 DEP 31.38.01.15-Gen,
Ep piping classes,sIpM.
74 DEP 32.80.10.10-Gen,
Instrurnentation - protection Functions, SIPM.
15 Personal Protective Equipment Guicle section 6.8
Re spiratory Prote ctive
Equipment, SSHC,June 1ggg.
16

AIJSI cGA G'7 '1, Compressed Gas Association Comrnodity


Specification G7.1 Breathing Air Grade D, A\ISi.

1 7 BS 4275:1974,
Recornmenclations for the selection. use and maintenance
of
respiratory protective equiprnent. BSI.
18

AS 1776,Respiratory Protective Devices, Standard.s


Association of
Australia, 1984.

1 9 DII'I 3188,Compressed air for respiratory equipment,


safetl- requirements
and testing, DIN. September1gE4.

2 0 RP 44, Recommended Practice for Sampling Petroleum


Reservoir Fluids,
API, January 1gGG.

2T R'P45'Recommended Practice for Anall,sis of Oil-Field


Waters. Seconcl
22

Edition, API, November'r g6E(Reiss'eclJuly lgs 1).


H1'drogen sulphiclc Guicla'ce. trESE/14. shell Expro

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:

Twenty four Hours (3 Days)

Intended for:

Trainers instructing perconnel working in an offshore or


onshore environment where the presence of Hydrogen Sulfide is
known or suspected.

Aim:

To give pensons the necessarT skills to impart the nece$sary


information to provide students with the skills necessary to work
in an HzS environment

Objectives:

Upon completion of this course, the attendee should be able to:


1. Describe the physical properties and hazards of H2S and
S()2.
2. Show an understanding of proper work procedures while
working in the presence of IIzS.
3. Show an understanding of HzS detection and monitoring.
4. Show an understanding of the contingency plan.
5. Show an understanding of basic rescue in an H2S
environment
6. Safely don and starf up Self Contained Breathing Apparafus

(scBA).
7. Understand and explain an Air Loop (Cascade)system.
8. Passa wriften test
Contenfi

A. Introduction and Registration


B. Aims and Objectives

S::iffi:"lffiu*o orHzs
and
soz
E.
F.
G.
H.
I.

Hazards of HzS, Symptoms of Exposure


Respiratory Profection
Moniforing & Detection
Safety Procedures & Contingency Plan
Rescue Techniques - basic

ii 3:ffiffi# fff#:.1h"s

anAirLoop
sysrem.

L. Written Test
Approvals:

Association of Risk Management, Maersk Oil, Qatargas, Rasgas

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