H2S

PROTECTION
 Unit 1
Introduction
H2S IS A SILENT KILLER

can be found in many different

locations on land and sea.
is a natural by-product of
organic decay.
should always be in petroleum
locations.
 H2S is a toxic gas
Hydrogen sulfide is a toxic
gas, it is hazardous to the
crew and equipment of
drilling rig. Very small
concentrations can be
fatal in a very short time
a few minutes or less.
 H2S POISONING
Case 1 CASES
in 1997, during the pipeline acid
cleaning operation, H2S is produced in
chemical reaction, and poisoned three
people to death one after another at third
production factory of ZPEB.
 Case 2
On Mar 24,1998, at WenQuan4
well of SiChuan OilField,
Shutting in well when a kick
occurs at depth of 1700
meters .Because surface casing is
too shallow, H 2S in the well goes
into tunnel of coal mine and made
11 people poison to death, 34
people injure, 25 coal wells
stopped producing.
 Case 3

In Zhao-48 well of HuaBei oil

field, Tripping cable out In
the process of testing leads
to out of well control , A
large of H 2S is sent out and
made 6 people poison to death
and many people injure and
200000 people escape.
 Case 4
In Wei Yuan-23 well of Si Chuan Oil Field,
Running in N-80 intermediate casing,
welding connection of thread, But H2S
Content is high in this well , wellhead
pressure is high and weld seam is broken
very soon and wellhead is blown over
resulting in explosion. Flame is about 100
meters high ,after 3 minutes the derrick is
fallen and loss is more than 100,000,000
Yuan.
 Case 5
on Dec. 23 2003, in Sichuan oilfied,
while tripping out, because the drilling
personnel didnt fill mud in time, the
hydrostatic pressure cant balance the
formation pressure, blowout happened,
poison more than 240 people to death.

 Contents
A. Source and characteristics of
H 2S
B. harmfulness of H2S to human
being and first aid
C. damages of H2S to equipment
and corrosion inhibition.
D. detection equipment and
personnel protection.
E. Safety operation in the
sulphureous area.
 Unit 2
Source and
characteristics of H2S
.SOURCE OF H2S IN THE
OIL AND GAS WELL

1. When heat exerts

reservoir, organic
sulphide in the
petroleum decomposes
and produces H2S.
.SOURCE OF H2S IN THE OIL AND
GAS WELL
2 In deep well , Mud conditioners produce
H2S by high temperature thermal
decomposition.
Sulforated phenolic resin decomposes and
produces H2S at 100.
Brown coal, red coal decompose and
produce H2S at 150.
 .DISTRIBUTION
LAW
1.Content of H2S is increasing
with depth increasing .

2. Content of H2S is in great

difference in different area.
.DISTRIBUTION LAW
3.In most cases, H2S exists
in carbonate rock zone---
evaporates rock zone ,
especially carbonate
associated sulfate
depositional environment.
 .GAS RESERVOIR
CLASSIFICATION
Numb Type Content
er of H2S
1 Non-sour gas <0.0014%
reservoir
2 Low sour gas 0.0014-
reservoir 0.3%
3 sour gas reservoir 0.31.0%
4 Medium gas 1.05.0%
reservoir
5 high sour gas >5.0%
reservoir
.SULFUREOUS AREA IN CHINA

SiChuan oilfield
Hua Bei oilfield.
Xinjiang oilfield
JingBian area in ChangQing oil
field
 Overseas
In Texas gas field of South America,
content of H2S is about 98%.
In former Soviet Union, 70% of oil
and gas wells content H2S.
 .characteristics of H2S
1. Very toxic.
Fatal concentration of HCN is 300ppm.
Fatal concentration of H2S is 500ppm.
Fatal concentration of SO2 is 1000ppm

2.Colorless/invisible.
Boiling point: -60C.
 .characteristics of H2S

3.Relative density is 1.19,

approximately 20%
heavier than air, easy to
settle in lower places.
 .characteristic of H2S

4. Smells like rotten eggs.

5. It is easily dispersed
by the wind.
6. It is extremely
flammable
 .characteristics of H2S
7. Explosive limits: 4.3% to
46%. (percent by volume in
air), in contrast the explosive
limits for natural gas range
only from 4.8 to 13.5%.
8. H2S is highly soluble in
water and hydrocarbons such
as gasoline, kerosene, and
crude oil. At atmospheric
pressure water will absorb
approximately three times its
own volume of H2S .
.
 .characteristics of H2S
9. H2S is highly
corrosive to certain
metals, especially for
solution containing
CO or O2
 . CONCEPTION OF
1.volume concentration--H
CONCENTRATION 2S volumetric
proportion in air.
1ppm=1/1000000
2.weight concentration the weight of H2S
in 1 m3 air. (mg/L, g/L, mg/m3)
 Unit 3
HARMFULNESS OF
H2S TO HUMAN BEING
AND FIRST AID AND
TREATMENT TO THE
VICTIM
 .HARMFULNESS OF H2S TO
HUMAN BEING
1. How does the H2S affect
peoples health.
Mouth respiratory tract
lungblood
all the organs (hemoglobin
O2+Hemoglobin organs
cause pulmonary organs
H2S+ Hemoglobin edema.
2. Symptoms
irritation case

Exposure to low concentrations

(50 to 100ppm) of H2S will cause
coughing, eye irritation, and loss
of sense of smell after 2 to 15
minutes; altered respiration, pain
in the eyes and drowsiness
 acute case
Breathing of H2S concentrations
of500to1000ppmorhigherwill
cause almost immediate loss of
consciousness.Symptomsinclude
breathing difficulties, cramps,
paralysis,andlossofcolor.
.HARMFULNESS OF H2S TO
HUMAN BEING
3.safe critical concentration- --man
can be exposed for an 8-hour
workday, 10ppm(international
standard).
dangerous critical concentration
---allowed to expose for 10min,
100ppm.
Dead critical concentrationonly in
one breath lead to death, 2000ppm .
 .FIRST AID

1. Put on breathing apparatus and

then remove from the
contaminated area into fresh air
as soon as possible.
2. If breathing has stopped and no
pulse, start artificial respiration
and CPR immediately.
3. Keep the victim warm and at
rest.
 .FIRST AID
4. Get the victim to a doctor, but
continue artificial respiration
enroute if breathing stops.
5. If an oxygen resuscitator is
available, use it instead of artificial
respiration, as concentrated
oxygen oxidized H2S more quickly
into the blood, however, begin with
artificial respiration rather than
wait for a resuscitator.
 .FIRST AID
6. For conjunctivitis
(irritation of eyes), wash
eyes with a 1% boric acid
solution followed 10%
argyrol drops. Ophthalmic
boric acid ointment will
also give some relief
.CAUTION IN THE PROCESS
OF MEDICAL TREATMENT
1.When victim restore, fed tea or
coffee drink and treated by
special nurse.
2.If eyes are injured slightly,
completely washing with fresh
water or keeping eyes cool with
cooling thing.
3.Keep him warm in winter and
avoid sunstroke in summer.
4.The victim should be at
 Unit 4
DAMAGES OF H2S TO
EQUIPMENT &TOOLS
AND ITS CORROSSION
PROOF
 .TYPES Of CORROSION
1.Weightlessnesscorrosion
(electrochemical corrosion only under water
existence)
Fe+H2S---FexSy+2H+
H2S--H++HS-
HS---H++S2-
ProductFexSyisaloosematter.Itcanmakesteel
materialpitted,spotted,resultinginequipment
thinning,piercedanddecreasingstrengthand
fracturing.
2. Sulfide Stress corrosion
Weightlessness corrosion is first produced only
under water existence and make steel material pitted,
spotted and shed. meanwhile water in the surface of
metal exist a lot of hydrogen atoms and most of them
combine molecules, but under high concentration of
H2SandHS-(ion). thispreventsrateofcombinationand
therearecertainconcentrationhydrogenatoms,someof
atoms seep into inside of metal and collect in the
deficiency and combine hydrogen molecule. The space
hydrogenmoleculeis20timelargerthanhydrogenatom
andleadhighpressureinsidemetal.Alotofgasbubbles
appear.thiscausessoftmetalhardenandhighstrength
steelcrisped.
 tensile

CRACK

H + HHHHH H H+ H+ H+

H2
 chasm

No deformation
 Properties of sulfide stress
corrosion

1.Chasm is flat and not plastic deformation.

2.Mainly happen under tension stress, crack is
vertical with tension.
3. Sulfide Stress corrosion cracking usually
happen suddenly , no signs.
4.Source of cracking often happens where stress is
concentrated.
.Influence Factors

1.temperature
Weightlessness corrosion
speed is fast with
temperature increasing.
Stress corrosion
Corosion
speed
speed is
fastest at 25 .

temperature
25
 .Influence Factors
2.PH
value corrosion speed
become slow with PH
value increasing and is
fast with hydrogen and co2
in solution
3. Properties of
steel
A. Metallographic
structure
B. Degree of hardness
HRC< 22.The harder
metal is easy to
corrode.
.ANTICORROSIVE MEASURES
1.Tubing and casing
A. Select sulfur resistant tubular.
Tube and casing at lower gel
strength is more suitable than at
higher gel strength in the H2S
well. For example, NKAC-95
tubular and NKK955 drill pipe
made in Japan.
B. Reversing circulation added
anticorrosive agent.
 .ANTICORROSIVE
MEASURES
A..Drill
2 pipe properly.
Select materials
HRC<22
B. Maintain working situation of drill pipe.
Alkaline drilling fluid , PH>10.
Using sulphur removal agent.
[ 3Zn(OH)2ZnCO3] +4H2S=4ZnS+CO2+7
H2O
Using oil based mud, fresh
water mud is prohibited.
.ANTICORROSIVE MEASURES

C. Using internal coating

drill pipe.
D. Using oxygen scavenger.
E. Drill pipe defect
detection periodically.
F. Balanced- pressure
drilling technology
 Unit 5
DETECTING EQUIPMENT
& PERSONNEL
PROTECTION
 .Detecting to H2S
1.Chemical reagent method
A. Lead acetate indicator paper
Formula 10g lead acetate +100ml
acetic acid or distilled water
---Principle
Pb(CH3COO)2+ H2S=
PbS (brown or black)+2CH2COOH
B. Ampere bottle method
There are white Pb(CH3COO)2 solid
grain in the bottle. Sponge block up its
mouth
 2.Electronic monitoring
device
A. Portable device
Frequent inspections of all poorly
ventilated areas should be made with a
portable gas detection instrument. This
instrument should be capable of reading
a minimum of 10ppm of H2S.
Detection devices should be available for
use by all personnel on site.
 2.Electronic monitoring
device
Cautions:
1.Protect the sensor,especially dont cover
the sensor with mud,if the sensor is
covered, the detector cant exactly show
the concentration of H2S.
2.Detection heads require regular calibration
to retain their accuracy
 B. Fixed device
Each drilling facility shall have a fixed H 2S
monitoring and detection system that
activates audible and visual warning alarms
at a level of 10ppm H2S in the air.
Fixed systems shall have a central readout
panel located in an area where it will be
constantly monitored.
 B. Fixed device
Required locations for sensor heads:
drillers console
mud tank
shale shaker
ventilation system of living quarters
wellhead cellar
.Breathing apparatus
A. Chemical cartridge respirators
1. Basic principle---absorb toxic gas with
chemical product. Filtration capacity is
gradually reducing with medicine in the
cartridge consumed.
2.TF-1 type ---
mask, air conduit and
cartridge
 3.Selecting Mask
Sum of perimeter from top of head
through two cheeks to jaw and length of
forehead through eyebrow to ear saddle.
Selecting mask code according to the
sum.

Size <94 95-97 98-100 >101

(cm)
code 1 2 3 4
Caution
Select canister properly. (grey NO.4).
Check sealing property.
If smelling toxic gas, leave off toxic
gas area quickly.
if oxygen content is less than 18% in the
air or poisoning gas content is more than
2%, all canisters doesnt work .
Disinfecting mask after used.
canisters must be sealed properly, stored
in dry, clean and ventilate area to prevent
wet.
 CARTRIDGE TYPE
NUMBER COLOR GAS NAME
1L Grass green phosgene
and white
1 Grass green hydrogen
cyanide
3 Brown benzene
4 Grey NH3, H2S
5 White CO
6 Black mercury
7 yellow SO2
 B. Compressed air breathing
apparatus
---principle
Supply compressed air in the bottle,
isolated with the contaminated
atmosphere, no need to select the mask,
the pressure of the air in the bottle is
about 30Mpa (4285psi), the pressure will
be decompressed through pressure relief
valve to supply positive pressure into full
face mask.
 B. Compressed air breathing
apparatus
Composition:
--external mask mould in rubber or silicone.
--wide visibility visor moulded in polycarbonate.
--assembly which unites the connector for B.A, the
inhalation valve, two exhalation valves and the
speech device into a compact body.
--small inner dead space reduction mask moulded in
rubber, provided with two air circulation valves which
prevent the visor from steaming up.
--five strap headharness moulded in rubber or silicone
with quick-fastening buckles.
--bottle
 B. Compressed air breathing
apparatus
Cautions:
1. Before you use the breathing
apparatus, check its working pressure and
its sealing property, then open the valve.
2. When the work pressure is lower than
the red line, escape quickly.
 B. Compressed air breathing
apparatus
Locations for breathing apparatus should include:
rig floor
derrick monkey boards
mud logging unit
shale shaker unit
pump rooms (mud and cement)
crew quarters
toolpushers and company drilling supervisors
office
each designated briefing area
 Unit 6
Safety requirement
in the
sulphureous area
 . Equipment requirement
Ram- type blowout preventers
The ram bodies must be heat treated and certified
for H2S service by the manufacturer. The following
parts must be new and certified for H 2S service.
1. Bonnet Seals
2. Connecting rod seals
3. Connecting rod (heat treated)
4. Ram packer
5. Ram rear seal
 . Equipment requirement
Annularpreventer
Thebodymustbeheattreatedandcertifiedfor
H2S service by the manufacturer. The rubber
elementcanbenaturalrubberorBunaN;both
are suitable for H2S service. The upper and
lower piston and piston head seals should be
newwhenthepreventerisinstalled.
 . Equipment requirement
Spoolsandcross
Thespoolsandcrossesmustbeflanged
andthelowcarbonsteeltypescertified
forH2Sservicewithamaximumhardness
ofRc22.
Accumulatorunits:
Accumulatorsshouldbelocatedinsafeplace
thatiseasilyaccessibletorigpersonnelinan
emergency. Whentheaccumulatorisnot
permanentlyfixed,itshouldbelocatedasafe
distanceupwindfromtheriginthedirection
oftheprevailingwind.
 Remote choke control panel
A remote choke control panel to operate the
choke manifold should be set a safe distance
upwind from the rig in the direction of the
prevailingwind.
 . Equipment requirement
Vacuum degassers/atmospheric mud-gas
separator (poor boy separator)
Thevacuumdegassersshouldbecapableof
effectivelyremovinggasescontainingH2S
fromthedrillingfluid.Theventoutletonthe
vacuumdegassershallbeextendedsothatthe
extractedgascanberoutedtoaremotearea
forflaringorconnectedintotheatmospheric
mud-gasseparatorline.
 . Equipment requirement
Flarelines :
Flare lines should be installed from the
degasser, choke manifold, and mud-gas
separator. All flare lines should be equipped
with the means for constant Flare lines should
beinstalledfromthedegasser,chokemanifold,
andmud-gasseparator.Allflarelinesshouldbe
equipped with the means for constant or
automaticignition.
 . Equipment requirement
Drillpipe:

Lowergradesofdrillpipe,orpipemadefrom
steel with anti-corrosive properties, should be
used in order to minimize hydrogen
embrittlementofsulphidestresscracking.
Additional safety equipment:
The following items should be available on the rig:
Chalkboards and note pads or other communication
aids
Bullhorns
Resuscitators
Wind indicators
Bug blowers
Hazard warning signs
first-aid kit
Stretcher
Blankets
Eye wash station
.Drilling well site layout
1. There should be three briefing areas
in well site, one should be in the
upwind
2. Well site should be at spacious place.
3. Well derrick, crew quarters and
briefing areas should be equipped with
wind indicator.
.Drilling well site layout

4. Drill pipe should be deposited in upwind

area.
5. Mud tank, shale shaker, flare pit should be
in the downwind area.
.Drilling well site layout
6. explosive-proof blower fans should
be installed at the place where H2S
easily gathered.
In the drilling site, H2S is always
found in the following area: mud
return line, BOP area, substructure,
shale shaker area, degasser, choke
manifold, mud pumps, mud piping
system, waste pit, rig floor, flare pit,
lowering areas around the rig.
 .Drilling well site layout
7. There should have two relief lines which
should be in vertical direction, the lines should
be 100 meters far from the wellhead.
8. One kill line should be in the upwind of the
prevailing wind.
9. No welding at the connection of wellhead,
casing and high pressure area of blowout
prevention line.
. Additional safety requirements
1. Tubular goods that could possibly
be exposed to H2S (surface and
protective casing) should be
inspected and their hardness limited
to Rc22 or less.
 2. Drillstring components should
be limited to maximum yield
strength of 95,000psi. This will
eliminate catastrophic failure due
to hydrogen embrittlement if the
drilling mud becomes
contaminated with H2S.
3. Corrosion inhibitors for drillpipe
protection (i.e. filming amines)
should be on location and applied
before an H2S zone is penetrated.
4. drillpipe, safety valves, and all
downhole tools should be certified for
H2S service.
 5. two flare lines, manifolded to
the choke manifold degasser and
the mud gas separator, should be
installed on opposite sides of the
well, perpendicular from the well
to the prevailing winds.
 6. flare and other lines subject to
corrosion by H2S may be susceptible
to some sulfide stress cracking, if
the steel contains residual stresses.
Yield strength of steel used should
be limited to approximately 95,000psi
maximum and or a hardness of Rc22.
Also, working stresses should be
limited to 80 percent of the yield
strength.
 7. all welds and heat affected
zones should be stress relieved
and their hardness limited to
Rc22.
8.breathing air supply stations,
resuscitators, and SCBA units
should be located in strategic areas,
with SCBA units assigned to each
person on location.
9. mud logging units should have
devices with alarms continuously
monitoring for H2S.
 10. all personnel should
have ear plugs, or have their
drums checked for puncture
by a doctor.
11. Drilling fluid PH value>10
 12. while tripping, breathing
apparatus should be worn by
personnel in the working area
prior to circulating bottoms-up in
case H2S is indicated in
sufficient quantities to require
the use of breathing apparatus.
 13. Coring operations in H2S-bearing
zones
Breathing apparatus should be worn
from 10 to 20 stands in advance of
retrieving the core barrel and
especially while the cores are being
removed from the barrel. Cores to be
transported should be sealed and
marked indicating the presence of
H2S.
14.During the above operations,
warning signs indicating
DANGER-POISON GAS shall be
displayed in languages understood
by all personnel on the rig. On land
rigs, flags at the location entrance
gate are to be used to indicate that
a hazardous situation exists.
 H2S DRILL
Introduction:
1. Every one should hear the alarm
in the wellsite.
2. Safe area should be marked
clearly at the entrance of
wellsite, and equipped with
breathing apparatus.
3. All vehicle should put out fire .
 H2S DRILL
H2S drill program
1.allthepeopleatwellsiteshouldwear
breathingapparatuswhilealarming.
2 driller and two floormen wear breathing
apparatus.
3. shut in the well according to the part As
requirements.
4.driller and two floormen equipped with
breathing apparatus should wait for
instructions on the rig floor
 H2S DRILL

5. Toolpusher and assistant driller wear

breathing apparatus to check whether the
well is shut-in and the source of H 2S, and
command on the rig floor.
6. foreman and roustabout wear
breathing apparatus to check whether
there are people at well site, then go
to safety area.
 H2S DRILL
7. all the other people go to safety
area.
8. doctor take first aid box and
oxygen bottle to safety area and
should be responsible for head count,
then report to supervisor.
9.people in safety area should work in
pairs to rescue victim anytime.
 Contingency plan
Acontingencyplanandanevacuationplanshouldbe
prepared for each well capable producing an
atmospheric concentration of H2S in excess of
10ppm. Capable of the plan should be maintained at
therigsiteandpostedsothattheyareavailabletoall
personnel.Theseplansshouldatleastinclude:
 Contingency plan
1. Responsibilities of personnel,
such as the man-in-charge, and
should define essential and
nonessential personnel
 Contingency plan
2. Location of residences, businesses,
park, school, churches, roads, medical
facilities, etc. within a one mile radius
from the well. A larger radius may be
required depending on well conditions,
terrain, atmospheric conditions and
concentrations of H2S.
.
.
 Contingency plan
3. Emergency telephone numbers
including emergency services
(ambulance, hospital, doctor,
helicopter, etc.), government
agencies, operator and contractor
personnel, and service companies.
 Contingency plan
4. Emergency and warning
procedures.
5. Safety equipment and
supplies.
6. Training of personnel