ELEMENT 4 HYDROGEN SULFIDE INSTRUCTOR & TECHNICIAN COURSE HSI004

ELEMENT FOUR

Properties and Characteristics of H2S

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ELEMENT 4 HYDROGEN SULFIDE INSTRUCTOR & TECHNICIAN COURSE HSI004

4.1 WHAT IS H2S?

H2S is a highly toxic gas. It is more deadly than carbon monoxide and hydrogen
cyanide gas. It is a colorless, transparent gas that is heavier than air. It tends to
accumulate in low-lying areas. It is very corrosive to certain metals. It can paralyze
your respiratory system and kill you in minutes. At low concentrations it has an
offensive odor similar to rotten eggs. At high concentrations no smell can be detected
because H2S rapidly deadens your sense of smell. Consequently, your nose can not
be depended on to detect H2S.

4.2 WHAT ARE THE FOUR FACTORS THAT PLAY A ROLE IN HOW AN
INDIVIDUAL IS AFFECTED BY H2S?

Duration:
• The length of time an individual is exposed.
Frequency:
• How often has the individual been exposed?
Intensity:
• How much concentration the individual was exposed to.
Individual Susceptibility:
• The individual’s psychological make-up.

4.3 HYDROGEN SULPHIDE SUMMARY

Characteristics of Hydrogen Sulfide and Sulfur Dioxide
• Hydrogen Sulfide, or H2S, is a highly toxic, colorless gas.
• H2S is a heavy gas, in fact heavier than air and can accumulate in low areas or
places where ventilation is poor.
• In low concentrations, H2S smells like rotten eggs, but can rapidly deaden your
sense of smell at higher concentrations.
• H2S is formed by the decomposition of organic matter and is found in a variety of
places.
• Natural gas formations can contain large quantities of H2S, and H2S can be found
in sewers, underground mines, commercial laboratories, and refineries.
• In addition, H2S is flammable in concentrations between 4.3% and 46% by
volume in air and auto ignites at 500 degrees ˚F (260 degrees Celsius).
• H2S burns with a blue flame (sometimes hard to distinguish in daylight) and
another toxic gas is produced when you burn H2S.
• When you burn H2S, you can expect to burn about 80% of the gas.
• Sulfur Dioxide is the byproduct you get when you burn H2S.
• Sulfur Dioxide or SO2 is also a heavy gas, but will rise with increased temperature
and settle downwind as it cools.
• SO2 will react with water to form an irritable acid.

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ELEMENT 4 HYDROGEN SULFIDE INSTRUCTOR & TECHNICIAN COURSE HSI004

• H2S is very corrosive to certain metals and can cause a form of hydrogen
embrittlement known as Sulfide Stress Cracking.
• One byproduct of H2S corrosion is called Iron Sulfide and can spontaneously
combust when exposed to air.
• H2S is soluble in water and can become dissolved in drilling fluids.
• Common locations of fixed sensors includes Rig Floor, Bell Nipple, Shaker, Mud
Pits and other areas where H2S may accumulate.
• The preset alarm levels are usually determined by government regulation.
• In the United States, audible alarms in federal waters are set to go off at 20ppm
H2S in air.

4.4 HAZARDS
The principal hazard is death by inhalation. When the amount of gas absorbed
into the blood stream exceeds that which is readily oxidized, systemic poisoning
results, with a general action on the nervous system. Labored respiration occurs
shortly and respiratory paralysis will follow immediately at higher concentrations.

Death will occur from asphyxiation unless the exposed person is removed
immediately too fresh air and breathing stimulated by rescue breathing.

Other levels of exposure may cause the following symptoms individually or in

combinations:
• Headache – Dizziness – Excitement
• Nausea – Coughing – Drowsiness
• Dryness and sensation of pain in the nose, throat and chest
• Detection of H2S solely by smell is highly dangerous as the sense of smell is
rapidly paralyzed by the gas.
• H2S is extremely toxic, ranking second to Hydrogen Cyanide and five (5) to six
(6) times more toxic than Carbon Monoxide.
• Colorless.
• Offensive odor, often described as that of rotten eggs.
• Heavier than air – Vapor Density 1.1895 (Air = 1.00 @ 60 degrees ˚F). Vapors
may travel considerable distance to a source of ignition and flashback.
• Forms an explosive mixture with air in concentrations between 4.3% (LEL) and
46% (UEL) by volume.
• Auto-ignition temperature of 500 degrees ˚F or 260 ˚C; Cigarette burns at 1,400
degrees ˚F.
• Burns with a blue flame and produces Sulfur Dioxide (SO2), which is less toxic
than H2S, but very irritating to eyes and lungs and can cause serious injury.
Chemical pneumonia can develop in a few hours.
• Soluble in water and liquid hydrocarbons, H2S dissolves in water forming a weak
hydrosulphurous acid.

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ELEMENT 4 HYDROGEN SULFIDE INSTRUCTOR & TECHNICIAN COURSE HSI004

• Produces irritation to eyes, throat, and respiratory system.

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ELEMENT 4 HYDROGEN SULFIDE INSTRUCTOR & TECHNICIAN COURSE HSI004

4.5 CORROSIVE EFFECTS OF HYDROGEN SULFIDE

There are three types of corrosion effects resulting from the attack of H2S on metals.
In the presence of water, an acidic solution results which can cause general metal loss
and loss of strength.

Pitting or localized corrosion which can cause rapid penetration of the metal.
Sulfide stress cracking or hydrogen embrittlement. There is little evidence of
metal loss, but the stresses develop when atomic hydrogen generated by the corrosion
penetrates the metal and causes early failures. The atomic hydrogen diffuses into the
crystal structure of the steel then expands as molecular hydrogen is formed and
produces stress cracking.

The corrosion effects may not be severe without the presence of carbon dioxide or
oxygen. Hydrogen sulfide alone reacts with steel to form a film of iron sulfides that
tends to retard corrosion. If carbon dioxide is present, it combines with water to form
carbonic acid. This acid reacts with steel to eat away the metal. It also eats away the
protective sulfide films that may be developing. Corrosion then continues unchecked.
The rusting or oxidation of steel is accelerated by H2S as it reacts with the oxide to
form an iron sulfide and water. The combined effects of oxygen and hydrogen sulfide
for corrosion are thus more severe.

Copper, zinc and some of their alloys (brass, bronzes, etc.) are rapidly consumed by
H2S corrosion. This should not be overlooked when making specifications for valves,
metering equipment and pressure gauges. Copper tubing and bourdon tubes should be
substituted with austenitic stainless steel. Aluminum bronze is an exception; it is
resistant to H2S attack.

The hazards of Sulfide Stress corrosion cracking in steel can be minimized by limiting
the hardness to Rockwell HRC-22. Close observation of normalizing, tempering and
stress relieving are necessary to prevent failures. At elevated operating temperatures
above 150 degrees – 175 degrees higher tensile strength steels can be used safely.

4.6 OCCURRENCE OF HYDROGEN SULPHIDE

The following is an excerpt from NIOSH “Interim Work Practice Recommendations
for Hydrogen Sulfide”, August, 1976. (Out of Print)

“Hydrogen sulfide is found in solution in some crude oils. The gas begins to pass off
as it reaches the surface with the process being greatly accelerated by heat, especially
during refining. It is generally believed that excessive exposure can occur at many
points in the oil drilling and refining operations.

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ELEMENT 4 HYDROGEN SULFIDE INSTRUCTOR & TECHNICIAN COURSE HSI004

Some of the areas/activities in which there might be a potential exposure to hydrogen

sulfide are as follows:
• Drilling operations: Recycled drilling mud, water portion from the sour crude
wells, blowouts (infrequent).
• Tank gauging (the opening of the tank hatch to measure the liquid level in the tank
car results in the release of buildup hydrogen sulfide). Includes run-down tanks,
storage tanks at pipeline stations, and crude oil storage tanks in refineries, storage
tanks for intermediate and finished products.
• Field maintenance of wells (replacements of packing, pulling of pumping rods,
etc.).
• Entry into confined spaces including trenches, pits, process vessels and tanks.
• Leaks in pumps or lines (consideration of corrosion and embrittlement).
Equipment maintenance.
• Stripping of hydrogen sulfide and carbon dioxide from crude oil at the oil field
and at the refinery.
• Sulfur recovery during desulfurization of sour crude; and from contaminated
molten sulfur.
• Injection of sour gas back into formation to stimulate oil production.
• Asphalt storage and associated operations.
• Acid cleaning of well and process units.

4.7 REGULATIONS
Acceptable Concentrations
Acceptable Eight-hour Time Weighted Average (TLV/TWA) (ACGIH)
To avoid discomfort, the 8-hour threshold limit value/time-weighted averaged
concentration of hydrogen sulfide shall not exceed 10ppm in the USA, 5ppm UK, and
7ppm Kazakhstan. The TLV may differ per country standards.

Permissible Exposure Limits (PELs) (OSHA-USA)

Time-Weighted Average (TWA) is the employee’s average airborne exposure in any
8-hour work shift of a 5 day work week which shall not exceed 10ppm (revised).
Short Term Exposure Limits (STEL) is the employee’s 15-minutetime-weighted
average exposure which shall not be exceeded an time during a work day – 15ppm.

Facial Hair
CGS-OCS Standard No. 1, Reference Document 32.2; 29 CFR 1910.134 USA.
Respirators shall not be worn when conditions prevent a good face seal…Facial hair
lying between the sealing surface of a respirator face-piece and the wearer’s skin will
prevent a good seal…”
Therefore, no person having a beard, moustache, or sideburns that passes between the
face and the sealing surface of a respirator face-piece shall be allowed to enter into an
AOGC H2S work-site unless approved by the location supervisor because that person
will not be expected to utilize breathing equipment.

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ELEMENT 4 HYDROGEN SULFIDE INSTRUCTOR & TECHNICIAN COURSE HSI004

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4.8 BURNING AND FLARING H2S

Burning and flaring hydrogen sulfide is an accepted engineering method for

disposing of the gas. In addition to regulatory requirements associated with the
emissions, there are a number of inherent problems in this process.
Although H2S has an ignition temperature of 500 degrees ˚F, it only generates 680
btu/hr during the burning process. This is a fairly low number which is indicative that
H2S is a poor fuel gas. The wide flammability range of 4.3% - 46% assists in the
combustion, but the flame generated by the flaring has a tendency to go out unless the
gas is mixed with a more efficient fuel gas such as methane.

Due to the incomplete combustion of the hydrocarbons, a number of toxic gases are
produced during the burning and flaring of H2S. Among these we are most concerned
with sulfur dioxide (SO2), which is an irritant gas and extremely harmful in itself.
Other toxics formed are carbon monoxide (CO), carbon dioxide (CO2, oxides of
nitrogen (NOx), and some portion of the H2S which remains unburned.

The toxic properties of SO2 demand that additional training be provided to all affected
personnel relating to the hazards of SO2. This training may be presented in
conjunction with the H2S module and a thorough review of the SO2 material safety
data sheet is essential.

The engineering characteristics of flare and stack design are critical in obtaining
optimum performance from the system. Qualified engineers or engineering
consultants should be employed in this process to ensure maximum efficiency.

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