Hydrogen Sulfide химические свойства, назначение, производство
Описание
Hydrogen Sulfide is a colorless, very poisonous, flammable gas with the
characteristic foul odor of rotten eggs. It often results
from the bacterial breakdown of organic matter in the
absence of oxygen, such as in swamps and sewers where
anaerobic digestion can take place. It also occurs in
volcanic gases, “natural gas”, and some well waters.
Hydrogen sulfide has numerous names, some of which
are archaic.
Small amounts of hydrogen sulfide occur in crude oil,
but natural gas can contain up to 90%. About 10% of the
total global emission of H2S is due to human activity.
Химические свойства
Hydrogen sulfide is a colourless gas with strong odour of rotten eggs (odour threshold ca 0.2 ppt).
Физические свойства
H2S is soluble in
carbon disulfide, methanol, acetone and alkanolamines. A solution of hydrogen sulfide in water is initially
clear but over time turns cloudy. This is due to the
slow reaction of hydrogen sulfide with the oxygen dissolved in water, yielding elemental sulfur, which
precipitates out.
Вхождение
Reported found in heated French beans, beef broth, vapors of canned beef, canned beef, beef extract, heated
beef fat, raw beef, beer, bread, heated Brussels sprouts, cabbage, cooked celery, cheddar cheese, cooked and raw chicken, chives,
heated coconut, codfish, ground and roast coffee, heated corn, heated egg, grapefruit juice, cooked herring, citrus juices, strawberry,
cabbage, onion, potato, rutabaga, tomato, blue cheese, buttermilk, raw and boiled eggs, coffee, potato chips, rice, soybeans, okra,
sweet corn, sake, squid, shrimps, cooked, fatty fish and other natural sources
История
Hydrogen sulfide is a colorless, flammable, toxic gas with the characteristic odor of rotten eggs.It is produced naturally from the anaerobic bacterial decomposition of organic wastes, occurs in volcanic gases and hot springs, is a product of animal digestion, and is generated in industrial processes. Hydrogen is a natural component of natural gas and petroleum; it is only a small fraction of oil (hundreds of ppm), but may form an appreciable component of natural gas. Natural gas typically contains up to 5% hydrogen sulfide. Natural gas is considered sour if the hydrogen sulfide content exceeds 5.7 mg of H2S per cubic meter of natural gas. The process for removing hydrogen sulfide from sour gas is referred to as sweetening the gas. Because hydrogen sulfide is associated with anaerobic respiration in sewers and swamps, it is referred to as sewer gas, swamp gas, or stink damp.
Использование
Hydrogen sulfide is used as an analyticalreagent and in the manufacture of heavywater. It occurs in natural gas and sewer gas.It is formed by the reaction of a metal sulfidewith dilute mineral acid, and in petroleumrefining.
Методы производства
Hydrogen sulfide is produced during anaerobic respiration (fermentation). Anaerobic respirationenables organisms, primarily bacteria and other microbes, to meet their energy needsusing sulfate, elemental sulfur, and sulfur compounds as electron acceptors instead of oxygen.
Подготовка
By far the largest industrial route toH2S occurs in petroleum
refineries. The “hydrodesulfurization” process liberates
sulfur from petroleum by the action of hydrogen. The
resulting H2S is converted to elemental sulfur by partial
combustion via the Claus process that is a major source
of elemental sulfur (In the Claus process, hydrogen
sulfide is catalytically reacted with oxygen from the air
to produce sulfur and sulfur dioxide). Other anthropogenic
sources of hydrogen sulfide include coke ovens,
paper-mills (using the sulfate method), and tanneries,
where Na2S is used for processing cowhide to form
leather. H2S arises from virtually anywhere where
elemental sulfur comes in contact with organic material,
especially at high temperatures.
Определение
ChEBI: A sulfur hydride consisting of s single sulfur atom bonded to two hydrogen atoms. A highly poisonous, flammable gas with a characteristic odour of rotten eggs, it is often produced by bacterial decomposition of organic matter in the absence of oxygen.
Реакции
Fluorine, chlorine, bromine, and iodine react with H2S to form the corresponding halogen acid. Metal sulfides are formed when H2S is passed into solutions of the heavy metals, such as Ag, Pb, Cu, and Mn. This reaction is responsible for the tarnishing of Ag and is the basis for the separation of these metals in classical wet qualitative analytical methods. Hydrogen sulfide reacts with many organic compounds.
Реакции воздуха и воды
Highly flammable; a flame can very easily flash back to the source of leak. Soluble in water to a maximum of 0.4% by mass at room temperature .
Профиль реактивности
HYDROGEN SULFIDE reacts as an acid and as a reducing agent. Explodes on contact with oxygen difluoride, bromine pentafluoride, chlorine trifluoride, dichlorine oxide, silver fulminate. May ignite and explode when exposed to powdered copper in oxygen [Mertz, V. et al., Ber., 1880, 13, p. 722]. May react similarly with other powdered metals. Ignites on contact with metal oxides and peroxides (barium peroxide, chromium trioxide, copper oxide, lead dioxide, manganese dioxide, nickel oxide, silver oxide, silver dioxide, thallium trioxide, sodium peroxide, mercury oxide, calcium oxide) [Mellor, 1947, vol. 10, p. 129, 141]. Ignites with silver bromate, lead(II) hypochlorite, copper chromate, nitric acid, lead(IV) oxide and rust. May ignite if passed through rusty iron pipes [Mee, A. J., School Sci. Rev., 1940, 22(85), p. 95]. Reacts exothermically with bases. The heat of the reaction with soda lime, sodium hydroxide, potassium hydroxide, barium hydroxide may lead to ignition or explosion of the unreacted portion in the presence of air / oxygen [Mellor, 1947, vol. 10, p. 140].
Опасность
Highly flammable, dangerous fire risk,
explosive limits in air 4.3–46%. Toxic by inhalation,
strong irritant to eyes and mucous membranes.
Угроза здоровью
The acute toxicity of hydrogen sulfide by inhalation is moderate. A 5-min exposure
to 800 ppm has resulted in death. Inhalation of 1000 to 2000 ppm may cause coma
after a single breath. Exposure to lower concentrations may cause headache,
dizziness, and upset stomach. Low concentrations of H2S (20 to 150 ppm) can cause
eye irritation, which may be delayed in onset. Although the odor of hydrogen sulfide
is detectable at very low concentrations, it rapidly causes olfactory fatigue at higher
levels, and therefore is not considered to have adequate warning properties.
Hydrogen sulfide has not been shown to be carcinogenic or to have reproductive or
developmental effects in humans
Пожароопасность
Compound is heavier than air and may travel a considerable distance to source of ignition and flash back. HYDROGEN SULFIDE forms explosive mixtures with air over a wide range. Also reacts explosively with bromine pentafluoride, chlorine trifluoride, nitrogen triiodide, nitrogen trichloride, oxygen difluoride, and phenyl diazonium chloride. When heated to decomposition, HYDROGEN SULFIDE emits highly toxic fumes of oxides of sulfur. Incompatible with many materials including strong oxidizers, metals, strong nitric acid, bromine pentafluoride, chlorine trifluoride, nitrogen triiodide, nitrogen trichloride, oxygen difluoride and phenyl diazonium chloride. Avoid physical damage to containers; sources of ignition; storage near nitric acid, strong oxidizing materials, and corrosive liquids or gases.
Воспламеняемость и взрывоопасность
Hydrogen sulfide is flammable in air in the range of 4.3 to 45.5% (NFPA rating = 4).
Combustion products (sulfur oxides) are also toxic by inhalation. In the event of a
hydrogen sulfide fire, stop the flow of gas if possible without risk of harmful
exposure and let the fire burn itself out.
Сельскохозяйственное использование
Hydrogen sulphide (H2S) is a colorless, poisonous, flammable gas with an odor of rotting eggs. It is found in cesspools and mines and is a by-product of decomposed substances containing sulphur. It is one of the gaseous end-products of the reduction of sulphate in highly degraded paddy fields. Hydrogen sulphide is also produced in the laboratory for use as an analytical reagent.
Использование в материалах
Dry hydrogen sulfide is satisfactorily handled
under pressure at normal ambient temperatures
in carbon steel or black iron piping. Carbon
steels in wet applications are known to be subject
to sulfide stress cracking and low- temperature
brittle fracture under some conditions
of temperature, stress, and pressure. While hydrogen
sulfide itself is relatively noncorrosive to
steel in many uses, factors such as impurities,
pH, erosive conditions, and high thermal or
mechanical stresses in the metal can cause severe
corrosion problems. High-strength steels
are subject to crack formation when exposed to
hydrogen sulfide.
Экологическая судьба
Hydrogen sulfide is a colorless, flammable compressed liquid
gas with a characteristic odor of rotten eggs. The solubility of
hydrogen sulfide in water is 3980 mg l-1 at 20 ℃ and it is
soluble in certain polar organic solvents, notably methanol,
acetone, propylene carbonate, sulfolane, tributyl phosphate,
various glycols and glycol ethers, gasoline, kerosene, crude
oil, and carbon disulfide. The calculated vapor pressure at
21.9 ℃ is 1929 Pa. Boiling point and melting point of the
substance are -60.33 ℃ and-85.49 ℃, respectively. Based
on the estimated Henry’s law constant of 468 atm mol-1 for
hydrogen sulfide, volatilization from water and soil is high.
хранилище
cylinders of hydrogen sulfide
should be stored and used in a continuously ventilated gas cabinet or fume hood.
Local fire codes should be reviewed for limitations on quantity and storage
requirements.
Методы очистки
Wash it, then pass the gas through a train of tubes containing saturated Ba(OH)2 (2x), water (2x), and dilute HCl [Goates et al. J Am Chem Soc 73 707 1951]. It is available in gas cylinders. HIGHLY POISONOUS.
Несовместимости
Hydrogen sulfide is incompatible with strong oxidizers. It will attack many metals,
forming sulfides. Liquid hydrogen sulfide will attack some forms of plastics, rubber,
and coatings. H2S reacts violently with a variety of metal oxides, including the
oxides of chromium, mercury, silver, lead, nickel, and iron.
Утилизация отходов
To respond to a release, use appropriate protective equipment and clothing. Positive
pressure air-supplied respiratory protection is required. Close cylinder valve and
ventilate area. Remove cylinder to a fume hood or remote area if it cannot be shut off.
Disposal Excess hydrogen sulfide should be returned to the manufacturer, according to your
institution's waste disposal guidelines. For more information on disposal procedures,
see Chapter 7 of this volume.
Hydrogen Sulfide препаратная продукция и сырье
сырьё
препарат