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CHAPTER 19: SULFUR AND SULFURIC ACID

SULFUR
Sulfur, symbol S, tasteless, light yellow nonmetallic element. Sulfur, also called brimstone, is in group VI
of the periodic table. Its atomic number is 16, and its atomic weight is 32.064. It exists in nature both in the free-
state and combined in ores such as pyrite (FeS2), sphalerite (ZnS), and chalcopyrite (CuFeS2).

Uses
Over ninety percent of the sulfur used is converted to sulfuric acid, but other industrial uses abound. Some
of these are: in the manufacture of wood pulp, carbon disulfide, insecticides, fungicides, bleaching agents,
vulcanized rubber, detergents, pharmaceuticals, and dyestuffs. Among some new uses being studied are: (a) as an
extender for paving asphalt, (b) sulfur concretes and mortars, (c) plant and soil treatment, (d) sulfur-alkali metal
batteries, and (e) foamed sulfur insulation.

MINING AND MANUFACTURE OF SULFUR

Frasch Process
A method of melting the sulfur underground or under the sea and then pumping it up to the surface. This
ingenious method was devised by Herman Frasch in 1890’s.
In this method three concentric pipes, with diameters of 20cm, 10cm and 3cm, are driven down into the
sulfur-containing deposits. Water, heated under pressure to 160°C, is forced through the outer pipe into the
deposit, melting the sulfur. Molten sulfur, being heavier than water, sinks and forms a pool around the base of the
well, where it enters through the lower perforations and rises in the space between the 10cm and the 3cm pipes.
When a sufficient quantity of sulfur has been melted, hot air is forced down the inmost pipe (3cm pipe) to form a
froth (bubbles that form in or on a liquid) with the molten sulfur, and the mixture is forced up to the surface
through the 10cm pipe. On the surface, the liquid sulfur moves through steam-heated lines to a separator where
the air is removed. Then the sulfur can be either solidified in large storage vats or kept liquid in steam-heated
storage tanks.

Figure 19.1 Schematic diagram of the Frasch process for mining sulfur.
Sulfur from Fuel Gases

Increasingly hydrogen sulfide is being removed during the purification of sour natural gas, coke-oven gas,
and from petroleum refinery gas by dissolving it in potassium carbonate solution or ethanolamine, followed by
heating to regenerate it. The H2S produced is burned to give sulfur dioxide for sulfuric acid. However, the
majority is converted to elemental sulfur.
3
𝐻2 𝑆(𝑔) + 2 𝑂2 (𝑔) → 𝑆𝑂2 (𝑔) + 𝐻2 𝑂(𝑔) ∆𝐻 = −518.8 𝑘𝐽
𝑆𝑂2 (𝑔) + 2𝐻2 𝑆(𝑔) → 3𝑆(𝑙) + 𝐻2 𝑂(𝑔) ∆𝐻 = −142.8 𝑘𝐽

SULFURIC ACID

Sulfuric Acid, H2SO4, is corrosive, oily, colorless liquid, with a specific gravity of 1.85. It melts at 10.36°
C (50.6° F), boils at 340° C (644° F), and is soluble in all proportions in water. When sulfuric acid is mixed with
water, considerable heat is released. Sulfuric acid is a strong acid, that is, in aqueous solution it is largely changed
to hydrogen ions (H+) and sulfate ions (SO42-). Each molecule gives two H+ ions, thus sulfuric acid is dibasic.
Production and Usage
Sulfuric acid is the agent for sulfate formation and for sulfonation. It is employed in the manufacture of
fertilizers, leather, and tin plate, in the refining of petroleum, and in the dyeing of fabrics. Other uses are listed.

Table 19.1 Uses of Sulfuric Acid for Different Concentrations


Uses
53-56̊ Be* Superphosphate manufacture, battery acid
60̊ Be manufacture of sulfates of ammonia, copper (bluestone), aluminum (alums), magnesium
(Epsom salts), zinc, iron (copperas), and organic acids such as citric, oxalic, acetic, and
tartaric; and for pickling iron and steel before galvanizing and tinning, refining and
producing heavy metals, electroplating, and preparing sugar, starch, and syrup
Strong sulfuric purification of petroleum products, preparation of titanium dioxide, alkylation of
acid, 93-99% isobutene, manufacture of many nitrogen chemicals, synthesis of phenol, recovery of fatty
acids in soap manufacture, and manufacture of phosphoric acid and triple superphosphate
Oleums Needed for petroleum, nitrocellulose, nitroglycerin, TNT, and dye manufacture
*Baume degrees: The Baumé scale is a pair of hydrometer scales developed by French pharmacist Antoine
Baumé in 1768 to measure density of various liquids.

MANUFACTURE OF SULFURIC ACID

Two process
1. Lead Chamber Process ( Obsolete )
This is an old process and was introduced in Europe in near the middle of 18th century. This
method uses nitrogen oxides as oxygen carrying catalysts for the conversion of sulfur dioxide to sulfur
trioxide. The reactions which produce the sulfur trioxide and sulfuric acid take place within the huge
lead chambers or in packed towers which may be substituted for the chambers. Chambers process
produced acid of concentration less than 80%. The major disadvantage includes the limitations in
throughput, quality and concentration of the acid produced.

2. Contact Process
This was first discovered in 1831 by Phillips, an Englishman, whose patent included the essential
features of the modern contact process, namely, the passing of a mixture of sulfur dioxide and air over
a catalyst, followed by the absorption of the sulfur trioxide in 98.5-99% sulfuric acid. In the contact
processes, the sulfur dioxide is converted to sulfur trioxide by the use of metal oxide catalyst.
Manufacture by the Contact Process

Figure 19.2 Flowchart for Contact Process

Outlined steps and conditions necessary for the industrial production of H2SO4 from its raw materials:

Step 1: Molten sulfur (or sulfide ore e.g. pyrite) is combusted to form sulfur dioxide(𝑆𝑂2 ).
𝑆 (𝑙) + 𝑂2 (𝑔) → 𝑆𝑂2 (𝑔) ∆𝐻 = −298.3 𝑘𝐽, 25°𝐶

Step 2: Sulfur dioxide gas is transferred to a catalytic converter where it is oxidized to sulfur
trioxide(𝑆𝑂3 ).
1
𝑆𝑂2 (𝑔) + 2 𝑂2 (𝑔) → 𝑆𝑂3 (𝑔) ∆𝐻 = −98.3 𝑘𝐽, 25°𝐶
Conditions necessary include a pressure of 1-2 atm, a small excess of 𝑂2, a catalyst of vanadium
(V) oxide, and temperature range of 400°𝐶 − 500°𝐶.

Step 3: Sulfur trioxide is dissolved in concentrated sulfuric acid (𝐻2 𝑆𝑂4 ) to form oleum (𝐻2 𝑆2 𝑂7 ).
Water is then added to the oleum to produce sulfuric acid.
𝐻2 𝑆2 𝑂7 (𝑙) + 𝐻2 𝑂(𝑙) → 2𝐻2 𝑆𝑂4 (𝑙)
𝑆𝑂3 (𝑔) + 𝐻2 𝑂(𝑙) → 𝐻2 𝑆𝑂4 (𝑙) ∆𝐻 = −130.4 𝑘𝐽, 25°𝐶

Figure 19.3 Typical flowchart for a sulfur-burning double-absorption contact sulfuric acid plant.
Contact Process Equipment

1. Burners
 Sulfurs and some sulfide ores are the usual raw materials
 It is then pumped from a storage tanks through heated lines and sprayed into a furnace using
burners very similar to those usually used for burning fuel oil.
 Ores are burned in fluidized beds or rotary roasters.
2. Treatment of the Burner Gas
 Sulfur dioxide burner gas may contain carbon dioxide, nitrogen, such impurities as chlorine,
arsenic, fluorine, and a small amount of dust. If sulfide ore is roasted, efficient dust collectors,
cooling and scrubbing towers, and electrostatic mist precipitators may be added.
 To prevent corrosion from the burner gas, it is customary to dry the air for burning the sulfur and
to dry the roaster gases before oxidizing the sulfur dioxide.
3. Heat Exchangers and Coolers
 Before the gases are fed to the converter, they are adjusted to the minimum temperature at which
the catalyst rapidly increases the speed of the reaction, usually 425-440̊C.
 For this purpose, cold air may be introduced (to cool by dilution), or boilers, steam superheaters,
or tubular heat exchangers may be employed.
 Heat exchangers usually consist of large cylinders containing many small tubes.
 The SO3-containing gases usually pass through the tubes and the SO2-containing gases surround
the tubes.
4. Converters
 The chemical conversion of SO2 to SO3 is designed to maximize the conversion by taking into
consideration that:
a. Equilibrium is an inverse function of temperature and a direct function of the oxygen
to sulfur dioxide ratio.
b. Rate of reaction is a direct function of temperature.
c. Gas composition and amount of catalyst affect the rate of conversion and the kinetics
of the reaction.
d. Removal of sulfur trioxide formed allows more sulfur dioxide to be converted.
 The successive lowering of the temperature between stages ensures an overall higher conversion.
 Conversion in a four-stage converter of a single-absorption plant is 98 percent or slightly higher.
5. Sulfur Trioxide Absorbers
 A concentration of 98.5-99 per cent sulfuric acid is the most efficient agent for the absorption of
sulfur trioxide.
 Water cannot be used because direct contact of SO3 and water results in an acid mist that is almost
impossible to absorb.

6. Blowers
 It is used to propel the air and/or sulfur-containing gases through the processing equipment.
 These are electric motor or steam turbine-driven single-stage centrifugal compressors of cast iron,
cast steel, or fabricated steel.
 It is the major energy consumer in the plant.
7. Acid Pumps
 Vertical shaft centrifugal submerged pumps of cast iron construction with alloy impellers and
shafts are used to circulate acid over the drying and absorption towers.
 These may be driven by electric motors or steam turbines.
8. Sulfur Pumps
 Vertical shaft submerged centrifugal pumps of cast iron construction are used to pump sulfur from
a pit to the atomizers in the sulfur burner.
 These pumps have steam-jacketed discharge piping to prevent cooling and solidification of the
sulfur.
9. Acid Coolers
 The acid circulating over the absorbing towers must be cooled to remove the heat of absorption
and the sensible heat of the incoming gas.
 The acid circulating over the drying tower must be cooled to remove the heat of dilution and heat
of condensation of moisture from the incoming gas or air.
 Shell-and-tube-type heat exchangers of alloy steel, often protected have been introduced.
10. Gas Purification
 Plants which must handle impure sulfur dioxide gases, such as those leaving smelters, ore roasters,
and other processes, may include waste heat boilers (for heat recovery while cooling the gases),
electrostatic dust precipitators (for recovering valuable calcine while cooling the gases), scrubbing
or wash towers (for further cooling the gases in order to adjust the temperature for water balance
in the plant while also removing additional dust), and finally electrostatic mist precipitators for
removal of acid mist and residual dust and fume.
11. Materials of Construction
 After the moisture has been removed in the drying tower, ordinary steel and cast iron are
satisfactory materials for use in handling the gas or air and the strong acid.
 The drying and the absorbing towers and the acid pump tanks associated with these towers are
constructed of brick-lined steel because of the corrosive and erosive effect of hot acid on steel.
 Cast iron is not suitable for use in the oleum system.
 In gas purification system, steel is used for handling sulfur dioxide gases having temperatures
above the acid dew point. For temperatures below the acid dew point and for liquids , lead, lead-
lined steel with or without a brick lining, alloy steels, and plastic materials are used for specific
conditions.