The contact process is the current method of producing
sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular fo ...
in the high concentrations needed for industrial processes.
Platinum
Platinum is a chemical element with the symbol Pt and atomic number 78. It is a dense, malleable, ductile, highly unreactive, precious, silverish-white transition metal. Its name originates from Spanish , a diminutive of "silver".
Pla ...
was originally used as the
catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
for this reaction; however, as it is susceptible to reacting with
arsenic
Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, b ...
impurities in the sulfur feedstock,
vanadium(V) oxide
Vanadium(V) oxide (''vanadia'') is the inorganic compound with the formula V2 O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because ...
(V
2O
5) is now preferred.
History
This process was patented in 1831 by British vinegar merchant Peregrine Phillips. In addition to being a far more economical process for producing concentrated
sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular fo ...
than the previous
lead chamber process, the contact process also produces
sulfur trioxide
Sulfur trioxide (alternative spelling sulphur trioxide, also known as ''nisso sulfan'') is the chemical compound with the formula SO3. It has been described as "unquestionably the most important economically" sulfur oxide. It is prepared on an ind ...
and
oleum
Oleum (Latin ''oleum'', meaning oil), or fuming sulfuric acid, is a term referring to solutions of various compositions of sulfur trioxide in sulfuric acid, or sometimes more specifically to disulfuric acid (also known as pyrosulfuric acid). Ol ...
.
In 1901
Eugen de Haën
Carl Johann Eugen de Haën (December 26, 1835 – November 16, 1911), often known as Eugen de Haën or Eugen de Haen, was a German chemist and entrepreneur. He was founder of the chemistry factory ''E. de Haën & Co''.
Education and career
De H ...
patented the basic process involving combining
sulfur dioxide
Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic a ...
and
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...
in the presence of
vanadium oxides, producing
sulfur trioxide
Sulfur trioxide (alternative spelling sulphur trioxide, also known as ''nisso sulfan'') is the chemical compound with the formula SO3. It has been described as "unquestionably the most important economically" sulfur oxide. It is prepared on an ind ...
which was easily absorbed into water, producing
sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular fo ...
. This process was improved remarkably by shrinking the particle size of the catalyst (e.g. :le 5000 microns), a process discovered by two chemists of
BASF in 1914.
Process
The process can be divided into four stages:
# Combining of
sulfur
Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formul ...
and
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...
(O
2) to form
sulfur dioxide
Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic a ...
, then purify the sulfur dioxide in a purification unit
# Adding an excess of oxygen to
sulfur dioxide
Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic a ...
in the presence of the catalyst
vanadium pentoxide at 450 °C and 1-2 atm
# The
sulfur trioxide
Sulfur trioxide (alternative spelling sulphur trioxide, also known as ''nisso sulfan'') is the chemical compound with the formula SO3. It has been described as "unquestionably the most important economically" sulfur oxide. It is prepared on an ind ...
formed is added to
sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular fo ...
which gives rise to
oleum
Oleum (Latin ''oleum'', meaning oil), or fuming sulfuric acid, is a term referring to solutions of various compositions of sulfur trioxide in sulfuric acid, or sometimes more specifically to disulfuric acid (also known as pyrosulfuric acid). Ol ...
(disulfuric acid)
# The oleum is then added to water to form sulfuric acid which is very concentrated. Since this process is an exothermic reaction, the reaction temperature should be as low as possible.
Purification of the air and sulfur dioxide (SO
2) is necessary to avoid catalyst ''poisoning'' (i.e. removing catalytic activities). The gas is then washed with
water
Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...
and dried with sulfuric acid.
To conserve energy, the mixture is heated by exhaust gases from the
catalytic converter
A catalytic converter is an exhaust emission control device that converts toxic gases and pollutants in exhaust gas from an internal combustion engine into less-toxic pollutants by catalyzing a redox reaction. Catalytic converters are usual ...
by heat exchangers.
Sulfur dioxide and dioxygen then react as follows:
:2 SO
2(g) + O
2(g) ⇌ 2 SO
3(g) : Δ''H'' = -197 kJ·mol
−1
According to the
Le Chatelier's principle
Le Chatelier's principle (pronounced or ), also called Chatelier's principle (or the Equilibrium Law), is a principle of chemistry used to predict the effect of a change in conditions on chemical equilibria. The principle is named after French ...
, a lower temperature should be used to shift the chemical equilibrium towards the right, hence increasing the percentage yield. However too low of a temperature will lower the formation rate to an uneconomical level. Hence to increase the reaction rate, high temperatures (450 °C), medium pressures (1-2
atm), and
vanadium(V) oxide
Vanadium(V) oxide (''vanadia'') is the inorganic compound with the formula V2 O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because ...
(V
2O
5) are used to ensure an adequate (>95%) conversion. The catalyst only serves to increase the rate of reaction as it does not change the position of the
thermodynamic equilibrium
Thermodynamic equilibrium is an axiomatic concept of thermodynamics. It is an internal state of a single thermodynamic system, or a relation between several thermodynamic systems connected by more or less permeable or impermeable walls. In the ...
. The mechanism for the action of the catalyst comprises two steps:
# Oxidation of SO
2 into SO
3 by V
5+:
#: 2SO
2 + 4V
5+ + 2O
2− → 2SO
3 + 4V
4+
# Oxidation of V
4+ back into V
5+ by dioxygen (catalyst regeneration):
#: 4V
4+ + O
2 → 4V
5+ + 2O
2−
Hot sulfur trioxide passes through the heat exchanger and is dissolved in concentrated H
2SO
4 in the absorption tower to form oleum
: H
2SO
4 + SO
3 → H
2S
2O
7
Note that directly dissolving SO
3 in water is impractical due to the highly exothermic nature of the reaction. Acidic vapor or mists are formed instead of a liquid.
Oleum is reacted with water to form concentrated H
2SO
4.
:H
2S
2O
7 + H
2O → 2 H
2SO
4
Purification unit
This includes the dusting tower, cooling pipes, scrubbers, drying tower, arsenic purifier and testing box. Sulfur dioxide has many impurities such as vapours, dust particles and
arsenous oxide. Therefore, it must be purified to avoid catalyst poisoning (i.e.: destroying catalytic activity and loss of efficiency). In this process, the gas is washed with water, and dried by sulfuric acid. In the dusting tower, the sulfur dioxide is exposed to a steam which removes the dust particles. After the gas is cooled, the sulfur dioxide enters the washing tower where it is sprayed by water to remove any soluble impurities. In the drying tower, sulfuric acid is sprayed on the gas to remove the moisture from it. Finally, the
arsenic oxide is removed when the gas is exposed to
ferric hydroxide.
Double contact double absorption
The next step to the contact process is ''double contact double absorption'' (DCDA). In this process the product gases (SO
2) and (SO
3) are passed through absorption towers twice to achieve further absorption and conversion of SO
2 to SO
3 and production of higher grade sulfuric acid.
SO
2-rich gases enter the catalytic converter, usually a tower with multiple catalyst beds, and are converted to SO
3, achieving the first stage of conversion. The exit gases from this stage contain both SO
2 and SO
3 which are passed through intermediate absorption towers where sulfuric acid is trickled down packed columns and SO
3 reacts with water increasing the sulfuric acid concentration. Though SO
2 too passes through the tower it is unreactive and comes out of the absorption tower.
This stream of gas containing SO
2, after necessary cooling is passed through the catalytic converter bed column again achieving up to 99.8% conversion of SO
2 to SO
3 and the gases are again passed through the final absorption column thus achieving not only high conversion efficiency for SO
2, but also enabling production of a higher concentration of sulfuric acid.
The industrial production of sulfuric acid involves proper control of temperatures and flow rates of the gases as both the conversion efficiency and absorption are dependent on these.
See also
*
Lead chamber process
Notes
References
* ''The Repertory of Patent Inventions'', no. 72 (April 1831)
page 248
* (Anon.) (1832) "English patents: Specification of the patent granted to Peregrine Phillips, Jr. of Bristol, in the county of Somersetshire, Vinegar Maker, for an improvement in manufacturing Sulphuric Acid. Dated March 21, 1831." ''Journal of the Franklin Institute'', new series, vol. 9
pages 180-182.* Ernest Cook (March 20, 1926) "Peregrine Phillips, the inventor of the contact process for sulphuric acid," ''Nature'', 117 (2942) : 419–421.
Lunge, ''Theoretical and Practical Treatise on the Manufacture of Sulphuric Acid and Alkali, with the Collateral Branches'', 3rd ed., vol. 1, part 2 (London, England: Gurney and Jackson, 1903), page 975
External links
*
*
* {{cite web , title = Absorption Tower , url = http://www.mining-enc.ru/a/absorbcionnaya-kolonna , website = Mining Encyclopedia
Chemical processes
Vanadium
Sulfur
Catalysis