CHAPTER TWO SULPHURIC ACID PRODUCTION

Sulphuric acid is a highly corrosive strong mineral acid with the molecular formula H2SO4 and molar mass of 98.08g/mol.The historical name of this acid is oil of vitriol. It is a diprotic acid General Properties of Sulphur 1) It is a clear, colourless, odourless and viscous liquid. 2) It is soluble in water at all concentration 3) Has a density of 1.84g/cm3. 4) Reacts violently with water and produces large amount of heat, therefore it is called an exothermic reaction. 5) Extremely corrosive and causes burns. The corrosiveness of it is mainly due to its strong acidic nature, strong dehydrating property and if concentrated strong oxidizing property 6) Harmful if inhaled, ingested or skin contact Processes Used in producing Sulphuric acid (H2SO4) There are two (2) major processes for the production of H2SO4 namely; i) ii) Lead Chamber Process Contact Process

Lead Chamber Process

The lead chamber process was an industrial method used to produce sulphuric acid in large quantities. It has been largely supplanted by the contact process. In 1746 in Birmingham, England John Roebuck developed the lead chamber process for the manufacture of sulphuricacid. Prior to this time, sulphuric acid had been produced in glass bottles several pounds at a time, but the lead process could producesulphuric acid by the ton. This allowed the effective industrialization of sulphuric acid production and with several refinements; this process remained the standard method of production for almost two (2) centuries. In the original lead chamber process, sulphur and potassium nitrate are ignited in a room lined with lead foil. Potassium nitrate or saltpeter is an oxidizing agent oxidizes the sulphur to sulphur trioxide according to the reaction: 6 KNO3(s) + 7S(g) -----> 3 K2S + 6 NO(g) + 4 SO3(g) The floor of the room was covered with water. When the sulphur trioxide reacted with the water, sulphuric acid was produced: SO3(g) + H2O(l) -----> H2SO4(aq) This process was a batch process and resulted in the consumption of potassium nitrate.

In 1835, Joseph Gay-Lussac invented a process for recovering the nitrogen in nitrogen monoxide and recycling it to replace the saltpeter as a source of nitrogen. 4 NO(g)+ O2(g) + 2 H2O(l) -----> 4 HNO2(l) 4 HNO2(l) + 2 SO2(g) -----> 2 H2SO4(aq)+ 4 NO(g) This accomplished two things simultaneously: i) ii) It reduced the dependence on expensive saltpeter and It sharply reduced nitrogen monoxide emissions.

The only requirement now for saltpeter was to make up for the lost nitrogen monoxide. The classic lead chamber process consists of 3 stages; Glover tower, lead chambers and Guy-Lussac Tower. The process starts with hot sulphur dioxide gas entering the bottom of a reactor called a Glover tower where it is washed with nitrous vitriol (sulphuric acid with nitric oxide, NO, and nitrogen dioxide, NO2, dissolved in it) and mixed with nitric oxide and nitrogen dioxide gases. The Glover tower serves two functions; i) Concentration of the chamber acid and
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ii)

Stripping of nitrogen oxides from the liquid to the gas

Concentration of the chamber acid (62% to 68% H2SO4) is achieved by the hot gases entering the tower which evaporate water from the acid. Some of the sulphur dioxide is oxidized to sulphur trioxide and dissolved in the acid wash to form tower acid or Glover acid (about 78% H2SO4). The dissolved nitrogen oxides are stripped from the acid and carried with the gas out of the Glover tower into the lead chambers. From the Glover tower a mixture of gases (including sulphur dioxide and trioxide, nitrogen oxides, nitrogen, oxygen, and steam) is transferred to a leadlined chamber where it is reacted with more water. The chamber may be a large, boxlike room or an enclosure in the form of a truncated cone. Sulphuric acid is formed by a complex series of reactions; it condenses on the walls and collects on the floor of the chamber. There may be from three to twelve chambers in a series; the gases pass through each in succession. The acid produced in the chambers, often called chamber acid or fertilizer acid, contains 62% to 68% H2SO4. The reactions occurring in the lead chamber are: NO + O2-----> NO2 NO2 + NO + H2O -----> 2 HNO2 SO2 + H2O -----> H2SO3

2 HNO2 + 2 H+ -----> 2 NO + 2 H2O H2SO3-----> HSO3- + H+ NO+ + HSO3------> NOSO3- + H+ NO+ + NOSO3------> 2NO + SO3 SO3 + H2O -----> H2SO4 Overall Reaction: SO2 + O2 + H2O -----> H2SO4 After the gases have passed through the chambers they are passed into a reactor called the Gay-Lussac tower where they are washed with cooled concentrated acid (from the Glover tower); the nitrogen oxides and unreacted sulphur dioxide dissolve in the acid to form the nitrous vitriol used in the Glover tower. The waste gases exiting the Guy-Lussac tower are usually discharged into the atmosphere. Product acid at a concentration of 78% H2SO4 is drawn from the cooled acid stream that is circulated from the Glover tower to the Guy-Lussac tower. Nitrogen losses are made up with nitric acid which is added to the Glover tower.

Contact Process Contact process is a modern industrial method of producing large amounts ofsulphuric acid it has largely replaced the chamber, or lead-chamber, process. This process was patented in 1831by the British vinegar merchant Peregrine Phillips. In addition to being a far more economical process for producing concentrated sulphuric acid than the lead chamber process, the contact process also produces sulphuric trioxide andoleum. The process can be divided into five stages: 1. Purification of sulphur dioxide: Sulphur dioxide is produced by burning sulphur or roasting of iron sulphide in air in pyrite burners. S + O2 -> SO2 4FeS2+ 11O2 -> 2Fe2O3 + 8SO2 2. Purifying sulphur dioxide in the purification unit; Purifying unit consists of dust remover, cooling pipes, scrubbers, drying tower and testing box. Dust particles are removed from the mixture of SO2 and O2with steam. These gases are passed through lead pipes to cool them to 100 C. Cooled gases are
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washed by spray of water. The gases are then dried with concentrated sulphuric acid trickling through coke filled in the tower. The purified gases are dried and passed through a beam of light to confirm the absence of solid particles. 3. Oxidation of SO2 to SO3in the presence of catalyst vanadium oxide: 2 SO2(g) + O2(g) 2 SO3(g) : H = 197 kJ mol1 According to the Le Chatelier's principle, 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 (V2O5) are used to ensure a 96% conversion.Platinum was formerly employed as a catalyst for the reaction, but it is susceptible to poisoning by arsenic impurities in the sulphur feedstock and also very costly, vanadium (V) oxide (V2O5) is now preferred. The catalyst only serves to increase the rate of reaction as it does not change the position of the thermodynamic equilibrium. The mechanism for the action of the catalyst comprises two steps:

1. Oxidation of SO2 into SO3 by V5+: 2 SO2 + 4V5+ + 2 O2- 2 SO3 + 4V4+ 2. Oxidation of V4+ back into V5+ by oxygen (catalyst regeneration): 4 V4+ + O2 4 V5+ + 2 O24. Production of sulphuric acid: Sulphur trioxide from the contact tower is passed onto absorption tower where it is absorbed by descending stream of 98% sulphuric acid to form oleum. It is diluted with water to get sulphuric acid of desired concentration. H2SO4(l) + SO3(g) H2S2O7(l) H2S2O7(l) + H2O(l) 2 H2SO4(l) Purification of air and SO2 is necessary to avoid catalystpoisoning (i.e. removing catalytic activities. Double Contact Double Absorption (DCDA) The next step to the Contact Process is DCDA or Double Contact Double Absorption. In this process the product gases (SO2) and (SO3) are passed through absorption towers twice to achieve further absorption and conversion of SO2 to SO3 and production of higher grade sulphuric acid.

SO2-rich gases enter the catalytic converter, usually a tower with multiple catalyst beds, and are converted to SO3, achieving the first stage of conversion. The exit gases from this stage contain both SO2 and SO3 which are passed through intermediate absorption towers where sulphuric acid is trickled down packed columns and SO3 reacts with water increasing the sulphuric acid concentration. Though SO2 too passes through the tower it is unreactive and comes out of the absorption tower. This stream of gas containing SO2, after necessary cooling is passed through the catalytic converter bed column again achieving up to 99.8% conversion of SO2 to SO3 and the gases are again passed through the final absorption column thus resulting not only achieving high conversion efficiency for SO2 but also enabling production of higher concentration of sulphuric acid. The industrial production of sulphuric acid involves proper control of temperatures and flow rates of the gases as both the conversion efficiency and absorption are dependenton these. Similarities between the two processes of sulphuric acid production In both processes sulphur dioxide is oxidized and dissolved in water.

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Differences Lead Chamber Process 1) Produces relatively dilute acid 2) Does not require the use of expensive catalyst. Contact Process 1) Produces a purer& more concentrated acid 2) Requires purer raw materials and the use of expensive catalyst Uses of Sulphuric Acid 1) Production of agricultural fertilizers 2) It serves as the electrolyte in the lead-acid storage battery commonly used in motor vehicles (acid for this use, containing about 33% H 2SO4 and with specific gravity about 1.25, is often called battery acid). 3) It is used in petroleum refining to wash impurities out of gasoline and other refinery products. 4) Concentrated sulphuric acid is used as a drying agent. 5) Sulphuric acid is used in processing metals, e.g., in pickling (cleaning) iron and steel before plating them with tin or zinc. 6) It is used in manufacturing dyes, glue, film, explosives, drugs, soaps. etc.

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REFERENCES

1. Edward M. Jones, "Chamber Process Manufacture of Sulfuric Acid," Industrial and Engineering Chemistry, Nov 1950, Vol 42, No. 11, pp 2208-10. 2. F. A. Gooch and C. F. Walker, Outlines of Inorganic Chemistry, MacMillan, London, 1905, pp 274. 3. Meyer, Beat (1964). "Solid Allotropes of Sulfur". Chemical Reviews64 (4): 429451. 4. Tebbe, Fred N.; Wasserman, E.; Peet, William G.; Vatvars, Arturs; Hayman, Alan C. (1982). "Composition of Elemental Sulfur in Solution: Equilibrium of S6, S7, and S8 at Ambient Temperatures". Journal of the American Chemical Society104 (18): 49714972.. 5. Nelson, D. L.; Cox, M. M. (2000.). Lehninger, Principles of Biochemistry (3rd ed.). New York: Worth Publishing. ISBN 1-57259-153 6. Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 421. 7. Vaughan, D. J.; Craig, J. R. "Mineral Chemistry of Metal Sulfides" Cambridge University Press, Cambridge (1978) ISBN 0-521-21489-0 8. Cremlyn R. J.; An Introduction to Organosulfur Chemistry John Wiley and Sons: Chichester (1996). ISBN 0 471 95512 4.

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9. Kutney, Gerald (2007). Sulfur: history, technology, applications & industry. Toronto: ChemTec Publications. p. 43. ISBN 9781895198379. OCLC 79256100. 10.Meyer, Beat (1976). "Elemental sulfur". Chemical Reviews76 (3): 367 388..

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