From Sulfur to Sulfuric Acid

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1 From Sulfur to Sulfuric Acid The Contact Process

2 History universe-review.ca/f13- atom.htm Process of burning sulfur with saltpeter was first described in the 15 th century 1746 lead chamber process 1831 contact process - use of catalyst - absorption of SO 3 into 98.5 % to 99 % H 2 SO 4 e/multimedia.js...

3 Process S (l) O 2 (g) SO 2 (g) Η = kj, 25 0 C SO 2 (g) 1/2O 2 (g) SO 3 (g) Η = 98.3 kj, 25 0 C SO 3 (g) H 2 SO 4 (l) H 2 S 2 O 7 (l) H = kj, 25 0 C Because sulphur is exothermic and burns in air, heat is generated and most sulphuric acid plants generate steam as a by-product. large plants can produce 1.3 tons in excess per metric ton of acid in some countries, energy from sulfuric acid plants is used in homes and offices saving ~ tons of fuel oil per day!

4 S (l) O 2 (g) SO 2 (g) Η = kj, 25 0 C SO 2 (g) 1/2O 2 (g) SO 3 (g) Η = 98.3 kj, 25 0 C SO 3 (g) H 2 SO 4 (l) H 2 S 2 O 7 (l) H = kj, 25 0 C How can more SO 3 (g) be produced? K p = P SO3 P SO2 P O2 1 2 x

5 But, rate of reaction increases with increase in temperature balance between rate of reaction and optimum conversion Temp, 0 C K p

6 Use of a catalyst: earlier catalysts included iron oxide and platinum replaced with V 2 O 5 (vanadium pentoxide) can last up to 20 years is used in the shape of hollow cylinders increased surface area together with good flow of gas through the catalyst How else can we optimize the conversion to SO 3? Four-pass Converter SO 2 (g) 1/2O 2 (g) SO 3 (g)

7 S (l) O 2 (g) SO 2 (g) Η = kj, 25 0 C SO 2 (g) 1/2O 2 (g) SO 3 (g) Η = 98.3 kj, 25 0 C SO 3 (g) H 2 O (l) H 2 SO 4 (l) H = kj, 25 0 C SO 3 (g) H 2 O (l) H 2 SO 4 (aq) X highly corrosive mist of sulfuric acid fumes

8 SO 3 (g) H 2 SO 4 (l) H 2 S 2 O 7 (l) Steel % sulfuric acid is a good absorber of SO 3 (g) lined with acid proof bricks with ceramic packing with conc acid flowing over it allows for SO 3 (g) to have close contact with the conc acid H 2 S 2 O 7 (l) H 2 O (l) 2 H 2 SO 4 (l) H 2 SO 4 (l) H 2 O H 2 SO 4 (aq) Absorbing tower concentrated acid is withdrawn and portion going back into tower is diluted with dilute H 2 SO 4 or water

9 Typical flow chart for a sulfur-burning single-absorption contact sulfuric acid plant. Monsanto Enviro-Chem from Shreve s Chemical Process Industries

10 Remove CO 2, N 2, moisture & other impurities Heart of the contact process. Discuss in terms of the equilibrium reaction, rate of reaction, rate of conversion and increased SO 3 formation? Furnace similar to that used for burning fuel oils Removes heat from sulfur burner gas steam Cooling gases between passing through catalyst why? Absorption of SO 3 into H 2 SO 4 Recirculated H 2 SO 4 is cooled

11 What is a furnace?

12 Schematic diagram of an industrial process furnace air blower directs air towards burner that is powered by fuel heat transferred to tubes in radiant section flow of liquid through the tubes is heated to desired temperature combustion gases vented via the stack but their heat is recovered in the convection section first

13 Secondary combustion chamber where vaporized sulfur is burned o C O 2 gas introduced to molten sulfur Steam heating coil Melt vessel where the sulfur is melted Combustion chamber where the molten sulfur is partially burned and vaporized ine.com/ pdf

14 What is a heat exchanger? A device that allows for the exchange of heat from a fluid on one side of a barrier to fluid on the other side of the barrier without the two liquids coming into contact with each other. Give examples of heat exchangers. wer.aspx?path=hm&name=a4heatex

15 Rate of heat transfer is dependent on: - temperature difference between hot and cold fluids/surfaces - surface area available for heat transfer the geometry and physical properties of a system will also influence the heat transfer system, for eg., if fluids are involved then the flowrate is important

16 heat exchange or transfer is used in industry to - heat or cool reactions - keep raw materials at an optimal temperature (eg., keep solid fats in a liquid state) - conserve energy (eg., re-use of steam condensate) most commonly used between liquids but may get transfer between gas and liquid or between 2 gases.

17 Types of Heat Transfer Equipment Jacketed vessel External coil lower surface area smaller contact area not generally used for temperature control in reactors used in low duty heating requirements, for eg., maintaining the temperature in raw material tanks or heating pipe lines

18 Internal helical coil Internal baffle type coil Used in reactors even if contains viscous material. High surface area for heat transfer Problem? Makes cleaning of reactor difficult and interferes with mixers in reactors

19 External Heat Exchangers external heat exchanger solution is pumped to outside the vessel where heat transfer occurs

20 Double pipe heat exchanger Hot and cold liquids move in a counter current direction outer annulus inner tube Most efficient operation is achieved when inlet and outlet temperatures are as close together as possible

21 Single pass tubular heat exchanger directs the flow of liquid counter current divides the header from the rest of the apparatus & prevents the fluid from entering the shell larger surface area many tubes inside a shell or cavity

22 Provide labels for this diagram

23 Plate heat exchanger is a series of metal plates 2 fluids pass through the metal plates and are in contact with each other through the plates but do not mix plates are sealed with high temperature rubber gaskets for easy cleaning or repair usually used where there is a lot of fouling and the system needs a lot of cleaning

24 Remove CO 2, N 2, moisture & other impurities Heart of the contact process. Discuss in terms of the equilibrium reaction, rate of reaction, rate of conversion and increased SO 3 formation? Furnace similar to that used for burning fuel oils Removes heat from sulfur burner gas steam Cooling gases between passing through catalyst why? Absorption of SO 3 into H 2 SO 4 Recirculated H 2 SO 4 is cooled

25 Is Continuous or Batch Processing Better? the aim is to produce the maximum amount of product the types of solutions dealt with on the plant determine which process is better costs of labour, amount of product, research and instrumentation also play a role in determining which process is used.

26 Continuous process: - runs continuously - fairly automated minimize labour - have much less material in process therefore lower chance of ruining large quantities of feedstock - more uniform operating conditions requires good quality instrumentation for concise control

27 - suitable for processes that are liquids or gases. Why? - entire plant cannot be shut down for maintenance shut down small sections of the plant at a time to carry out repairs and maintenance - Disadvantage very expensive to build

28 Batch process: - Relatively smaller quantities of feedstock are processed in individual reactors produce smaller quantities of product - Precise quantities for each batch can be weighed out accurately but temperature control can be a problem - Easier to control the reaction in a small reactor - Maintenance is easier - Disadvantage very labour intensive

29 What type of process does the Contact Process use? Contact process: - Gaseous feedstock produce liquid product - Large demand for end product

30 Environmental Awareness What are the main pollutants in a sulfuric acid process? Identify, on the process chart, where these pollutants would be present. Why are these regarded as pollutants? Describe in detail the methods that can be used to reduce these pollutants

31

32 Why are these regarded as pollutants? - SO 2 is a throat and nose irritant and causes breathing problems if high concentrations are inhaled. - Damage to vegetation and animals - SO 3 combines with water vapour in the atmosphere to form sulfuric acid mist.

33 Use of higher stacks: - Tall stacks help to disperse the SO 2 gas higher into the atmosphere away from ground life - Climate conditions and topography of the surrounding must be considered during emission of gases and building of stacks

34 Use of scrubbers: - Scrub with water (very effective in reducing % of SO 2 ) soda ash (produce sodium bisulfite as byproduct) lime slurries salt solutions (slightly alkaline, heated conc salt soln) Cleaning/LandfillGas.jpg

35 Removal of acid mist - The smaller the mist particles the greater the visibility which results in plumes from stacks - Removal of acid mist is carried out by: Packed bed separators containing sand, coke or fibers of glass or metal which cause the particles to coalesce Wire mesh mist eliminators cause particles to coalesce when high velocity gas pass through them b/3/31/packedtowerex.gif/250px-packedtowerex.gif

36 Porous ceramic filter tubes made up of aluminium are effective in collecting acid mist that passes through it from the top downwards Electrostatic precipitators Sonic agglomerators use sound waves to cause small particles to stick together to form a large particle which is then removed by cyclones

37 What is Sulfuric Acid Used for? ~ 70 % used to make superphosphate fertilizers Processing of metal ores Manufacture of detergents Manufacture of paper Manufacture of rayon and other polymers Manufacture of paints and pigments Electrolyte in heavy duty batteries Laboratory reagent

38 Economic Role of Sulfuric Acid sulfuric plays an important role in a countries industrial economy Post war ( ) greatest economic growth WW1 ( ) WW2 (1938) Stock market crash (1929)

39 Most produced chemical in the US About 40 million tons produced per year (US ) Cost of sulfuric acid is affected by supply & demand which is affected by the demand for the chemicals it is used to make Sulfuric_acid_prices_continue_to_decline_as_demand_dries_up.php#52758

40 We may judge with great accuracy the commercial prosperity of a country from the amount of sulfuric acid it consumes 1840 Liebig

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