CM1100 LECTURE NOTES HISTORY OF THE CHEMICAL INDUSTRY

1. CM1100 LECTURE NOTESHISTORY OF THE CHEMICAL INDUSTRY M A MORRIS E-MAIL m.morris@ucc.ie Rm: 108 Kane Building Industrial Inorganic Chemicals: Production and Uses, Ed. R Thompson The Chemical Industry, Ed. A Heaton

2. Introduction • Chemicals were known by the ancients • Ancient Egyptians used ‘soap’ • Soda (sodium carbonates, natron in Egypt) plus fats to wash corpses prior to during mummification • Cement dates back to Egyptians passed to Romans and the Greeks (forgotten for 2000 yrs) volcanic ash + rock + caustic soda (NaOH) • 500 yrs ago Mayan Indians used latex balls in games and in clothing

3. Recipe for a mummy…. • Four jars hold the liver, lungs, intestines, and stomach. The heart is kept inside the body and the other internal body organs fried. • The brain is pulled thru the nose with a hook. Stuff the head with tree resin and sawdust. • Soak the body in natron for 40 days. The body is put on a inclined couch and the liquids and natron fall to the bottom into a pan. • Rub the body with olibanum oil to make the skin supple. • Pack the body to make it more lifelike (with spices or sawdust). • Use wax to seal any incisions. • Tear fine linen into strips 16 yards long and 2-8 inches wide. • Wrap the smaller extremities (toes and fingers) first. • Next, wrap the limbs, and finally, the torso. • Sing appropriate chants over each body part. • Secure linen with tree resin. • Tuck in an amulet after every few layers. Isis, Osiris, and Set

4. Modern Chemical Industry • Began in UK around 1750-1800 • Lead-Chamber Method was developed in England in 1749 to make sulfuric acid. • Was sponsored by the industrial revolution with demands for chemicals for other industries. • Soap manufacture (alkali + animal fat) • Cotton – bleach • Glassmaking – sand (SiO2) and soda (sodium carbonate)

5. Three key chemicals needed to be manufactured…….. • Sulphuric acid - oil of vitriol Largest volume chemical in the world – used for steel processing, dehydration, sulphate fertilizers, sugar treatment (after removal). Used in pharmaceutical and dye manufacture. Lead acid batteries. Production of alum (Al2(SO4)3) for water treatment. Around 200 Mt made very year. • Soda – sodium carbonate Sodium Carbonate (Soda ash, Sal Soda, Washing Soda) (Na2CO3) & Sodium Bicarbonate (baking soda) (NaHCO3) are used to manufacture glass, soap, textiles, paper, and as a disinfectant, cleaning agent, and water softener • Caustic soda – sodium hydroxide Alkali Hydroxides (usually just called "Alkali") are used to produce glass, paper, soap, and dyestuffs for textiles, aid in oil refining, make bleaching compounds, and preparing leather. • Johnny was a chemist's son, but Johnny is no more. • What Johnny thought was H2O was H2SO4.

6. Sulphuric acid an early route - copperas • Jabir-Ibn-Hayyan (721-815) distinguished between green vitriol and blue vitriol, ferrous sulphate and copper sulphate respectively • Green vitriol (FeSO4.7H2O) was used extensively in the textile (as dyestuffs) and metallurgical industries and for a number of other purposes. • 17th C manufacture copperas containing stones were collected from the beach placed in oak vessels and packed with chalk. After several years a liquor a mixture of sulphuric acid (source of this for many years) and iron sulphate solution was collected. Further iron was added to bring it up to stoichiometery. • Sulphate crystals were collected by drying in sun. Twigs etc were added to promote crystallisation processes. • Took place at Tankerton in Kent and in Dorset but soon move to the NW of England • It was the first heavily capitilised industry requiring large scale investments                                             <> Tankerton, nr. Whitstable, Kent. : Copperas industry.

7. Sulphuric acid • First chemical process on an industrial scale • This source became green vitriol ( FeSO4.7H2O) recovered from mineral pyrites and was first material that Joshua Parr attempted to make at Mynydd Parys - Angelsey (1795). • FeS2(s) + 11O2→ 2Fe2O3(s) + 8SO2(g) • Eventually sulphide/S mines in N. Wales sent material to Liverpool (Garston sulphuric Acid Co.). Start of the NW chemical industry. • Parr was never successful and direct oxidation of S (as pyrite also) was in air to give SO2 became the economically better route. Saltpeter (KNO3) was used as catalyst releasing NOx • Water in reaction chamber absorbed gases • Reactions took place in small glass lined vessels but scale of production was increased by Roebuck and Gardner (1749) using large lead lined chambers. • Roebuck took no patent protection and eventually his business collapsed View of Carron Works, 19th century (Roebuck) Roebuck later worked with Watt on 1st steam engine

8. Nitrates • Potassium Nitrate (saltpeter, Nitre) (KNO3) Was obtained primarily from India and used to prepare matches, explosives, and fertilizers. • Chile saltpeter, an impure form of sodium nitrate (NaNO3), which was deposited along the Pacific coast by large flocks of birds. • Lime saltpeter (Norwegian saltpeter) which is composed of calcium nitrate (CaNO3) • These are only source of nitrates until Haber process • They were extensively used in manufacture of explosives – the Haber process was developed to reduce German reliance on Chile saltpeter during WW1 (UK blockaded ports) and extended war.

9. Sulphuric acid improvements • Gay-Lussac towers (1837)– introduced oxygen to form SO3 in increased amounts and recovered NOx reducing requirement for the KNO3. Improved by Glover (UK) and towers common in 1870s • 1880s saw further increases. Phillips (UK vinegar merchant) patented Pt catalysed oxidation of SO2 to SO3. Was not used until catalyst reactor built in Germany in 1875. But technology widely used by 1890. • In the 20C Pt replaced by vanadium oxides Absorption tower

10. Modern Contact process • Most of the sulfuric acid manufactured is produced using the Contact Process, a process involving the catalytic oxidation of SO2 to SO3. • Solid sulfur, S(s), is burned in air to form sulfur dioxide SO2S(s) + O2(g) -----> SO2(g) • The gases are mixed with more air then cleaned by electrostatic precipitation to remove any particulate matter • The mixture of SO2 and air is heated to 450oC and subjected to a pressure of 1 - 2 atmospheres in the presence of a vanadium catalyst (V2O5) to SO3(g), with a yield of 98%.2SO2(g) + O2(g) -----> 2SO3(g) • Any unreacted gases from the above reaction are recycled • SO3(g) is dissolved in 98% (18M) sulfuric acid, H2SO4, to produce disulfuric acid or pyrosulfuric acid, also known as fuming sulfuric acid or oleum, H2S2O7.SO3(g) + H2SO4 ------> H2S2O7This is because if water is added directly to SO3 to produce sulfuric acid SO3(g) + H2O(l) -----> H2SO4(l)the reaction is slow and tends to form a mist in which the particles refuse to coalesce. • Water is added to the disulfuric acid, H2S2O7 to produce H2SO4 H2S2O7(l) + H2O(l) -----> 2H2SO4(l)

11. Soda ash manufacture • By 1800 the only native source of soda ash on the British Isles was kelp (seaweed). Imports of Alkali, from America in the form of wood ashes (potash) or Spain in the form of barilla (a plant containing 25% alkali) or from soda mined in Egypt, were all very expensive due to high shipping costs. Needed an industrial process for generating soda. • Based on the synthesis of H2SO4 • Leblanc process (1810):- • 2NaCl + H2SO4 → Na2SO4 + 2HCl • Na2SO4 + CaCO3 + 2C → Na2CO3 + CaS + 2CO2 • The salt came from the Cheshire salt plain • NaOH was prepared from the sodium carbonate: • Na2CO3 + Ca(OH)2 → 2NaOH + CaCO3

12. Pollution • The HCl was a major problem. James Muspratt (the most important figure in developing the NW chemical industry). The fumes were so dense that visibility in the area was <90m. • A petition against the Le BlancProcess in 1839 complained that "the gas from these manufactories is of such a deleterious nature as to blight everything within its influence, and is alike baneful to health and property. The herbage of the fields in their vicinity is scorched, the gardens neither yield fruit nor vegetables; many flourishing trees have lately become rotten naked sticks. Cattle and poultry droop and pine away. It tarnishes the furniture in our houses, and when we are exposed to it, which is of frequent occurrence, we are afflicted with coughs and pains in the head...all of which we attribute to the Alkali works." • Led to the Alkali Act in 1863 first legislation to limit air pollution.

13. Solvay process • John Hutchison – pioneered NW chemical industry recognising efficiency of scale • 1847 founded chemical works (Halton – Runcorn) • Three key recruits: Towers – analysis; Brunner – manager; and Mond from Germany as scientific officer In 1872 formed Brunner-Mond (part of the giant ICI) 1874 introduced the Solvay process Ernest Solvay 1838-1922

14. Solvay process • Ernst Solvay Belgium 1838-1922 • Several similar processed but difficult on large scale (Muspratt had almost gone bankrupt). Used to much NH4 which was not widely available • Advantages of Solvay were:- use of brine, less waste (low volume CaCl2 vs high vol CaSO4), CO2/NH3 recovered, costs some 70% less. However, plant cost was greater • 1890 Solvay was 90% of market • Process centred on iron towers where rising CO2 was mixed with brine spray

15. Solvay process • CO2(g) + H2O(l) + NH3(g) + Na+(aq) →NaHCO3(s) + NH4+(aq) at 0-15°C (1) • NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(g) at 300°C (2) • CO2 could be recycled and NH3 could be recovered. Ammonia is required to make sure mixture remains non-acidic (i.e. prevents HCl formation which would convert all carbonate to CO2) • NH4Cl + Ca(OH)2 → CaCl2 + 2NH3 + 2H2O • The Solvay reaction is carried out by passing concentrated brine through two towers. In the first, ammonia bubbles up through the brine and is absorbed by it. It the second, CO2 bubbles up through the brine and precipitates sodium bicarbonate. CO2 for this step is produced by heating calcium carbonate: • In 1938, large natural deposits of the mineral trona were discovered near the Green River in Wyoming. Sodium carbonate can be mined from this source less expensively than it can be produced by the Solvay process, and since 1986, there have been no Solvay-based plants operating in North America. Throughout the rest of the world, however, the Solvay process remains the major source of soda ash.

16. Schematic diagram of the manufacturing process 

17. Ammonia production • Vital chemical in several industries • Dyes, cotton treatments, plastics, fertilizer and Solvay process • It was difficult to make – hydrogen is expensive and the N2/H2 reaction was very high temperature • Before 1800s from distillation of natural products • 1800s Distillation of coal became primary source for organics and ammonia and town gas. All towns had a gas works. • 1880s Solvay designed his own coke ovens (source of C for iron). • Coal was heated at very high temperatures in reducing atmospheres (coal hydrocarbons) • In this very reducing atmosphere significant quantities of ammonia were produced. • First fertilizer was ammonia sulphate from reaction of NH4Cl plus sulphuric acid

18. The Haber process The Haber Process is a method of producing ammonia developed in WWI.  The Germans needed nitrogen to for making their explosives but the Allies blocked off all sources of sodium nitrate and potassium nitrate.  The chemist Fritz Haber developed the Haber Process in WWI via reaction of nitrogen and hydrogen             N2(g) + 3H2(g) <--> 2NH3(g) + 92 kJ. This uses an iron oxide catalyst. Nitrates are made by ammonia oxidation using a rhodium-platinum wire gauze catalyst, the primary product is nitric oxide: 4NH3 + 5O2 -> 4NO + 6H2O This NO is oxidised to NO2 in air and dissolved in water to yield nitric acid Nitrates used in fertilizer and explosive production The laboratory apparatus designed by Fritz Haber and Robert Le Rossignol for producing ammonia from hydrogen and nitrogen, which was scaled up in the Haber-Bosch process. The catalytic process took place in the large cylinder on the left.

19. Fritz Haber • By 1905 Fritz Haber (1868–1934) had developed the catalyst for fixing nitrogen from air. The process was soon scaled up by BASF's great chemist and engineer Carl Bosch—hence the name "Haber-Bosch" process. The nitric acid produced from the ammonia was then used to manufacture agricultural fertilizers as well as explosives. • He studied at several German universities, earning a doctorate in organic chemistry in 1891. In 1911 he was invited to become director of the Institute for Physical Chemistry and Electrochemistry at the new Kaiser Wilhelm Gesellschaft in Berlin, where academic scientists, government, and industry cooperated to promote original research. • During the war he further supported the German side and developed a new weapon—poison gas, chlorine, and supervised its initial deployment on the Western Front at Ypres, 1915. His promotion of this frightening weapon precipitated the suicide of his wife who shot herself with his gun • Controversy reigned when he got Nobel Prize in chemistry for 1918 for the synthesis of ammonia • He was a Jew and proud German and had to resign German positions in view of Nazi sentiment and was on his way to senior research job in Palestine when he died.

20. Cement and lime • Lime (limestone CaCO3, lime CaO and slaked lime) were central to most chemical processes in the 1800s • Also central to cement – Portland cement was the first advanced materials. • Joseph Aspdin (Leeds bricklayer) patented Portland cement in 1824 • Limestone came originally from S Coast of UK • Most common preparation of cement is mixture of limestone, clay and sand heated (1500C) in a Kiln to produce klinker pellets, a mixture of calcium silicates, calcium aluminates and calcium aluminosilicates • CaCO3 = CaO + CO2 • These are ground to a fine powder with gypsum and iron oxides.

21. Chlorine • Is a strong bleaching agent and disinfectant used in textiles and medical application. Was originally used as chlorine water. • Charles Tennant (Glasgow) opened a factory there in 1799 that produced bleaching powder which was much less harmful than the bleach based on chlorine in an aqueous solution • At the time Cl2 was produced by reaction of salt with sulphuric acid and manganese dioxide • In the 1860's two industrial chemists, Walter Weldon and Henry Deacon, devised a way of recovering chlorine from the waste hydrochloric acid produced by the Leblanc soda factories. • MnO2 + 4HCl → Cl2 + MnCl2 + 2H2O

22. Chlorine • The MnO2 could be recovered. The manganese chloride was treated with milk of lime (a thin cream of slaked lime and water) to make ‘Weldon Mud’ (a mixture of calcium manganite CaO.2MnO2 and manganese manganite MnO.MnO2).This was separated from the CaCl2 solution and used again in the chlorine production process. • 1870 Deacon developed the process2HCl + 1/2O2→ H2O + Cl2 used copper as a catalyst • Gaskell, Deacon & Company based at Widnes exploited this technology • Eventually all of the Leblanc companies merged to form United Alkali Company who later where one of the companies merged to form ICI

23. Chlorine • All of the chlorine technologies were dirty • Electrochemistry would be cleaner and first observed by Cruikshank in 1800 • First patent based on a porous diaphragm was 1851 to Watt • However, the lack of domestic electricity supplies limited technology • United alkali company operated first membrane cell in 1890 Cell technologies NaCl + H2O → NaOH + ½H2 + ½Cl2 • Regardless of cell type, the evolution of chlorine takes place at the anode (positive electrode) of the cell: Based on cell type, hydrogen and the hydroxide ions to form sodium hydroxide are generated, directly or indirectly, at the cathode (negative electrode) of the cell: