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  • CM1100 LECTURE NOTES: HISTORY OF THE CHEMICAL INDUSTRY M A MORRISE-MAIL [email protected]: 108 Kane BuildingIndustrial Inorganic Chemicals: Production and Uses, Ed. R ThompsonThe Chemical Industry, Ed. A Heaton

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  • PengantarBahan kimia (Chemicals) telah diketahui oleh nenek moyang kitaMesir Ancient (Egyptians) telah menggunakan apa yang disebut SABUNSoda (sodium carbonates, natron in Egypt) + lemak digunakan untuk mencuci MAYAT (corpses) sebelum proses mumifikasiSemen telah diketahui oleh Egyptians, Romans dan Greeks (forgotten for 2000 yrs) dari ABU VOLKANIK + BATU + SODA KAUSTIK (NaOH)500 th lalu suku Indian MAYA menggunakan LATEX untuk main bola dan pakaian.

  • Modern Chemical IndustryDimulai di UK sekitar th 1750-1800Lead-Chamber Method dikembangkan di England th 1749 utk membuat sulfuric acid. Di picu oleh industrial revolution dg permintaan chemicals utk keperluan industri lainSoap manufacture (alkali + animal fat)Cotton bleachGlassmaking sand (SiO2) and soda (sodium carbonate)

  • Three key chemicals needed to be manufactured..Sulphuric acid - oil of vitriolJumlah terbesar chemical di dunia 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 carbonateSodium Carbonate (Soda ash, Sal Soda, Washing Soda) (Na2CO3) & Sodium Bicarbonate (baking soda) (NaHCO3) dipakai utk membuat glass, soap, textiles, paper, disinfectant, cleaning agent, dan water softener Caustic soda sodium hydroxideAlkali Hydroxides (usually just called "Alkali") digunakan utk memproduksi glass, paper, soap, pewarna textiles, aid in oil refining, bahan bleaching compounds, dan penyiapan leather.

  • Sulphuric acid an early route - copperasJabir-Ibn-Hayyan (721-815) distinguished between green vitriol and blue vitriol, ferrous sulphate and copper sulphate respectivelyGreen 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. Took place at Tankerton in Kent and in Dorset but soon move to the NW of EnglandIt was the first heavily capitilised industry requiring large scale investments

  • Bhn kimia pertama yg diproses pd industrial scaleThis 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 NOxWater in reaction chamber absorbed gasesReactions 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

  • Potassium Nitrate (saltpeter, Nitre) (KNO3) diperoleh sebagian besar dari India dan digunakan utk membuat matches, explosives,dan fertilizers. Chile saltpeter, bentuk tdk murni dari sodium nitrate (NaNO3), terendapkan di spj pantai Pasifik oleh large flocks of birds.Lime saltpeter (Norwegian saltpeter) which is composed of calcium nitrate (CaNO3)These are only source of nitrates until Haber processThey 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.

  • Sulphuric acid improvementsGay-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 1870s1880s 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 oxidesAbsorption tower

  • 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 SO2 S(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 ------> H2S2O7 This 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)

  • Soda ash manufactureBy 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 + 2HClNa2SO4 + 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

  • 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

  • Solvay processJohn Hutchison pioneered NW chemical industry recognising efficiency of scale1847 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

  • Solvay processErnst Solvay Belgium 1838-1922Several similar processed but difficult on large scale (Muspratt had almost gone bankrupt). Used to much NH4 which was not widely availableAdvantages 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 greater1890 Solvay was 90% of marketProcess centred on iron towers where rising CO2 was mixed with brine spray

  • Solvay process

    CO2(g) + H2O(l) + NH3(g) + Na+(aq) NaHCO3(s) + NH4+(aq) at 0-15C (1) NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g) at 300C(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.

  • Schematic diagram of the manufacturing process

  • Ammonia productionVital chemical in several industriesDyes, cotton treatments, plastics, fertilizer and Solvay processIt was difficult to make hydrogen is expensive and the N2/H2 reaction was very high temperatureBefore 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

  • The Haber processThe 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 hydrogenN2(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 + 6H2OThis NO is oxidised to NO2 in air and dissolved in water to yield nitric aci