Di adopsi dari :LECTURE NOTES: HISTORY OF THE CHEMICAL CM1100

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

Pengantar
Bahan kimia (Chemicals) telah diketahui oleh nenek

moyang kita Mesir Ancient (Egyptians) telah menggunakan apa yang disebut SABUN Soda (sodium carbonates, natron in Egypt) + lemak digunakan untuk mencuci MAYAT (corpses) sebelum proses mumifikasi Semen 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 Industry

Dimulai di UK sekitar th 17501800 Lead-Chamber Method dikembangkan di England th 1749 utk membuat sulfuric acid. Di picu oleh industrial revolution dg permintaan chemicals utk keperluan industri lain Soap manufacture (alkali + animal fat) Cotton bleach Glassmaking sand (SiO2) and soda (sodium carbonate)

Three key chemicals needed to be manufactured..

Sulphuric acid - oil of vitriol

Jumlah 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 carbonate

Sodium 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 hydroxide

Alkali Hydroxides (usually just called "Alkali") digunakan utk memproduksi glass, paper, soap, pewarna textiles, aid in oil

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. 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

Bhn kimia pertama yg diproses pd 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

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 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.

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

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

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

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 Blanc Process 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.

Solvay process

John Hutchison pioneered NW chemical industry recognising efficiency of scale 1847 founded chemical works (Halton Ernest Solvay 1838-1922 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

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

Solvay process

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

(1) (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 Solvaybased 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 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

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 rhodiumplatinum 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 Haber process

The Haber process

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.

Fritz Haber

By 1905 Fritz Haber (18681934) had developed the catalyst for fixing nitrogen from air. The process was soon scaled up by BASF's great chemist and engineer Carl Boschhence 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 weaponpoison 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.

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.

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

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 process 2HCl + 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

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 + H2 + Cl2

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: