Laval University From the SelectedWorks of Fathi Habashi December, 2017 Success and Failure of the Canadian Metallurgical Industry Fathi Habashi Available at: https://works.bepress.com/fathi_habashi/ 268/ Fathi Habashi, SF J Metallurgical Science, 2017, 1:1 SciFed Journal of Metallurgical science Research Article Open Access Success and Failure in the Canadian Metallurgical Industry * Fathi Habashi * Department of Mining, Metallurgical, and Materials Engineering Laval University, Quebec City, Canada Abstract The mining and metallurgical industries are important contributor to the Canadian economy. There were successes and failures in these industries in the past fifty years. Examples of the success story of Sherritt Gordon Mines in Alberta for hydrometallurgy, the International Nickel Company in Sudbury for pyrometallurgy, the aluminum industry in the Province of Quebec for electrometallurgy, and the Bottom Blown Oxygen Converter for the steel industry by Liquid Air engineers in Montreal. The failure took place in the asbestos industry, magnesium production, the titanium pigment plant of Tioxide Canada, Noranda, and Orbite - - all in Quebec, will be presented as witnessed be the author. Keywords Sherritt Gordon INCO; Aluminum industry; Oxygen converter; Gold, Asbestos; Magnesium; Titanium pigment; Orbite; Thompson Refinery; Tar sands; Potash; Uranium; Engineering firms Introduction Canada is a world leader in the metallurgical industry. The Canadian mining and metallurgical industries contribute about 40 billion dollars to national economy. Many metallurgical processes were developed or invented in Canada thanks to the new organizations that were created for these purposes: • The Canadian Institute of Mining and Metallurgy, founded in 1898, was responsible for promoting the development of the industry by organizing meetings where academic people met industrial engineers and metallurgical processes were discussed. • The Mines Branch in Ottawa was created in 1907 was also responsible for creating and helping many of the new metallurgical processes. • The Canadian National Research Council founded in 1916 was behind the magnesium process discovered in Canada. SF J Metallurgical Science ISSN:xxxx-xxxx SJOMS, an open access journal • The engineering firms created in 1947 and later were responsible for installing many plants in Canada and abroad. Canada has also the tallest chimney in the world (Figure 1). It is located in Sudbury and is 381 m tall. Some Canadian metallurgical plants are also producing fertilizers, for example, ammonium sulfate by Sherritt and ammonium phosphate at Trail. This shows the strong relation between the metallurgical and the chemical industry. Atlas Steel in Welland, Ontario was the first in 1950s to adopt continuous casting [1]. *Corresponding author: Fathi Habashi, Department of Mining, Metallurgical, and Materials Engineering Laval University, Quebec City, Canada. E-mail: Fathi.Habashi@arul.ulaval.ca; Tel: [418] 651-5774 Received June 14, 2017; Accepted October 27, 2017; Published November 13, 2017 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Copyright: © 2017 Fathi Habashi. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. Volume 1 · Issue 1 · 1000001 page 1 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Table 2: Name change of major mining and metallurgical companies in Canada Figure 1: Chimney at Sudbury Original name New names Alcoa Aluminium Company of Canada, Alcan, Rio Tinto Alcan Consolidated Mining & Smelting Company Cominco, Teck Cominco Eldorado Nuclear Cameco Falconbridge xstrata, Glencore Canada International Nickel Company INCO, CVRD Inco, Vale Inco, Vale Canada Noranda xstrata Quebec Iron and Titanium QIT Fer et Titan, Rio Tinto QIT Kilborn Engineering The industry achieved many successes as well as some failures. The successes are in the fields of hydro-, pyro-, and electrometallurgy as well as in industrial minerals such as the tar sands and the potash industries. The failures are mainly in the asbestos industry, the white pigment manufacture, magnesium recovery, and the recovery of alumina from clay [2]. Certain metals produced as by-products of main metals (Table 1). In the past few years the company names has changed (Table 2). The treatment followed here is as much as possible historic. Roland Kenneth Kilborn (1902 - 1959) (Figure 2) founded in 1947 Kilborn Engineering the first major engineering firm in Canada that designed and built some of North America’s largest mines and became an industry leader in gold milling, potash refining and uranium processing. Kilborn graduated from Queen’s University in 1927 with degree in civil engineering. After two decades of working and gaining experience at a variety of mining projects in northern Ontario, he formed the engineering firm that took part in Canada’s uranium industry as well as Canada’s coal mines and washing plants, and most of the country’s asbestos mines and plants Figure 2- Roland Kenneth Kilborn (1902:1959) Table 1: By-product metals By-product metal or metalloids Major metal Antimony Lead Arsenic Copper, gold Bismuth Lead Cadmium Zinc Cobalt Nickel Platinum metals Nickel Selenium Copper, nickel Tellurium Copper, nickel SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Kilborn Engineering also built most of Canada’s potash refinery capacity in Saskatchewan and New Brunswick. In addition, the company designed and built a number of gold mines and plants in North and South America. By 1982, the company had grown to more Volume 1 · Issue 3 · 1000001 page 2 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. than 1,500 employees, with offices across Canada and in Denver, Colorado. It is now part of the SNC-Lavalin which built the largest autoclaves in the world [see Nickel in Madgascar]. Magnesium Thermal Process Lloyd Pidgeon (1903-1999) (Figure 3) is best known for the development of the process for the production of high¬ purity magnesium. He was born in Markham, Ontario, graduated in 1925 in chemistry from the University of Manitoba, and a PhD from McGill University in 1929. After several years at Oxford University, Pidgeon joined the National Research Council of Canada where he developed the process for the production of magnesium metal using the reaction between calcined dolomite and ferrosilicon: Province of Quebec on the western side of Saint Lawrence River, Norsk Hydro constructed a 40,000 t/y magnesium production plant in 1986 (Figure 4). It was the largest primary magnesium producer in the world based on the dissolution of imported magnesite, MgCO3, in hydrochloric acid, evaporating the magnesium chloride obtained, and its electrolysis. It was shut down in 2006 because it was not able to compete with the Chinese companies at this time. Figure 4: Norsk Hydro magnesium plant in Becancour Figure 3- Lloyd Pidgeon (1903-1999) MagCan 4 MgO.CaO + 2 Si → 2Ca2 SiO4 + 4 Mg A group of prominent mining men from Toronto became interested in the project and raised capital that enabled Pidgeon to establish a pilot plant. Pidgeon's discovery led to the formation of Dominion Magnesium, which he joined in 1941 as a director of research. The plant is now owned and operated by Timminco. Because of the demand for magnesium during the Second World War, six magnesium plants were built throughout North America. Magnesium was used for a variety of military efforts and was considered to be the metal of choice where strength with lightness was required, as for example, in aircraft. In 1943, Pidgeon was appointed professor and head of the department of metallurgical engineering at the University of Toronto, a post he held until his retirement in 1969. The MagCan plant (Figure 5) north of High River in Alberta opened in 1991 at 30% of its capacity, with support from the Alberta government in an attempt to diversify the economy away from oil and gas when the price of natural resources declined sharply. It was based on chlorination of imported magnesite with chlorine and CO to produce MgCl2 for electrolysis. It closed down after less than a year in operation. The company started its activity at a moment when the magnesium price was low. The Province provided a $103 million loan guarantee and 145 people lost their jobs. Figure 5- MagCan plant in Alberta Nosrk Hydro Process In Becancour just opposite to Trois Rivieres in the SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 3 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Magnola See “Asbestos”. Mines Branch The Mines Branch now called Canadian Centre for Mineral and Energy Technology, and abbreviated Canmet is responsible for the discovery and development of many metallurgical processes. One of these discovered by Downes and Bruce in 1955 is the recovery of elemental sulfur from pyrrhotite containing nickel - - a process that was applied in 2000 in Voisey Bay in the Canadian North. This marks for the first time nickel recovery from sulfides by hydrometallurgical method: concentrates of copper, nickel, and cobalt since they form soluble ammine complexes. The process has minimum corrosion problems and any pyrite present will not be attacked. Ammonium sulfate is a by-product; it is marketed as a fertilizer. The overall reaction is: Figure 7: Pressure leaching of Ni-Cu-Co sulfides in ammonia 2 FeS + 1½O2 → Fe2 O3 + 2 S Nickel in the sulfide is found in solution. Sherritt Gordon Mines Sherritt Gordon Mines (Figure 6) in Fort Saskatchewan, Alberta is a pride of the Canadian Metallurgical industry. It produces the metals nickel and cobalt as well as the fertilizers ammonium sulfate, ammonium phosphate, and urea. It is a progressive company had its success in the collaboration with the University of British Columbia and the Mines Branch in Ottawa in the 1950s. It is also a consulting firm that built plants all over the world to produce nickel and cobalt from laterites as well as to liberate gold from refractory ores to be followed by cyanidation [3]. Sherritt also was a pioneer in powder metallurgical applications. Figure 6: Sherritt Gordon Mines in Fort Saskatchewan, Alberta MS + nNH 3 + 2O2 →  M ( NH 3 )n  2+ + SO42 − Where M stands for Ni, Cu, and Co. Pressure Hydrometallurgy The company introduced modern hydrometallurgy in the world and specially pressure reactors. It precipitated nickel directly from ammoniacal solution by hydrogen under pressure instead of the long known process at that time - - the first in the world by the reaction: M 2+ + H 2 → M + 2 H + Crystals of cobalt were also produced by the same process (Figure 8). Example of the reactors used by Sherritt (Figure 9) [4]. Figure 8: Cobalt crystals precipitated from aqueous solution by hydrogen under pressure Ammonia Leaching Process The process (Figure 7) is used for treating SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 4 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Figure 9:Typical pressure reactor used by Sherritt the leaching step thus no SO2 and the necessity to make sulfuric acid: Figure 12 : Leaching of zinc sulfide concentrate in an autoclave Sherritt Mint Sherritt also produced by hydrometallurgical methods 5-cents nickel coins for Canada for 40 years (Figure 10) as well as the Canadian dollar from nickel covered by a thin layer of brass (Figure 11). Figure 10: 5-cents coins produced by Sherritt ZnS + 2 H + + ½O2 → Zn 2 + + S + H 2 O In the old method the sulfide ore was roasted, the calcine leached with sulfuric acid, and the zinc sulfate solution was electrolyzed to get pure metallic zinc. Sulfur dioxide formed during the roasting step is transformed to acid which was always used to treat phosphate rock to produce fertilizer. The new process freed the zinc industry from the need to produce fertilizers. Laterites Figure 11: One dollar produced by Sherritt Sherritt designed the plant for nickel recovery by pressure leaching plant for laterites in Madagascar. The autoclaves (Figure 13) built by SNC-Lavalin were the largest in the world. Figure 13: Autoclaves at Ambatovy in Madagascar Zinc Industry Sherritt also introduced in 1980 a zinc process that made the industry independent of the fertilizer industry (Figure 12). In one step the zinc concentrate was treated with sulfuric acid and oxygen in an autoclave to produce a solution of zinc sulfate which can be electrolyzed to pure metallic zinc while elemental sulfur is produced during SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Falconbridge Falconbridge Company developed a commercial process for the treatment of a mixture of Cu2S–Ni3S2 obtained by smelting a copper–nickel sulfide concentrate: Volume 1 · Issue 3 · 1000001 page 5 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Ni3S2 is solubilized in concentrated HCl while Cu2S is not. The leaching reaction is: Ni3 S2 + 6 HCl → 3 NiCl2 + 2 H 2 S + H 2 Cu2S is separated by filtration for copper recovery, while NiCl2 solution is first purified from dissolved H2S by air oxidation and removal of the sulfur formed, then crystallized as NiCl2.2H2O. Since it is technically difficult to reduce NiCl2 by hydrogen to nickel, the chloride is first calcined to NiO then reduced: Separation of Nickel and Copper Sulfides The separation of CuS2 from Ni3S2 obtained from the Sudbury ore by matte formation was a problem since its discovery. The tops and bottoms process, also known as Orford process, based on fusion with sodium sulfide was used for 60 years from 1890. It was based on the fact that Cu2S is soluble in molten Na2S while Ni3S2 is practically insoluble. Figure 15: The system Cu2S–Na2S NiCl2 ·2 H 2 O → NiO + 2 HCl NiO + H 2 → Ni + H 2 O Equity Silver The presence of arsenic and antimony in copper sulfide concentrates is undesirable because these metals complicate the smelting and refining of copper. As a result there is interest to remove them before smelting. A copper sulfide concentrate containing 4 % as and 7 % Sb is treated in British Columbia by Equity Silver Company by sodium sulfide [5]. The finely divided concentrate is leached for 16 hours at 110°C to solubilize arsenic and antimony sulfides: Figure 16: The system Ni3S2–Na2S As2 S3 + 3S 2 − → 2 AsS33− Sb2 S3 + 3S 2 −− → 2 SbS33− After filtration, the copper concentrate is shipped to smelters. The company, however, stopped production. International Nickel Sudbury The International Nickel became known as INCO then Vale is a pioneer in many extractive metallurgy processes that is became the world capital of nickel [6]. Figure 17- The Orford Process Figure 14: 200 years nickel in Sudbury [1751- 1951] SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 6 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Figure 18: Orford process or tops and bottoms process furnace was adopted to treat copper - nickel sulfides using oxygen instead of air. Figure 20 - INCO flash smelting furnace In 1950 it was replaced by slow cooling of the binary sulfides followed by grinding then a more economical flotation process (Figure 19). It was also possible to separate an alloy containing the platinum metals. Figure 19: Separation of CuS2 from Ni3S2 by slow cooling, grinding, and flotation Converter The company introduced in 1960s the Top Blown Rotary Converter (Figure 21) to convert directly nickel sulfide to metallic nickel instead of oxidation of nickel sulfide to oxide then reduction to metal thus shortening the treatment which is a great advantage: Figure 21- Top Blown Rotary Converter Ni3 S2 + 2O2 → 3 Ni + 2 SO2 Flash Smelting The invention of flash smelting for copper concentrates by Outokompu in Finland and INCO took place simultaneously in 1940s. It was based on the use of the heat generated by the oxidation of sulfides to melt the charge instead of using an extra fuel in a reverberatory furnace (Figure 20). The difference between the two was in some details but the principle was the same. The same SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Carbonyl Process The pressure carbonyl process developed by INCO permitted the production of nickel carbonyl very fast at a higher temperature (Figures 22 and 23). The carbonyl process is used for refining nickel. Nickel carbonyl is very poisonous. Carbon monoxide gas reacts with nickel for form gaseous nickel carbonyl. By this method pure nickel Volume 1 · Issue 3 · 1000001 page 7 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. powder is obtained. Figure 22 - Carbon monoxide gas reacts with nickel for form gaseous nickel carbonyl purified solution is returned to the cathode compartment, which is separated from the anode by a porous diaphragm in the form of a box enclosing the cathode, at such a rate that a hydrostatic head of solution builds up relative to the rest of the electrolyte (Figure 24). This prevents impurity ions from diffusing into the cathode compartment. Figure 24 - Introducing the purified solution in the cathode compartment of diaphragm cell Figure 23 - The pressure carbonyl process developed by INCO Pressure Leaching of Nickel Sulfide Electrolysis of Nickel Sulfide Sulfides are semiconductors and conduct the electric current. At Thompson Refinery in Manitoba INCO cast nickel sulfide white metal into anodes and by electrolysis it was possible to get pure nickel at the cathode and elemental sulfur at the anode: Anodic reaction: Cathodic reaction: Ni + 4CO → Ni ( CO )4 Ni 2 + + 2e → Ni With the discovery of the Voisey Bay sulfide deposits in the Canadian North it was decided in 2005 to use a pressure leach¬ing process to produce elemental sulfur instead of SO2 (Figures 25 and 26). The deci¬sion was made because the Government of Newfoundland refused that the concen¬trate be shipped outside the Province. This is the first acid pressure leaching process for nickel sulfides and was originally developed at the Mines Branch in Ottawa by Downes and Bruce in the 1950s. The sulfide concentrate is mainly pendlandite - pyrrhotite containing 1.6% nickel. Figure 25 - Pressure leaching process for treating the Voisey Bay concentrate Thus, it would be possible to recover the metal and the sulfur directly in one step, instead of roasting the sulfide to oxide, reduction of the oxide to metal, and then casting the metal in form of anodes for electrolytic refining. In this direct electrolysis it is possible to recover the sulfur in the elemental form instead of emitting it in the form of SO2. Pure Nickel by Electrolysis INCO developed a purification step to prepare pure nickel by electrolysis in a diaphragm cell. To keep impurities at a tolerable level a calculated volume of the electrolyte is continuously bled to a purification circuit. The SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 8 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Figure 26- Nickel sulfide pressure leaching plant under construction at Argentia in New¬foundland as Sorelslag containing 72% TiO2 (Figures 28,29). The slag was used to make TiO2 white pigment. Later, the slag was upgraded to 95% TiO2 by pressure leaching with hydrochloric acid to remove calcium and magnesium. The technology of manufacturing Sorelslag was adopted before the hydrometallurgical route for making “synthetic rutile”. Figure 28 - QIT Fer et Titan electric furnace plant on the top left in Sorel, Quebec Ammonia Leaching in Nickel Metallurgy In 1960s INCO built anammonia leaching pilot plant. In this plant, nickel sulfide concentrate containing about 0.8% Ni was roasted to oxide, the oxide reduced to metal, and the metal was leached with ammonia to get a solution from which nickel oxide containing 80% Ni was precipitated (Figure 27). The plant was operated for nearly a year when it was shut down because it proved to be uneconomical. Figure 27- INCO ammonia leaching pilot plant for pyrrhotite Figure 29 - QIT Fer et Titan Sorelslag Iron Powder Sorel QIT Fer et Titan In 1955 QIT Fer et Titan in Sorel, Quebec built nine electric furnaces to partially reduce ilmenite containing 36% TiO2 to iron and titanium slag known SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal A successful iron powder industry was created in Quebec next to QIT Fer et Titan (Figure 30). Highpressure water jets are used to break up the stream of molten iron. There is a need for iron powder for use in powder metallurgy applications, for welding rod coating, for fireworks, and other applications. Most iron powders are used for automobile parts which are easier to produce than by other methods (Figure 31). Volume 1 · Issue 3 · 1000001 page 9 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Figure 30- Production of iron powder Aluminum Industry The aluminum industry was first established in Canada in Shawinigan, Québec in 1901 by the Northern Aluminum Company (now Alcan Aluminum). Over the next 5 decades, Alcan established a network of smelters and an alumina refinery in Québec and one smelter in British Columbia (Figure 33). The availability of abundant hydroelectric power led to the establishment of the aluminum industry in Canada. Canada is the world's fourth largest producer of aluminum, after the US, Russia and China. Figure 33 - Aluminum plants in Canada. All plants are in Quebec except Kitimat in British Columbia Figure 31- Articles produced from iron powder Alumina and Aluminum Industry Alumina Although Canada is the third largest producer of aluminum in the world, all its alumina is imported except one plant in Saguenay which is producing alumina from bauxite imported from Jamaica. Any attempt to recover alumina from silicates by hydrochloric acid cannot compete with bauxite using alkaline solution because of the low tenor of aluminum in the raw material as compared to bauxite and the ease with which aluminum hydroxide is recovered from the basic solution (Figure 32). Orbite in Cap Chat in Quebec tried to obtain alumina from clay but after 5 years operation and spending $ 127 million has announced bankruptcy and suspended operation in 2017 [7]. Søderberg electrodes which caused pollution were replaced by prebaked electrodes (Figure 34), fluorine capturing systems were added (Figure 35), and pollution problems were solved by installing gas scrubbing systems (Figure 36). Figure 34- Prebaked electrodes Figure 32 - Alumina production from clay. Orbite process SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 10 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Figure 35- Fluorine capturing systems Pelletization The iron ore industry in Quebec has advanced greatly in Quebec and the Province has one of the largest iron ore pelletization plants in the world using inclined rotating disc (Figure 37) [8]. Figure 37 - Iron ore pelletization plant in Quebec Figure 36 - Gas scrubbing system Midrex Process Iron and Steel Industry General Sidbec Dosco in Contrecoeur, Quebec was one of the first to adopt the Midrex process for steel production in 1973 (Figure 38). A larger plant was installed in 1977. Oxide pellets are charged in a vertical furnace to which a reducing gas is introduced at the bottom (Figure 39). The reducing gas is a reformed natural gas. The metallized pellets are then discharged from the furnace and melted in an electric furnace to produce steel. Beside the use of blast furnaces (Table 3) Canada pioneered in direct reduction processes: Figure 38- Midrex plant in Contrecoeur, Quebec - The H-iron fluid bed process as developed by Imperial Oil Company at Dortmouth, Nova Scotia - Stelco piloted the world’s first SL/RN rotary kiln process Table 3: Steel production in Canada Source % Blast furnaces 60 Scrap 30 Direct reduction 15 Ilmenite 15 100 SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 11 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Figure 39 - Midrex plant in Contrecoeur, Quebec Figure 41 - An electric furnace under construction in 1973 at the Union Carbide plant at Beauharnois in Quebec showing the 3-metre diameter openings at the top for the carbon electrodes Oxygen in Steelmaking Bottom Blown Oxygen Converter for the steel industry was invented by engineers at Liquid Air in Montreal. The use of oxygen accelerates greatly the oxidation of impurities. The use of a small volume of natural gas for cooling due to a cracking reaction eliminates the deterioration of refractories [9] (Figure 40). The fact that oxygen is introduced at the bottom of reactor away from slag renders the process fast and efficient. It is a success story that is used all over the world. Figure 40 - Bottom Blown Oxygen Converter Ferro Alloys Due to the cheap electric power, Quebec became the center of ferroalloys by electric furnaces (Figure 41). Ferrosilicon, ferromanganese, and ferrochromium are produced by reducing the corresponding oxide with coke. In the case of the reduction of silica sand at SKW in Becancour, Quebec it was found that silicon monoxide, SiO, volatilized then oxidized to very fine SiO2 in the recovery system. Such fine silicon dioxide found application in the concrete industry. For ferronoibium see below. SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Niobium and Ferroniobium Since 1977 Niobec owned by Cambior has been producing high quality niobium in Saint Honoré in the Saguenay region. The most important niobium mineral is pyrochlore, (Ca,Na)2 -mNb2O6(O,OH,F)1 - n.xH2O. The lattice positions of Na and Ca can also be occupied by Ba, Sr, rare earths, Th, and U. The latter two elements are responsible for the radioactivity of some pyrochlore concentrates. The ore contains 0.5-0.7% Nb2O5. Pyrochlore mineral is processed by primarily physical processing technology to give a concentrate ranging from 55 to about 60% niobium oxide. Ferroniobium contains 63-68% niobium is produced by the aluminothermic process. Niobium oxide, Nb2O5, is generally the starting chemical for the production of other compounds. Niobium metal is produced by the aluminothermic reduction of the oxide followed by electron beam refining. Niobium powders can be produced by the reduction of potassium niobium heptafluoride (K2NbF7) with sodium, or by the reduction of niobium oxide with magnesium. Uranium Rich uranium deposits were found in Saskatchewan (Figure 42) and as a result the uranium industry is well developed in Canada. Uranium refinery is in Port Hope, Ontario. Leaching uranium ore with sodium carbonate was introduced in Canada when the ore contained acidconsuming gangue. Volume 1 · Issue 3 · 1000001 page 12 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Figure 42 - Uranium processing plants in Canada Figure 43 - Effect of cyanide and oxygen on the rate of dissolution of silver [Deitz and Halpern, 1953] POTASH Gold Canada produces about 200 tons of gold every year of which about 80% comes from 70 mines and the rest is by-product of copper and nickel production. Explanation of the cyanidation process was done in Canada when the effect of cyanide concentration and oxygen concentration were studied (Figure 43). This led to the establishment of the theoretical equation based on the formation of anodic and cathodic areas [10]: Canada is the world's largest potash producer and exporter. In 1943, it was discovered in Saskatchewan in the process of drilling for oil. Active exploration began in 1951. Underground and solution mining is practiced (Figure 44). Figure 44 - Canadian potash in Saskatchewan – 2AD – D O 2 [ CN ] [ O 2 ] CN Rate = ---------------------------------------------------------------------– δ ( D – [ CN ] + 4D O 2 [ O 2] ) CN Where: DCN- and DO2 = the diffusion coefficients of cyanide and dissolved oxygen, cm2.sec–1, [CN–] and [O2] = the concentration of CN– and O2 in the bulk of the solution in mole/mL, δ = the thickness of the boundary layer, in cm, and A = the total surface area of metal in contact with the aqueous phase. At low cyanide concentration the term [CN-] can be neglected in the above equation and the rate becomes: Rate = DCN-[CN-] which agrees with the experimental data. If on the other hand at high cyanide concentration the term [O2] can be neglected in the above equation and the rate becomes: Rate = DO2 [O2] which again agrees with the experimental data. SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Tar Sands Oil is now produced in Canada from tar sands in Alberta (Figures 45-48). Tar is a mixture of many organic substances, which are separated by distillation at different temperatures. The distillation residue is pitch. The tar sands of north-eastern Alberta constitute one of the largest deposits of liquid hydrocarbons in the world. The tar sands extend over an area of over 900 × 106 km2 and are estimated to contain 126 × 109 tons from which at least 35 × 109 tons of crude oil are expected to be produced. A part Volume 1 · Issue 3 · 1000001 page 13 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. of the deposit located at Athabasca is amenable to surface mining, while the major part is expected to be available by in-situ techniques. Figure 48 - Processing of tar sands Figure 45 - Tar sands Engineering Firm The mining method generally used is mixing the oil sand with warm water to create slurry which can be transported by pipeline to a separating vessel where the sand settles to the bottom and air bubbles form froth on the top. The bitumen froth is skimmed off, mixed with solvent, and spun in a centrifuge to remove the water and solids. The bitumen can then be processed into crude oil. Hatch is one of the most successful Canadian metallurgical engineering firms in Canada [11]. It was founded by Gerald G. Hatch (1922-2014) (Figure 49). The company has grown from six people in one office in Toronto in 1958 to over 11000 employees in 65 offices worldwide. The company is owned by the employees. One of the recent achievements is the world’s largest tube autoclaves for processing Saudi Arabian bauxite to prepare alumina for aluminum production (Figure 50). Among the many donations offered by Hatch is the Hatch Center at McMaster University in Hamilton, Ontario (Figure 51). Figure 49- Gerald G. Hatch (1922-2014) Figure 46 - Tar sands in Alberta Figure 50 - Tube autoclaves Figure 47 - Exploiting the tar sands Figure 51 - Hatch Center at McMaster University in Hamilton, Ontario SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 14 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Canadian Mint Royal Canadian Mint (Figure 52) founded in 1901 operates a technically advanced refinery in which it refines precious metals from a variety of sources including primary producers, industry, recyclers and financial institutions. The Mint refines raw gold to 995 fines through the Miller chlorination process. The gold is then cast into anodes for electrolytic purification to 9999 fine using the Wohl will process. On metallurgical events the mint issued a commemorative coin on the occasion of 250 years of the first Canadian iron making plant at Saint Maurice in Quebec (Figure 53). by 1895 mining started to be mechanized. This marks the beginning of a stage of unprecedented growth. The number of workers grew with the demand for asbestos. Figure 54 - Early mining of asbestos in Quebec Figure 52 - Royal Canadian Mint in Ottawa Figure 55 - Crushing room at Johnson Mine in Quebec, 1900. Note the girls were using hammers to crush the ore Figure 53 - Commemorative dollar on the occasion of 250 years of Forge Saint Maurice the first Canadian iron making plant Asbestos is recovered from the crushed and ground rock by aspiration (Figure 56). The air-tight building housing the equipment is under slight pressure to make sure that no fibers are released in the work place. This is done by re-circulating the clean air sucked by the fans at the top of the building through air-pressurized rooms. Figure 56 - Recovery of asbestos fibers from the rock Asbestos Exploitation in Quebec Although known in ancient times it has been first discovered in economic mines in 1876 in Thetford Township in Quebec [12]. The exploitation was simple and the workers often inexperienced (Figures 54-56) but SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 15 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Uses Figure 50- Asbestos brake lining set Asbestos is an industrial mineral of great economic importance. About 70% of the asbestos is used in the fabrication of asbestos cement whereby the fibers are slurried in water with Portland cement for making pipes and other construction materials (Figures 57-60). Such material contains 12 - 15% of asbestos which increases greatly its resistance. Asbestos in admixture with plastics and asphalt enters in the manufacture of a variety of tiles and sheets used as a covering material. Figure 57- Asbestos cement pipes Because of its heat resistance, asbestos mixed with metallic fibers and resins to the extent of 40% is used in the manufacture of what is called friction materials, e.g., brakes for motorcars and aeroplanes (Figure 56). Asbestos also enters in the manufacture of certain industrial paper and gaskets. Asbestos was also used for the brakes in the elevators in skyscrapers. Nationalization Figure 58 - Asbestos panels for roofs As Minister of Natural Resources in 1976, Yves Bérubé (1940-1993) (Figure 61) presided over the creation of State Corporation for Research, Prospection, and Promotion of Asbestos. In 1978 the National Society of Asbestos was created as a Quebec Government organization located in Sherbrooke, Quebec. The Society had a Research Department directed by Jean Marc Lalancette, Chemistry Professor at the University of Sherbrooke. In 1980 the Quebec Government decided to nationalize the industry. Figure 61 - Dr. Yves Berube (1940-1993) The growing railroad industry was among the first to make extensive use of asbestos in refrigeration units, as insulation for pipes, boilers, and fireboxes (Figure 55). Ship builders also made extensive use of asbestos material. It was also used in the building industry as wall insulation, for floor and ceiling tiles, in exterior siding, and in roofing. Figure 59 - Asbestos articles for insulating materials Carcinogenic Mineral The nationalization of the industry was followed by a campaign against asbestos as a carcinogenic mineral resulting in a drastic decreased production. It was at the turn of the twentieth century that researchers began to notice a large number of deaths and lung problems in asbestos mining towns. In 1917 and 1918, it was observed SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 16 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. by several studies that asbestos workers were dying young. In 1924 a woman had been working with asbestos since she was thirteen. She died when she was thirty-three years old, and an English doctor determined that the cause of death was what he called "asbestosis". Because of this, a study was done on asbestos workers in England. Twenty five percent of them showed evidence of asbestos-related lung disease. Laws were passed in 1931 to increase ventilation. In the 1930s major medical journals began to publish articles that linked asbestos to cancer. The use of asbestos was at its highest in the 1940s to 1970s. The warnings and regulations of the 1970s and beyond put an end to much of the production although the industry greatly improved its operation with respect to ventilation and dust control. Its use was banned in many countries. e.g., bromocresol purple and phenolphthalein, although they are not dyestuffs, they color asbestos. It was found that some dyes, e.g., Thiazol Yellow G and Trypan Blue decreased the toxicity of the fibers. Unfortunately, the project was abandoned due to lack of financing, retiring of the inventor, and departure of the chemist doing the job. At that time all financial efforts were directed to the attorneys defending the case with the US Environment Agency. Asbestos Tailings Asbestos tailings became also a problem because to produce one tonne of asbestos about 30 tonnes of tailings have to be discarded. Is Quebec about 600 million tons of tailings were piled up in the form of a mountain (Figure 63) which contains about 40% MgO. Figure 63 - Asbestos tailings in Quebec Research towards Asbestosis Chrysophosphate The Research Center of Societe National de l’Amiante in Sherbrooke, Quebec developed in 1980s a process for decreasing the toxicity of asbestos by treatment with vapours of POCl3 (Figure 62). The product was known as Chrysophosphate. The process was uneconomical and technically unsound. Treatment of asbestos with phosphate ion in aqueous solutions was found to have the same effect: 3Mg ( OH )2in Asbestos + 2 HPO4 2 − ( aq ) → 6 Mg3 ( PO4 )2 + 4OH + 2 H 2 O Figure 62 - Chrysophosphate pilot plant in Sherbrooke Magnola Project In 1996, a magnesium pilot plant was running at CEZinc in Valleyfield, Quebec to recover magnesium from asbestos tailings containing 24% Mg. In 1997, Noranda Company approved construction of the Magnola magnesium plant at a cost of approximately $730 million to be located in Danville, Quebec next to the tailings disposal heap (Figure 64). Figure 64 - View of Magnola magnesium plant in Danville, Quebec Coloring with organic dyes Chrysotile asbestos has the advantage of a large surface area and can be coloured by organic dyes. The appearance of new peaks in its X-ray diffraction patterns and in infrared spectra of the dyed product together with the absence of precipitates supports that chelates are formed with its Mg(OH)2 component. Some organic compounds, SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 17 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Magnola production capacity would be 63,000 tonnes of magnesium per year, or close to 20% of world supply. Plant construction began in 1998 and metal production began in late 2001. The process involved hydrochloric acid leaching, brine purification, drying to produce granular magnesium chloride which are melted and electrolysed to produce metallic magnesium. The metallic magnesium is tapped and then cast in ingots. Chlorine produced during electrolysis is converted into acid to be used in the leaching stage. It is washed with water and compressed. Then HCl gas is synthesized by burning chlorine with hydrogen. The gas is stripped and distilled so that 99%-HCl gas can be fed into the chlorinator. The hydrochloric acid coming off the chlorinator undergoes a thermal quench and oxidization. It then passes through activated carbon to absorb any chlorinated hydrocarbons that are present. The clean, 35% HCl acid is used in the leach and neutralization circuit. In January 2003 the plant was shut down for economic reasons. The cost of filtration of the brine was a major cost item because the large volumes of residue to be filtered while other processes using magnesite the residue to be filtered is insignificant. If the process were developed to solve an environmental problem then the amount of tailings consumed annually would be insignificant as compared to the hundreds of millions of tonnes already accumulated. Tioxide Canada Tioxide Canada in Tracy next door to QIT Fer et Titan in Sorel, Quebec where ilmenite (Figure 65) was treated in electric furnaces to produce iron and Sorelslag (Figure 66). The company treated Sorelslag produced by QIT by concentrated sulfuric acid to produces pure titanium dioxide which is a white pigment (Figure 67). The process produced dilute sulfuric acid which was uneconomical to concentrate and recycle in the process. As a result the dilute acid was thrown in the Saint Lawrence River for many years. When the Province of Quebec formed the Ministry of Environment in the 1960 it warned the industry from throwing the acid in the river. As a result the industry was shut down in the 1980s. Figure 65- Museum sample of ilmenite, FeTiO2 (59.4 % TiO2) SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Figure 66- Ground titanium slag, FeTi4O10 (70-80 % TiO2) Figure 67 - Titanium white, ~ 100% TiO2 The solution to this problem was to treat the Sorelslag by hydrochloric acid so that dilute HCl can be economically concentrated and recycled. Incidentally, a process was developed in Canada to treat ilmenite concentrate by concentrated HCl at 80oC to get synthetic rutile (Figure 68) which can be converted to white pigment by thermal methods thus bypassing the electric furnace. Figure 68- Synthetic rutile, 98% TiO2 NORANDA Noranda closed in 2002 its copper smelter in Murdochville, Quebec because the ore deposit exploited since 1950s was depleted. It also closed in 2002 its Technology Center near Montreal created in 1970 (Figure 69). It abandoned its process for the recovery of copper in one reactor (Figure 70) because of rapid deterioration of Volume 1 · Issue 3 · 1000001 page 18 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. refractories. Figure 69- Noranda Technology Center Anodic slimes Anodic slimes remaining in the cells after copper electrorefining are treated to recover gold, silver, selenium, and tellurium beside pure copper. Baking with sulfuric acid was used for a long time, e.g. Cu2 Se + 4 H 2 SO4 → 2CuSO4 + Se + 4 H 2 O + 2 SO2 Cu2Te + 4 H 2 SO4 → 2CuSO4 + Te + 4 H 2 O + 2 SO2 Figure 70 - Noranda reactor The problem with this process is the formation of SO2. Pressure leaching at 125oC was then used in which selenium was volatilized and recovered while tellurium was recovered from solution: Cu 2 Se + 4 H + + O2 → 2Cu 2+ + Se + 2 H 2 O Cu 2Te + 2 H + + 5 / 2O2 → 2Cu 2 + + TeO42 − + H 2 O Further development led to the use of oxidation of anodic slimes in top-blown rotary converter to get directly doré metal. Gases evolved during this treatment are collected for selenium and tellurium recovery. Cominco Copper refinery Noranda has a copper refinery in Montreal East (Figure 71) the largest in the world. It also produces copper sulfate for agricultural purposes (Figure 72). Figure 71- Canadian Copper Refinery in Montreal East - - the largest in the world World War I Consolidated Mining & Smelting Company in Trail, British Columbia together with Anaconda in USA introduced during World War I the leaching – electro winning process for zinc to replace the retort process which was uneconomical (Figure 73). Incidentally, the process was replaced in the 1980s by the pressure leaching process referred to earlier. Figure 73- The retort process [left] was replaced by the hydrometallurgical process [right] during World War 1 ZnS concentrate Figure 72 - Production of copper sulfate at Canadian Copper Refinery SO2 O2 Carbon Oxidation Acid plant H2SO4 Zinc oxide calcine Reduction Residue Condenser Purification Pure zinc SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 19 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. World War II Figure 56- Kivset process In World War II 6 tonnes/year electrolytic heavy water plant started operation in 1943 (Figure 74). Heavy water constitutes only one part in 4,500 in ordinary water. The production of heavy water by electrolysis is based on the fact that H2O breaks apart more readily than D2O, and the residual water left after electrolysis is relatively rich in D2O. By reprocessing the residual water over and over again, it was possible to eventually isolate heavy water. This was Canada’s contribution to Manhattan project for the fabrication of an atomic bomb in USA. Heavy water is used in nuclear reactors as a moderator to slow down neutrons. Figure 74 - Plan for heavy water production at Trail Conclusions Canada is a top producer of minerals and metals. Many new technologies and new processes in extractive metallurgy were invented in Canada together with theories of metal extraction were formulated. While some processes proved to be a success others were shut down for being non economical [13]. QSL versus Kivset The company in 1966 became known as Cominco. It used QSL reactor for few years to produce lead (Figure 75). However, the engineers were unable to operate the American plant and as a result they scrapped it and used the Russian technology known as Kivset (Figure 76). Figure 75- QSL-lead plant References 1. Crossfield ET (1998) Pride and Vision. The Canadian Institute of Mining, Metallurgy, and Petroleum 1898-1998, Canadian Institute of Mining, Metallurgy, and Petroleum. 2. Habashi F (1998) Principles of Extractive Metallurgy, Amalgam and Electrometallurgy, Metallurgie Extractive Quebec, Quebec City, Canada 4. 3. Habashi F (1999) A Textbook of Hydrometallurgy, Metallurgie Extractive Quebec, Quebec City, Canada. 4. Habashi F (2014) Pressure Hydrometallurgy, Metallurgie Extractive Quebec, Quebec City, Canada. 5. Deitz GA, Halpern J (1953) Reaction of silver with aqueous solutions of cyanide and oxygen. J Metals 5: 1109-1116. 6. Habashi F (1994) A History of Metallurgy, Metallurgie Extractive Quebec, Quebec City, Canada. 7. Fournier J (2017) Orbite sous respirateur artificiel, Le Soleil. 8. Habashi F (2002) Textbook of Pyrometallurgy, Metallurgie SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 20 of 21 Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. Extractive Quebec, Quebec City, Canada 660. 9. Habashi F (2003) One Hundred Years of Liquid Air. Canadian Contribution, Bull. Can. Inst. Min. and Met. 96: 122-125. 10. Habashi F (1966) The Theory of Cyanidation, Trans. Soc. Min. Eng 236-239. 11. Ignatieff A (1981) A Canadian Research Heritage. An Historical Account of 75 years of Federal Government Research and Development in Minerals, Metals, and Fuels at the Mines Branch, Ministry of Supply and Services, Ottawa. 12. Habashi F (2011) Researches on Asbestos, Metallurgie Extractive Quebec, Quebec City, Canada. 13. Habashi F (2000) Extractive Metallurgy Today. Progress and Problems, Metallurgie Extractive Quebec, Quebec City, Canada. Citation: Fathi Habashi (2017) Success and Failure in the Canadian Metallurgical Industry. SF J Metallurgical Science 1:1. SF J Mat Res Let ISSN:xxxx-xxxx SFMRL, an open access journal Volume 1 · Issue 3 · 1000001 page 21 of 21