- Zinc smelting
Zinc smelting is the process of converting zinc concentrates (ores that contain zinc) into pure zinc.
The most common zinc concentrate processed is
zinc sulfide,Citation | title = Compilation of Air Pollutant Emission Factors | publisher = U.S. Environmental Protection Agency | year = 1995 | volume = 1 | url = http://www.epa.gov/ttn/chief/ap42/index.html.] which is obtained by concentrating sphaleriteusing the froth flotationmethod. Secondary (recycled) zinc material, such as zinc oxide, is also processed with the zinc sulfide.Citation | title = Zinc Smelting Process | url = http://www.nyrstar.com/nyrstar/en/products/productionprocess/ | accessdate = 04-13-2008.] Approximately 30% of all zinc produced is from recycled sources. [Citation| title = Zinc Casting: A Systems Approach| publisher = Interzinc| year = 1992| url = http://www.interzinc.com/documents/Zinc_Casting_Systems_Approach.pdf.]
There are two methods of smelting zinc: the pyrometallurgical process and the electrolysis process. Both methods are still used. [Citation | title = Our Facilities - Monaca | url = http://www.zinccorp.com/ourfacilities.php | accessdate = 04-13-2008.] Both of these processes share the same first step: roasting.
Roasting is a process of oxidizing zinc sulfide concentrates at high temperatures into an impure zinc oxide, called "Zinc Calcine". The chemical reactions taking place during the process are:
Approximately 90% of zinc in concentrates are oxidized to zinc oxide, but at the roasting temperatures around 10% of the zinc reacts with the iron impurities of the zinc sulfide concentrates to form zinc ferrite. A byproduct of roasting is
sulfur dioxide, which is further processed into sulfuric acid, a commodity.
The process of roasting varies based on the type of roaster used. There are three types of roasters: multiple-hearth, suspension, and fluidized-bed.
In a multiple-hearth roaster, the concentrate drops through a series of 9 or more hearths stacked inside a brick-lined cylindrical column. As the feed concentrate drops through the furnace, it is first dried by the hot gases passing through the hearths and then oxidized to produce calcine. The reactions are slow and can be sustained only by the addition of fuel. Multiple hearth roasters are unpressurized and operate at about convert|690|°C|°F|abbr=on|lk=off. Operating time depends upon the composition of concentrate and the amount of the sulfur removal required. Multiple hearth roasters have the capability of producing a high-purity calcine.
In a suspension roaster, the concentrates are blown into a combustion chamber very similar to that of a pulverized coal furnace. The roaster consists of a refractory-lined cylindrical steel shell, with a large combustion space at the top and 2 to 4 hearths in the lower portion, similar to those of a multiple hearth furnace. Additional grinding, beyond that required for a multiple hearth furnace, is normally required to ensure that heat transfer to the material is sufficiently rapid for the desulfurization and oxidation reactions to occur in the furnace chamber. Suspension roasters are unpressurized and operate at about convert|980|°C|°F|abbr=on|lk=off.
In a fluidized-bed roaster, finely ground sulfide concentrates are suspended and oxidized in a feedstock bed supported on an air column. As in the suspension roaster, the reaction rates for desulfurization are more rapid than in the older multiple-hearth processes. Fluidized-bed roasters operate under a pressure slightly lower than atmospheric and at temperatures averaging convert|1000|°C|°F|abbr=on|lk=off. In the fluidized-bed process, no additional fuel is required after ignition has been achieved. The major advantages of this roaster are greater throughput capacities, greater sulfur removal capabilities, and lower maintenace.
The electrolysis process, also known as the hyrdrometallurgical process, Roast-Leach-Electrowin (RLE) process, or electrolytic process, is more widely used than the pyrometallurgical processes.
The electrolysis process consists of 4 steps: leaching, purification, electrolysis, and melting and casting.
The basic leaching chemical formula that drives this process is:
This is achieved in practice though a process called double leaching. The calcine is first leached in a neutral or slightly acidic solution (of sulfuric acid) in order to leach the zinc out of the zinc oxide. The remaining calcine is then leached in strong sulfuric acid to leach the rest of the zinc out of the zinc oxide and zinc ferrite. The result of this process is a solid and a liquid; the liquid contains the zinc and is often called leach product; the solid is called leach residue and contains precious metals (usually lead and silver) which are sold as a by-product. There is also iron in the leach product from the strong acid leach, which is removed in an intermediate step, in the form of
goethite, jarosite, and haematite. There is still cadmium, copper, arsenic, antimony, cobalt, germanium, nickel, and thalliumin the leach product. Therefore it needs to be purified.
The purification process utilizes the cementation process to further purify the zinc. It uses zinc dust and steam to remove
copper, cadmium, cobalt, and nickel, which would interfere with the electrolysis process. After purification, concentrations of these impurities are limited to less than 0.05 milligram per liter (4x10-7 pounds per gallon). Purification is usually conducted in large agitated tanks. The process takes place at temperatures ranging from 40 to 85 °C (104 to 185 °F), and pressures ranging from atmospheric to convert|240|kPa|atm|abbr=off|lk=on|sp=us. The by-products are sold for further refining.
The zinc sulfate solution must be very pure for electrowinning to be at all efficient. Impurities can change the decomposition voltage enough to where the electrolysis cell produces largely hydrogen gas rather than zinc metal.cite book |title=Engineering Metals and their Alloys |last=Samans |first=Carl H. |authorlink= |coauthors= |year=1949 |publisher=MacMillan |location=New York |isbn= |pages= ]
Zinc is extracted from the purified zinc sulfate solution by
electrowinning, which is a specialized form of electrolysis. The process works by passing an electric current through the solution in a series of cells. This causes the zinc to deposits on the cathodes ( aluminiumsheets) and oxygen to form at the anodes. Sulfuric acid is also formed in the process and reused in the leaching process. Every 24 to 48 hours, each cell is shut down, the zinc-coated cathodes are removed and rinsed, and the zinc is mechanically stripped from the aluminum plates.
Electrolytic zinc smelters contain as many as several hundred cells. A portion of the electrical energy is converted into heat, which increases the temperature of the electrolyte. Electrolytic cells operate at temperature ranges from 30 to 35°C (86 to 95°F) and at atmospheric pressure. A portion of the electrolyte is continuously circulated through the cooling towers both to cool and concentrate the electrolyte through evaporation of water. The cooled and concentrated electrolyte is then recycled to the cells. This process accounts for approximately 1/3 of all the energy usage when smelting zinc.
There are two common processes for electrowinning the metal: the "low current density" process, and the "Tainton high current density" process. The former uses a 10% sulfuric acid solution as the electolyte, with current density of 270–325 amperes per square meter. The latter uses 22–28% sulfuric acid solution as the electrolyte with a current density of about 1,000 amperes per square meter. The latter gives better purity and has higher production capacity per volume of electrolyte, but has the disadvantage of running hotter and being more corrosive to the vessel in which it is done. In either of the electrolytic processes, each metric ton of zinc production expends about convert|3900|kW·h| GJ|abbr=on|lk=on of electric power.
Melting and casting
The final step is to melt the cathodes in an
induction furnace. It is then either cast into pure zinc (99.995% pure) ingots or alloyed and cast into ingots.
There are also several pyrometallurgical processes that reduce zinc oxide using carbon, then distill the metallic zinc from the resulting mix in an atmosphere of carbon monoxide. The major downfall of any of the pyrometallurgical process is that it is only 98% pure; a standard composition is 1.3% lead, 0.2% cadmium, 0.03% iron, and 98.5% zinc. This may be pure enough for galvanization, but not enough for die casting alloys, which requires Special-High Grade zinc (99.995% pure). In order to reach this purity the zinc must be refined.
The four types of commercial pyrometallurgical processes are the "Belgian-type horizontal retort" process, the "New Jersey Zinc continuous vertical-retort" process, the "blast furnace" process and the "St. Joseph Minerals Corporation's" process.
t. Joseph Mineral Company process
This process was developed by the St. Joseph Mineral Company in 1930, and is the only Pyrometallurgical process still used in the US to smelt zinc. The advantage of this system is that it is able to smelt a wide variety of zinc-bearing materials, including electric arc furnace dust. The disadvantage of this process is that it is less efficient than the electrolysis process.
The process begins with a downdraft sintering operation. The sinter, which is a mixture of roaster calcine and EAF calcine, is loaded onto a gate type conveyor and then combustions gasses are pumped through the sinter. The carbon in the combustion gases react with some the impurities, such as lead, cadmium, and halides. These impurities are driven off into filtration bags. The sinter after this process, called product sinter, usually has a composition of 48% zinc, 8% iron, 5% aluminium, 4% silicon, 2.5% calcium, and smaller quantities of magnesium, lead, and other metals. The sinter product is then charged with coke into an electric retort furnace. A pair of graphite electrodes from the top and bottom furnace produce current flow through the mixture. The coke provides electrical resistance to the mixture in order to heat the mixture to convert|1400|°C|°F|abbr=on|lk=off and produce carbon monoxide. These conditions allow for the following chemical reaction to occur:
The zinc vapor and carbon dioxide pass to a vacuum condenser, where zinc is recovered by bubbling through a molten zinc bath. Over 95% of the zinc vapor leaving the retort is condensed to liquid zinc. The carbon dioxide is regenerated with carbon, and the carbon monoxide is recycled back to the retort furnace.
Blast furnace process
This process was developed by the Imperial Smelting Corporation at
Avonmouth, England, in order to increase production, increase efficiency, and decrease labor and maintenance costs. L. J. Derham proposed using a spray of molten lead droplets to rapidly chill and absorb the zinc vapor, despite the high concentration of carbon dioxide. The mixture is then cooled, where the zinc separates from the lead. The first plant using this design opened up in 1950. One of the advantages of this process is that it can co-produce lead bullion and copper dross. In 1990, it accounted for 12% of the world's zinc production.
The process starts by charging solid sinter and heated coke into the top of the blast furnace. Preheated air at 190-1050 °C is blown into the bottom of the of the furnace. Zinc vapor and sulfides leave through the top and enter the condenser. Slag and lead collect at the bottom of the furnace and are tapped off regularly. The zinc is scrubbed from the vapor in the condenser via liquid lead. The liquid zinc is separated from the lead in the cooling circuit. Approximately convert|5000|MT|ST|abbr=off|lk=on|sp=us of lead are required each year for this process, however this process recovers 25% more lead from the starting ores than other processes.
New Jersey Zinc continuous vertical retort
The New Jersey Zinc process is no longer used to produce primary zinc in the U.S., Europe and Japan, however it still is used to treat secondary operations. This processes peaked in 1960, when 5% of the world production was done by this process. A modified version of this process is still used at Huludao, China, which produced 65,000 tons/year.
This process begins by roasting concentrates that are mixed with coal and
briquetted in two stages. The briquettes are then heated in a coker at convert|700|°C|°F|abbr=on|lk=off and then charged into the retort. There are three reasons to briquette the calcine: to ensure free downward movement of the charge; to permit heat transfer across a practical size cross-section; to allow adequate porosity for the passage of reduced zinc vapor to the top of the retort. The reduced zinc vapor that is collected at the top of the retort is then condensed to a liquid.
Overpelt improved upon this design by using only one large condensation chamber, instead of many small ones, as it was originally designed. This allowed for the carbon monoxide to be recirculated into the furnaces for heating the retorts.
This process was licensed to the Imperial Smelting Company (ISC), in Avonmouth, England, which had a large vertical retort (VR) plant in production for many years. It was used until the mid 1970's when it was superseded by the company's Imperial Smelting Furnace (ISF) plant. The VR plant was demolished in 1975.
Belgian-type horizontal retort process
This process was the main process used in Britain from the mid-19th century until 1951.Citation | last = Porter | first = Frank | title = Zinc Handbook: Properties, Processing, and Use in Design | publisher = CRC Press | pages = 16-17 | year = 1991 | url = http://books.google.com/books?id=laACw9i0D_wC | isbn = 0824783409.] The process was very inefficient as it was designed as a small scale batch operation. Each retort only produced convert|40|kg|lb|abbr=off|lk=off|sp=us so companies would put them together in banks and used one large gas burner to heat all of them.Citation | title = Zinc processing | url = http://concise.britannica.com/oscar/print?articleId=110671&fullArticle=true&tocId=82116 | accessdate = 04-18-2008.] The Belgian process requires redistillation to remove impurities of lead, cadmium, iron, copper, and arsenic.
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