I. Introduction Manganese is widely distributed in nature in various forms of compounds. Since 1770 was found from an aqueous manganese ore, people, manganese alloys, manganese and compounds belong to various methods of production of gold, widely used in industry and agriculture and military. Manganese was proposed from the manganese-containing raw materials by hydrometallurgical method. It was studied at the end of the 19th century and has a history of nearly one hundred years. During this period, with the advancement of materials technology, the production equipment is constantly updated. The traditional process for treating manganese ore has been greatly improved, but with the mining of manganese ore, the rich ore resources are becoming increasingly poor. How to treat manganese-poor ore by chemical metallurgy and comprehensive utilization of manganese ore data is very attractive. Human research methods, especially in terms of China's actual situation, rich manganese ore accounts for a small portion of total reserves, about 9.6%, most of which are lean manganese ore, and the research topic of comprehensive utilization of manganese-poor ore resources is becoming more and more important. It is. There are many methods for chemical extraction of manganese-depleted ore by chemical reagents, mainly by selecting appropriate chemical reagents to convert manganese in the ore into a soluble form into the solution, separating it from the gangue minerals, and then purifying the solution to remove manganese. The impurities dissolved together are Fe, Al, Si, P, Cu, Co, Ni, etc. Finally, the desired manganese products, such as electrolytic manganese, manganese oxide and various manganese salts, are prepared by electrodeposition, precipitation or crystallization. The chemical method for treating the manganese-poor ore can be classified according to the soluble manganese salt formed during the leaching process, such as the sulfate method, the nitrate method, the chloride method, the amino tetra-acid method, and the like. Each of these methods can be further differentiated according to the test used. Second, the method of processing low-grade manganese ore (a) Sulfate method In the sulphate method, manganese carbonate or reduced manganese oxide ore can be directly leached with sulfuric acid. This method is the most traditional hydrometallurgical method for treating manganese ore, for intermediate manganese ore with high price and low manganese. For example, manganite ore and manganite may be combined with sulfuric acid-sulfuric acid, and manganese dioxide ore may be directly leached with sulfurous acid. The process of leaching soft manganese ore with SO 2 is characterized by using MnO 2 slurry as an absorbent and absorbing water-soluble. SO 2 gas is directly converted into manganese sulfate and manganese disulfate. The manganese disulfate is unstable, decomposes in thermal decomposition, and dissociates into MnSO 2 and SO 2 . The US mining bureau ESLeaver has reported that sulfur dioxide passes at a relatively low temperature. Two rotating cylinders flow countercurrently through low grade pulp to produce manganese sulfate solution; R. Blumberg and TDMorgan performed the same test at higher temperatures, producing a very small amount of iron in the sulfate solution and no sulfurous acid Manganese and dithionite; a manganese mine company, a subsidiary of M.Ahanna, put the 1,000-tonne plant into production in 1943-1944, and leached manganese ore with SO2 in the reaction tower. Due to complex reactions and equipment problems, it is impossible to produce a sufficiently pure product, which is closed when it reaches 50% of its design capacity. Chemical engineering company invented a chemical treatment method to leaching manganese ore with sulfur dioxide in the presence of oxygen and high pressure. The pulp is used to increase the leaching rate and oxidize the dithionous acid, recover the manganese sulfate from the solution, and sinter it into oxides and sulfur dioxide, and the produced dioxide bowl can be recycled in the system; the sulfur dioxide is used to leach the seabed manganese nodules abroad. There are quite a few reports in the literature that the treatment of manganese nodules with sulfur dioxide can recover a variety of valuable metals such as nickel , cobalt and copper in addition to manganese. The use of sulfur dioxide to leach soft manganese ore has also been studied in China. The Changsha Chemical Plant uses manganese ore to absorb sulfur dioxide in the tail gas from the sulfuric acid production process, and uses the wet method to make the finished manganese sulfate. The production process is to first absorb the SO 2 with a four-layer lead-line foam tower. Exhaust gas, then the slurry is purified, crystallization, mother liquor treatment, the powder from the centrifugal separator will be crystallized into the drying furnace and dried at 400-500 ° C. The product meets the requirements of the first-class product, and the practice proves that the pyrolusite content is 45 ~ 60%, materiality - 100 mesh, sulfur dioxide content has little effect on SO 2 absorption, the concentration of SO 2 in the exhaust gas is 0.4-0.5%, the solid-liquid ratio of the slurry is 1:4, the temperature is 70-80 ° C, manganese the leaching rate of 90%, 97% sulfur dioxide leaching, exhaust gas containing SO 2 at 0.03% or less, in full compliance with environmental requirements; of SO2 flue Nanning aluminum smelting plant with pyrolusite absorption plant emissions copper concentrate roaster The use of pyrolusite to absorb flue gas containing sulfur dioxide emitted by non-ferrous smelters and some chemical plants has the advantages of simple and comprehensive use of the process and environmental protection. However, the main problem of the process is that the raw material consumption is large, and since the concentration of sulfur dioxide in the exhaust gas is generally low, the leaching time is long and the production efficiency is low. As early as 1940, the United States used sulfur dioxide and calcium chloride to leach pyrolusite to form manganese chloride. Later, based on this test, lime was added to develop a new process of dithiosulfate. The basic principle is to mine manganese ore. The powder is mixed into a slurry, and sulfur dioxide is introduced into the leaching tank to form manganese sulfate and manganese disulfate. The calcium sulfate is removed by filtration together with the residue, and lime milk is added to the filtrate to obtain a precipitate of manganese hydroxide product, and the filtered filtrate contains two consecutive products. Calcium sulfate, can be recycled. In 1949, the United States carried out an expansion test of the production process. The US Bureau of Mines conducted a semi-industrial test of the calcium disulfate method from 1951 to 1953 on the manganese-depleted ore containing 10% manganese in the Attilari mine. The processing capacity is 535 kg of manganese hydroxide per day, the final concentrate contains 55-60% manganese, and the manganese recovery rate is 89%; the former Soviet Union Mihanobu Dressing Design Institute in 1959 to Chatura and Nikobol The manganese ore sludge treated by the dithionous sulfuric acid method showed that manganese hydroxide concentrate containing 52-61% manganese was obtained, and the recovery rate of manganese was 83-84%. A lot of research work has been done on the dihydrosulfuric acid method in China. From 1964 to 1965, a series of tests were carried out on manganese oxide or soft manganese, and a semi-industrial test with a dose of 500 kg was carried out. Laboratory and semi-industrial test results were obtained. Basically, when the ore contains about 23% manganese, 54-60% manganese concentrate can be obtained, and the recovery rate of manganese is 84-85.3%. Semi-industrial test of de-tin-manganese nodules by calcium disulfate method When processing manganese manganese nodules containing 20% ​​manganese, manganese concentrates containing 60% manganese can be obtained; Guizhou manganese oxide ore contains 8.55-26% manganese, and after treatment with dihydrosulfuric acid, the manganese content of the concentrate can reach 51.87～54.14. %, the recovery rate is 78.83 ~ 78.70%. The product obtained by the calcium disulfate method has high purity and less impurities, and can be used as a high-quality raw material for smelting metal manganese and medium and low broken manganese iron, and the production cost is lower than other chemical treatment methods, and is a promising treatment method. (b) Carbamate method The carbamate method works well for manganese-depleted ore. It was reported that KMLeute transferred a patent to Electro Manganese Corp in 1943, and RDAan of the US Bureau of Mines obtained an improved patent in 1956, and the US Bureau of Mining also conducted The intermediate expansion experiment was later developed into an industrial scale by Manganese Chemicals Corp. The manganese oxide ore was initially broken to -3/4 inch, and the manganese dioxide was reduced in a baking furnace with carbon monoxide containing saturated water vapor at a temperature of 450 °C. For manganese monoxide, the iron in the ore is converted into Fe 3 O 4 , the reduced ore is ground to -30 mesh, and leached with a solution containing 18 mol/L of ammonia and 3 mol/L of carbon dioxide, and Fe 3 O 4 in the ore is insoluble. Manganese reacts according to the following formula: The leaching temperature should be controlled so that the formed complex can not be decomposed into a suitable, purified supernatant, directly heated by Fan steam to remove ammonia, so that the manganese complex decomposes and precipitates manganese carbonate and ammonia gas, and the ammonia gas is absorbed by water. The addition of carbon dioxide can be recycled, and manganese carbonate can be used to manufacture various chemical products or to be sintered into metallurgical manganese raw materials. (3) Nitrate method The US Bureau of Mines has extensively studied the use of nitrogen dioxide to leach manganese dioxide powder slurry and finally recover it in manganese form, and heat-decompose it into manganese dioxide and nitrogen dioxide. The nitrogen dioxide gas can be used, and the obtained manganese dioxide is almost reached. Chemically pure; ESNossen invented a similar process in which manganese in the ore is first reduced to manganese oxide and then leached with nitric acid; Bradley-Fitch CO's Wilson Bradley treats manganese iron ore with ammonium sulfate leachate at 90 ° C to obtain sulfuric acid Manganese recovers the released ammonia gas; ATSweet leaches manganese carbonate ore with ammonium sulfate, and releases ammonia and carbon dioxide released during leaching to form ammonium carbonate for treating the leaching solution containing manganese sulfate. Manganese is obtained in the form of manganese carbonate. Ammonium sulphate can be recycled; WSStringhan and GNSummers use manganese salts to calcine manganese ore at 450 ° C ~ 550 ° C, ammonia and carbon dioxide combined to precipitate manganese sulfate and manganese chloride, or separate manganese chloride precipitation , to make it into manganese carbonate precipitation, ammonium salt can be recycled. (4) Chloride method It is also used in the treatment of manganese-poor ore by the chloride salt method. The manganese nitrate ore is reduced by hydrochloric acid or the manganese oxide ore after reduction and calcination is one of the chloride methods. The other is to directly chlorinate the manganese ore with chlorine gas. One method is similar to the method of leaching with sulfuric acid or nitric acid. The latter method is to chlorinate the lean manganese or manganese-containing metallurgical slag with chlorine gas in the presence of carbon; some people are at 25-175 ° C (preferably 75-90 ° C). When the pH value is less than 1, the seabed manganese nodules are leached with concentrated hydrochloric acid, and the marine manganese nodules are processed by the hydrochloric acid leaching method. At room temperature, elements such as Ni, Co, Cu, Fe, Mn are dissolved, and the extraction method is used to remove the manganese nodules. After ferric chloride, manganese dioxide and hydrochloric acid are obtained, and the iron-removed solution is treated with metal manganese to obtain a mixed precipitate, and the mixed precipitate can be dissolved in ammonium carbonate solution to extract copper and nickel, and then The same and nickel are extracted and extracted from the refined product after the fractional extraction, and then the cobalt is extracted from the refined product after the fractional extraction, and the remaining aqueous solution after the precipitation is subjected to coagulation and recovery of manganese dioxide, and aluminum is used as The original agent is smelted at a temperature of 1273K to obtain manganese metal. The disadvantage of this method is that the whole process needs to use corrosion-resistant materials, but since this method can recover and use hydrochloric acid twice, it is more economical than the sulfuric acid method. Former Soviet scholars also used leaching of manganese with hydrochloric acid during the manganese carbonate ore processing. I. P. Whitehouse and MEGraham transferred a patent to Republic Steel Corp, a mixture of water and hydrogen chloride gas to remove manganese from manganese chloride ore, manganese leached in the form of chloride, and relatively separated iron; WEMorshall transferred a patent to Armco Steel Corp, a mixture of water vapor and hydrogen chloride gas, removes manganese from manganese chloride ore, and manganese is leached in the form of chloride to relatively separate iron; WEMorshall transferred a patent to Armco Steel Corp at 980 ° C At high temperatures, hydrogen chloride gas is used to oxidize manganese and iron, and there are several ways to separate these metal compounds. RTMcmillon, TLTumer and JE Conley have extensively studied solid oxidants such as CaCl 2 . The solid CaCl 2 is mixed with the ore at 1000 ° C, manganese and iron are converted into oxides, and separated by hydrometallurgy; some people mix MnO or MnCO 3 with CaCl 2 at a temperature of 900 ° C to 1200 ° C. The MgCl2-NaCl-KCl molten salt bath is kept at 500 °C, and 99.9% of manganese can be recovered from the molten salt by electrolysis; the treatment of the manganese-poor ore and seabed manganese nodules by the chloride method is reported in many materials. (5) Direct sea leaching method of soft manganese ore At present, several domestic manufacturers use pyrite and sulfuric acid to directly leach soft manganese ore to prepare manganese sulfate or electrolytic manganese dioxide. Guiyang Electrolytic Manganese Plant uses soft manganese ore and pyrite as raw materials, and atmospheric pressure sulfuric acid leaching to produce manganese sulfate monohydrate. First, the pyrolusite and pyrite are respectively ground into 100-200 mesh ore powder, and the water and the acid-breaking acid are first added to the compounding barrel, and the temperature is raised to 70-90 °C by the heating of the gas. Add the required MnO 2, FeS ore leaching 3 to 4 hours, after passing the liquid-solid separation analysis of iron ions, then MnCO 3 or lime neutralization, cooling was removed by filtration and then magnesium, calcium, manganese sulfate obtained qualified The solution is directly evaporated to obtain a qualified manganese sulfate monohydrate product, and the manganese ore is treated by this method. (6) ferrous sulfate-sulfuric acid reduction leaching Leaching of lean manganese ore by pickling waste water from rolling mills is a research method. The production scale of steel mills is huge, and the amount of pickling liquid produced is very large. Richard.D.Hoak and James Coull use acid washing waste liquid to treat grades. 14.7% to 26.9% of manganese oxide ore, manganese recovery rate of up to 98%; treatment of pyrolusite with ferrous iron, oxidation of ferrous ions, pH value of 5 ~ 5.5, precipitation Fe (OH) 3, can get a Manganese sulfate in water; SCDas, DKSahoo and PKPao in India leached pyrolusite with ferrous sulfate. When the temperature is 90 °C, the leaching time is one hour, and the manganese leaching rate is above 90%. When a certain amount of sulfuric acid is added, Prevent the formation of colloids; treatment of manganese dioxide ore with pickling waste liquid is a very promising method. (7) Bacterial metallurgy The use of bacteria to extract manganese from manganese ore has been reported at home and abroad. In the 1950s, Perhims of the US Bureau of Mines used Bacillus to extract manganese from four ore samples of low-grade manganese ore in Nevada and Minnesota. The average leaching rate was 97.5%. In 1962, an expanded test report was published. The scale of the experiment was 203-360 kg of mineral samples. Japanese scholars began to leaching manganese with Thiobacillus oxidans in 1962. The leached ore contained some manganese carbonate. Sulfur powder is added to the bacterial leachate as the bacterial energy source, so that the manganese in the manganese ore is dissolved in soluble manganese sulfate, and the manganese leaching rate is 97%. In 1979, Mao Yufan et al. used the ferric sulphate to treat the ferrous sulfate. Oxidation into high-sulfur sulfate for the leaching of sulphate and manganite ore, for the use of manganese-poor ore in the mine and the comprehensive utilization of low-sulfur dioxide, eliminating pollution, etc. has been a new attempt; in the past decade, the United States, the former Soviet Union, India and other scholars Heterotrophic microorganisms are immersed in manganese and reduced to divalent manganese which is soluble in water. Some heterotrophic bacteria can produce organic acids to convert manganese oxide into ionic state or The organic complex enters the solution to achieve the purpose of leaching. Some scholars believe that the biological extraction method of manganese nodules is slower than the non-biological hydrometallurgical extraction method, but the biological method can be carried out semi-continuously every day, requiring less Energy and reagents are low in cost and therefore have the potential for industrial production, but have not been reported so far. (8) Sulfation roasting method In addition to the liquid phase leaching, the treated ore may be converted into manganese sulfate by a sulphation roasting method, and then leached with water. It has been reported that sulfur dioxide gas and air are mixed to roast manganese-containing ore, and the formed manganese sulfate is leached with water. 75.62% of manganese can be extracted by a fixed bed, and only 65.70% by a fluidized bed. The optimum condition is that the fixed bed size is less than 60. Head, 700 ° C, sulfur dioxide is 60 ml per minute, air is 340 ml per minute, calcination time is 120 minutes; boiling bed particle size is less than 10 mesh, 700 ° C, roasting time is 40 minutes, sulfur dioxide flow rate is 15 liters per hour, air The flow rate is 85 liters per minute. The use of sulphation roasting to treat the manganese-poor ore can change the manganese in the ore into soluble manganese sulphate, and the iron exists in the form of insoluble iron. This can directly leaching the roasting ore, avoiding the iron removal process and directly producing sulfuric acid. manganese or manganese products; people use containing 200ppmSO 2, 3% O 2, 10% H 2 O, the remaining exhaust gas treating manganese nodules is N 2, a relatively low elution of iron, other metals such as Mn, Cu, Ni, The dissolution rate of Co is 20 to 50%. It has been reported that at 400 ° C, the dried manganese nodules are treated with a mixture of SO 2 -O 2 , and X-ray analysis shows that the oxides of manganese, copper, nickel and cobalt are all converted into the corresponding sulfates by sulfation. The main component of the ore is not sulfated, but is converted from a-FeOH (goethite) to a-Fe 2 O 3 (hematite), so iron can be separated from other metals and sulfated. When roasting, pyrite or other sulfur-containing agent can be directly added. (9) Other chemical methods HAHancock, DJFray uses carbon or coal to dissolve manganese dioxide in an acidic solution. In the presence of carbon or coal, the manganese dioxide in the ore is reduced to divalent manganese and dissolved in an acidic solution. This reaction requires very high temperature. Strong, preferably close to the boiling temperature of the solution, the recovery of manganese can reach more than 90%. In the presence of sugar or starch, acid-impregnated manganese ore or manganese nodules can recover manganese, 10 g of manganese nodules containing 21.4% of manganese, and the particle size is less than 100 mesh. In the presence of syrup, 3M concentration of sulfuric acid is leached at 90-100 ° C. Minutes, 0.2 grams of syrup per gram of tuberculosis, the recovery of Mn, Ni, Co, Cu can reach 100% in a few hands, and the recovery rate of iron is also 98%. Without syrup, Mn, Ni, Co, Cu and The recovery rates of Fe were 51%, 79%, 36%, 93% and 72%, respectively. J. C. Agarwal, HEBarner et al. The reaction of leaching manganese nodules with an aqueous solution of seawater containing monovalent copper ions, ammonia, ammonium carbonate: MnO 2 +2Cu(NH 3 ) 2 + +2NH 3 +(NH 4 )2CO 3 →MnCO 3 ↓+2Cu(NH 3 ) 4 2+ +2OH -The formation of Cu(NH 4 ) 4 2+ has the following reaction with the introduced CO 2Cu(NH 3 ) 4 2+ +CO+2OH - →2Cu(NH 3 ) 2 + +2NH 3 +(NH 4 ) 2 CO 3 The total reaction is: MnO 2 +CO→MnCO 3 , and the cuprous ion is a middle in this reaction. The product, by this method, can reduce 98% of the manganese in the ore to a divalent state. Some people use the underground leaching method to directly leaching the underground manganese dioxide ore. The underground leaching method can save the mining operation process, which is very beneficial to save costs. In the process of industrial production of hydroquinone, manganese sulfate can be recovered as a by-product. This method is one of the main sources of manganese sulfate in foreign countries. In the process of producing hydroquinone, pyrolusite is used as an oxidant to oxidize aniline. Hydroquinone, by-product waste liquid contains manganese sulfate, ammonium sulfate and free acid. The free acid can be neutralized with lime, and the solution is filtered to remove insoluble materials such as unreacted manganese dioxide and calcium sulfate, and the solution is evaporated to saturation and crystallized. Dry manganese sulfate product. Third, the conclusion In summary, there are many methods for treating manganese-poor ore. What method is used depends on the economic benefits, the type and nature of the ore that can be treated, the origin of the ore, the availability and price of various chemical reagents, and The type of demand is selected; China's steel production is huge, and the rolling mill discharges a large amount of pickling waste liquid, making full use of this part of waste acid to treat manganese oxide ore, which can eliminate the pollution of waste acid to the environment, is conducive to environmental protection, and can Comprehensive utilization of low-grade manganese ore resources, for similar situations should be organized to intensify research, in order to be able to produce low-quality and high-quality manganese metallurgical chemical products. 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