Rare scattered metal elements
2023-04-16 01:08:47
First, the characteristics and main uses
Tantalum is the rarest disperse metal with the most “dispersing†features, silvery white, density 5.904g/m3, melting point 29.78°C. It melts in the hand and is a liquid metal with a melting point below the human body temperature (镓, 铯, One of mercury). But its boiling point is very high, as high as 2403 °C.
The range of the liquid in the crucible is large, but the liquid range in the three low-melting, high-boiling liquid metals is the largest, reaching 2373°C. Therefore, the crucible is placed in a quartz thermometer and can be used to measure temperatures of 1500°C. People often use this kind of thermometer to measure the temperature of reactors and reactors.
The volume increases by 3.2% from liquid to solid and changes from silver to blue-gray. The first ionization energy of helium is only 5.999 electron volts, so the freezing point is very low. Due to the complex structure of stable solids, pure liquid helium has a significant tendency to supercool, remains liquid for a long time under the solid phase, and does not crystallize in ice water for several days.
At low temperatures, helium has good superconductivity, and the resistance is nearly zero at temperatures close to -373°C, and therefore has a place in the field of superconducting materials.
Tantalum is an electronic material with excellent performance. It is praised as the backbone of the electronics industry and is the basic resource of high technology.é•“ is mainly used for manufacturing semiconductor materials, optical glass, vacuum tubes, light emitting diodes, and gallium arsenide laser diodes.
The enamel is soft, brittle, malleable, and stable in the air. The density of liquids is higher than that of solids, the volume expansion when solidified, and the expansion rate is 3.1%. Due to its "cold shrinkage" properties, crucibles have better casting properties and are used to make lead alloys and make fonts. Clear.
In the nuclear industry, helium is used as a heat transfer medium to transfer heat from the reactor. Helium also has the ability to absorb neutrons, so in an atomic reactor, helium can play a role in controlling the number of neutrons and the reaction rate. Radioactive cesium can be used to diagnose cancer.
镓 Heating can dissolve in strong acids such as nitric acid and aqua regia, as well as in strong alkaline solutions. Therefore, helium has two properties. Reacts violently with boiling water but reacts only slightly with water at room temperature. The vapor pressure of the crucible is very low, only 10-3 Pa at 1000°C, so it can be used as a sealing liquid in vacuum equipment.
The chemical properties of lanthanum are inactive, chemical properties similar to those of aluminum, zinc, and bismuth, and valences of 2 and 3. Almost no reaction with oxygen and water at room temperature. It can work with most metals at high temperatures. Adding aluminum can produce easily heat-treated alloys. Tantalum alloy arc lamps have pure red light and prevent tin evaporation from adhering to the glass tube wall, preventing cracking during cooling. The alloys of niobium and gold are used in decorative and dental implants and can also be used as catalysts for organic synthesis. Niobium can increase the hardness of some alloys, and can improve the corrosion resistance of magnesium alloys. Niobium and many metals, such as niobium, lead, tin, cadmium, indium, bismuth, etc., generate fusible alloys with melting points below 60°C. For example, a 25% indium-gallium-indium alloy (melting point of 16°C) and an 8% tin-bearing tin alloy (melting point of 20°C) can be used in circuit fuses and various safety devices. When the temperature is high, they will Automatic melting disconnected, play a role in safety insurance.
It can enhance the refractive index of glass and can be used to make special optical glass. The crucible has a strong light-reflecting ability, and at the same time, it adheres well to the glass and withstands high temperatures. It can be squeezed between two heated glasses to form a good reflector. The mirror can reflect more than 70% of the light.
In a high-temperature environment, niobium reacts with sulfur, selenium, tellurium, phosphorus, arsenic, antimony, etc. The resulting cerium-based compounds, GaAs, GaP, and GaSb, are all high-quality semiconductor materials in the field of optoelectronics. The application of microwave communication is very extensive. It can be used to manufacture rectifiers, transistors, optoelectronic devices, injection lasers, microwave diodes, etc. It is considered to be the most promising semiconductor material and has become the new favorite of the electronics industry. The solar cell made from the compound semiconductor material of germanium can convert solar energy directly into electrical energy with an efficiency of up to 18%, and its ability to resist radiation is twice as strong as that of silicon cell, so it can be used as a satellite power source. People use gallium arsenide as a component to make a laser, which is a new type of laser with small size and high efficiency. Gallium phosphide is a good material for making semiconductor light emitting devices. The phosphide diodes can emit red and green light. The red and green light we see on the computer is released by it. For this reason, people will be hailed as "new foods for semiconductor materials."
Thorium can also be used to make cathode vapor lamps. The addition of cesium iodide to high-pressure mercury lamps can increase the radiation intensity of mercury lamps.
Antimony compounds can be used in analytical chemistry, organic synthesis, and catalysts in medicine.
Erbium compounds are also used in optical fiber communication systems and can be used to make large scale integrated circuits. As a heat carrier in the nuclear energy industry, they even have a place in the field of superconducting materials.
Second, resource reserves and their distribution
By the end of 2008, 166 mines have been identified in China's antimony mines and are distributed in 25 provinces (cities, districts) across the country. The reserves of resources are 136,600 tons, of which 0.71 million tons are basic reserves. Guangxi has the highest resources, reaching 29,000 tons, accounting for 21.2% of the country. The top five are Guangxi, Guizhou, Henan, Shanxi, and Yunnan, and the identified total reserves accounted for 88.2% of the country's total.
The world's resource reserves are about 180,000 tons. The reserves of foreign oysters are about 4 to 50,000 tons, while those of domestic oysters are about 1-340,000 tons. China's metal tantalum resources account for about 75% of the world's total.
III. The main types of industrial deposits and their occurrences
(I) Major industrial types
In nature, earthworms often symbiotically associate with trace elements and aluminum, zinc, or bismuth minerals. The crustal abundance of earthworms is 15×10-6, which is 1-2 orders of magnitude higher than that of other disperse elements. The content of earthworms in meteorites is high, and bauxite and sphalerite also contain a small amount of earthworms.
At present, China has not yet discovered an independent antimony deposit. In addition, in the currently known antimony-rich ore deposits, the general enrichment factor is about 4 to 5, and the enrichment factor in sphalerite and vermiculite in only a few ore deposits can be as high as about 330, and the ore formation cannot be controlled by other disperse elements. compared to.
The main industrial types of antimony deposits are: bauxite-bearing ores; bismuth-bearing copper, zinc ores, and other polymetallic ore sulfides; Hanyu coal mines.
(b) Occurrence status
The plutonium is always present in the relevant minerals in the same-type and in-phase form. It does not form an independent plutonium deposit with its own mining value. It can only be recycled in the selection and smelting process when the main metal deposit is mined.
In the provinces of Henan, Jilin, Shandong, and Guangxi, bismuth is mainly present in bauxite; bismuth in Heilongjiang and Yunnan provinces are mainly found in coal mines or tin mines; bismuth in Hunan and other provinces is mainly found in sphalerite.
Fourth, the extraction method
1. Extract cesium in the form of by-products. At present, industrial cesium is mainly extracted as a by-product from the sodium aluminate circulating solution used for the production of alumina from bauxite and the crude zinc distillation residue from the zinc blender wet zinc smelting process, and can also be extracted from coal coke dust. Recycling.
2. Extract the quinones by extraction. At a certain degree of acidity, the agent P538 can be used to obtain Ga, In, Ti from Ga, In and accompanying elements such as Zn, Co, Cd, Ni, and alkali and alkaline earth metal sulfate systems. A certain amount of back extractant can be used. Ga, In, and Ti are respectively extracted, and effective separation of Ga, In, and Ti can be achieved.
V. Analysis of Supply and Demand in Domestic and Foreign Markets
China is a big producer of plutonium, but its output is not stable. In 2000, the output of native oysters was 7.6 tons, in 2005 it was 17.78 tons, in 2007 it was 33.22 tons, and in 2008 it could reach 40 tons.
Based on demand projections, global production in 2008 totaled 85 tons. Among them, the output of Chinese metal tantalum (4N) accounts for about half of the global production.
In recent years, the rapid development of China's electronic information industry, the steady growth of domestic consumption. According to customs statistics, China exported 26 tons of unwrought metal oysters in 2008. Based on this measure, the apparent consumption of metal gallium in China in 2008 was about 14 tons.
According to China Electronic Materials Network's market research on GaAS, due to the maturity of GaAs crystal growth technology and device fabrication technology, it is expected that the demand for GaAs-based compound semiconductor materials and devices will average 10% over the next 10 years. % to 15% growth rate.
Since the global peak consumption of 200 tons in 2000, due to fluctuations in market prices and other factors, global consumption of germanium has fallen sharply, dropping to about 100 tons in 2006. The impact of the financial crisis on the real economy in the second half of 2008 exacerbated this downward trend. Last year, the consumption of cesium fell further to 85 tons. The consumption of cesium in our country accounts for about 16.5% of the world.
Under the influence of the global financial crisis, the price of China's metal tantalum all the way down in 2008. The price at the beginning of the year was 5,800-6,300 yuan/kg. After the low of 3,500 yuan/kg in mid-November, it slightly recovered at the end of the year. At the beginning of 2009, it further decreased to 3,400 to 3,700 yuan/kg.
6. Problems in the development and utilization of antimony ore resources in China
1. Difficulty in extracting earthworms. As a rare metal, there is almost no single, industrially exploited niobium deposit in nature, which can only be recovered from the by-products from the smelting process of other metals such as Al and Zn. However, since the content of antimony in other metal deposits is extremely low, it can only reach several hundred g/t after certain enrichment, so the extraction of antimony is very difficult.
2. Serious waste of resources. Most of the domestic enterprises are abandoning the use of waste materials, resulting in a lot of waste of resources.
3. The product has low added value. At present, there is no mastery of deep processing of metal ytterbium. The products are mainly exported in the form of primary raw materials. The added value is not high. A few companies such as Shandong Aluminum Company and Great Wall Aluminum Company have tried to purify 3~4N products to 6~7N products, and further processed them into GaAs and GaP products. However, the market is still a big obstacle and no significant progress has been made.
Seventh, the current policy of China's product management
1. The "2007 Catalogue of Goods Subject to Export License Management" and "2008 Catalogue of Goods Subject to Export License Administration" include unwrought ramie and wrought oysters in the list of goods subject to export license management.
2. Catalogue of Prohibited Commodities for Processing Trade in 2008 (Ministry of Commerce and General Administration of Customs Announcement No. 22 of 2008) stipulates that unrolled ramming, scrap, scrap, powdered, wrought and its products Export in the name of processing trade.
VIII. Policy recommendations
1. Strengthen the research on the extraction process of thorium and improve the comprehensive recovery and utilization level of thorium.
2. To increase export tariffs on unwrought ramie, scraps, scraps, thorium powders, wrought ytterbium and their products, and control excessive exports.
3. The country will implement a strategic reserve of base metals.
Tantalum is the rarest disperse metal with the most “dispersing†features, silvery white, density 5.904g/m3, melting point 29.78°C. It melts in the hand and is a liquid metal with a melting point below the human body temperature (镓, 铯, One of mercury). But its boiling point is very high, as high as 2403 °C.
The range of the liquid in the crucible is large, but the liquid range in the three low-melting, high-boiling liquid metals is the largest, reaching 2373°C. Therefore, the crucible is placed in a quartz thermometer and can be used to measure temperatures of 1500°C. People often use this kind of thermometer to measure the temperature of reactors and reactors.
The volume increases by 3.2% from liquid to solid and changes from silver to blue-gray. The first ionization energy of helium is only 5.999 electron volts, so the freezing point is very low. Due to the complex structure of stable solids, pure liquid helium has a significant tendency to supercool, remains liquid for a long time under the solid phase, and does not crystallize in ice water for several days.
At low temperatures, helium has good superconductivity, and the resistance is nearly zero at temperatures close to -373°C, and therefore has a place in the field of superconducting materials.
Tantalum is an electronic material with excellent performance. It is praised as the backbone of the electronics industry and is the basic resource of high technology.é•“ is mainly used for manufacturing semiconductor materials, optical glass, vacuum tubes, light emitting diodes, and gallium arsenide laser diodes.
The enamel is soft, brittle, malleable, and stable in the air. The density of liquids is higher than that of solids, the volume expansion when solidified, and the expansion rate is 3.1%. Due to its "cold shrinkage" properties, crucibles have better casting properties and are used to make lead alloys and make fonts. Clear.
In the nuclear industry, helium is used as a heat transfer medium to transfer heat from the reactor. Helium also has the ability to absorb neutrons, so in an atomic reactor, helium can play a role in controlling the number of neutrons and the reaction rate. Radioactive cesium can be used to diagnose cancer.
镓 Heating can dissolve in strong acids such as nitric acid and aqua regia, as well as in strong alkaline solutions. Therefore, helium has two properties. Reacts violently with boiling water but reacts only slightly with water at room temperature. The vapor pressure of the crucible is very low, only 10-3 Pa at 1000°C, so it can be used as a sealing liquid in vacuum equipment.
The chemical properties of lanthanum are inactive, chemical properties similar to those of aluminum, zinc, and bismuth, and valences of 2 and 3. Almost no reaction with oxygen and water at room temperature. It can work with most metals at high temperatures. Adding aluminum can produce easily heat-treated alloys. Tantalum alloy arc lamps have pure red light and prevent tin evaporation from adhering to the glass tube wall, preventing cracking during cooling. The alloys of niobium and gold are used in decorative and dental implants and can also be used as catalysts for organic synthesis. Niobium can increase the hardness of some alloys, and can improve the corrosion resistance of magnesium alloys. Niobium and many metals, such as niobium, lead, tin, cadmium, indium, bismuth, etc., generate fusible alloys with melting points below 60°C. For example, a 25% indium-gallium-indium alloy (melting point of 16°C) and an 8% tin-bearing tin alloy (melting point of 20°C) can be used in circuit fuses and various safety devices. When the temperature is high, they will Automatic melting disconnected, play a role in safety insurance.
It can enhance the refractive index of glass and can be used to make special optical glass. The crucible has a strong light-reflecting ability, and at the same time, it adheres well to the glass and withstands high temperatures. It can be squeezed between two heated glasses to form a good reflector. The mirror can reflect more than 70% of the light.
In a high-temperature environment, niobium reacts with sulfur, selenium, tellurium, phosphorus, arsenic, antimony, etc. The resulting cerium-based compounds, GaAs, GaP, and GaSb, are all high-quality semiconductor materials in the field of optoelectronics. The application of microwave communication is very extensive. It can be used to manufacture rectifiers, transistors, optoelectronic devices, injection lasers, microwave diodes, etc. It is considered to be the most promising semiconductor material and has become the new favorite of the electronics industry. The solar cell made from the compound semiconductor material of germanium can convert solar energy directly into electrical energy with an efficiency of up to 18%, and its ability to resist radiation is twice as strong as that of silicon cell, so it can be used as a satellite power source. People use gallium arsenide as a component to make a laser, which is a new type of laser with small size and high efficiency. Gallium phosphide is a good material for making semiconductor light emitting devices. The phosphide diodes can emit red and green light. The red and green light we see on the computer is released by it. For this reason, people will be hailed as "new foods for semiconductor materials."
Thorium can also be used to make cathode vapor lamps. The addition of cesium iodide to high-pressure mercury lamps can increase the radiation intensity of mercury lamps.
Antimony compounds can be used in analytical chemistry, organic synthesis, and catalysts in medicine.
Erbium compounds are also used in optical fiber communication systems and can be used to make large scale integrated circuits. As a heat carrier in the nuclear energy industry, they even have a place in the field of superconducting materials.
Second, resource reserves and their distribution
By the end of 2008, 166 mines have been identified in China's antimony mines and are distributed in 25 provinces (cities, districts) across the country. The reserves of resources are 136,600 tons, of which 0.71 million tons are basic reserves. Guangxi has the highest resources, reaching 29,000 tons, accounting for 21.2% of the country. The top five are Guangxi, Guizhou, Henan, Shanxi, and Yunnan, and the identified total reserves accounted for 88.2% of the country's total.
The world's resource reserves are about 180,000 tons. The reserves of foreign oysters are about 4 to 50,000 tons, while those of domestic oysters are about 1-340,000 tons. China's metal tantalum resources account for about 75% of the world's total.
III. The main types of industrial deposits and their occurrences
(I) Major industrial types
In nature, earthworms often symbiotically associate with trace elements and aluminum, zinc, or bismuth minerals. The crustal abundance of earthworms is 15×10-6, which is 1-2 orders of magnitude higher than that of other disperse elements. The content of earthworms in meteorites is high, and bauxite and sphalerite also contain a small amount of earthworms.
At present, China has not yet discovered an independent antimony deposit. In addition, in the currently known antimony-rich ore deposits, the general enrichment factor is about 4 to 5, and the enrichment factor in sphalerite and vermiculite in only a few ore deposits can be as high as about 330, and the ore formation cannot be controlled by other disperse elements. compared to.
The main industrial types of antimony deposits are: bauxite-bearing ores; bismuth-bearing copper, zinc ores, and other polymetallic ore sulfides; Hanyu coal mines.
(b) Occurrence status
The plutonium is always present in the relevant minerals in the same-type and in-phase form. It does not form an independent plutonium deposit with its own mining value. It can only be recycled in the selection and smelting process when the main metal deposit is mined.
In the provinces of Henan, Jilin, Shandong, and Guangxi, bismuth is mainly present in bauxite; bismuth in Heilongjiang and Yunnan provinces are mainly found in coal mines or tin mines; bismuth in Hunan and other provinces is mainly found in sphalerite.
Fourth, the extraction method
1. Extract cesium in the form of by-products. At present, industrial cesium is mainly extracted as a by-product from the sodium aluminate circulating solution used for the production of alumina from bauxite and the crude zinc distillation residue from the zinc blender wet zinc smelting process, and can also be extracted from coal coke dust. Recycling.
2. Extract the quinones by extraction. At a certain degree of acidity, the agent P538 can be used to obtain Ga, In, Ti from Ga, In and accompanying elements such as Zn, Co, Cd, Ni, and alkali and alkaline earth metal sulfate systems. A certain amount of back extractant can be used. Ga, In, and Ti are respectively extracted, and effective separation of Ga, In, and Ti can be achieved.
V. Analysis of Supply and Demand in Domestic and Foreign Markets
China is a big producer of plutonium, but its output is not stable. In 2000, the output of native oysters was 7.6 tons, in 2005 it was 17.78 tons, in 2007 it was 33.22 tons, and in 2008 it could reach 40 tons.
Based on demand projections, global production in 2008 totaled 85 tons. Among them, the output of Chinese metal tantalum (4N) accounts for about half of the global production.
In recent years, the rapid development of China's electronic information industry, the steady growth of domestic consumption. According to customs statistics, China exported 26 tons of unwrought metal oysters in 2008. Based on this measure, the apparent consumption of metal gallium in China in 2008 was about 14 tons.
According to China Electronic Materials Network's market research on GaAS, due to the maturity of GaAs crystal growth technology and device fabrication technology, it is expected that the demand for GaAs-based compound semiconductor materials and devices will average 10% over the next 10 years. % to 15% growth rate.
Since the global peak consumption of 200 tons in 2000, due to fluctuations in market prices and other factors, global consumption of germanium has fallen sharply, dropping to about 100 tons in 2006. The impact of the financial crisis on the real economy in the second half of 2008 exacerbated this downward trend. Last year, the consumption of cesium fell further to 85 tons. The consumption of cesium in our country accounts for about 16.5% of the world.
Under the influence of the global financial crisis, the price of China's metal tantalum all the way down in 2008. The price at the beginning of the year was 5,800-6,300 yuan/kg. After the low of 3,500 yuan/kg in mid-November, it slightly recovered at the end of the year. At the beginning of 2009, it further decreased to 3,400 to 3,700 yuan/kg.
6. Problems in the development and utilization of antimony ore resources in China
1. Difficulty in extracting earthworms. As a rare metal, there is almost no single, industrially exploited niobium deposit in nature, which can only be recovered from the by-products from the smelting process of other metals such as Al and Zn. However, since the content of antimony in other metal deposits is extremely low, it can only reach several hundred g/t after certain enrichment, so the extraction of antimony is very difficult.
2. Serious waste of resources. Most of the domestic enterprises are abandoning the use of waste materials, resulting in a lot of waste of resources.
3. The product has low added value. At present, there is no mastery of deep processing of metal ytterbium. The products are mainly exported in the form of primary raw materials. The added value is not high. A few companies such as Shandong Aluminum Company and Great Wall Aluminum Company have tried to purify 3~4N products to 6~7N products, and further processed them into GaAs and GaP products. However, the market is still a big obstacle and no significant progress has been made.
Seventh, the current policy of China's product management
1. The "2007 Catalogue of Goods Subject to Export License Management" and "2008 Catalogue of Goods Subject to Export License Administration" include unwrought ramie and wrought oysters in the list of goods subject to export license management.
2. Catalogue of Prohibited Commodities for Processing Trade in 2008 (Ministry of Commerce and General Administration of Customs Announcement No. 22 of 2008) stipulates that unrolled ramming, scrap, scrap, powdered, wrought and its products Export in the name of processing trade.
VIII. Policy recommendations
1. Strengthen the research on the extraction process of thorium and improve the comprehensive recovery and utilization level of thorium.
2. To increase export tariffs on unwrought ramie, scraps, scraps, thorium powders, wrought ytterbium and their products, and control excessive exports.
3. The country will implement a strategic reserve of base metals.
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