I. Mineral Name Serpentinite
Second, the type of deposits and their distribution
(1) The genetic type of the deposit
Serpentine is a product of olivine and pyroxene in ultrabasic rocks, which are replaced by high-temperature hot liquid. Dolomite can also form serpentine by hydrothermal replacement. Thus serpentine deposits (mainly chrysotile) by genetic types of deposits can be divided into: mass ultramafic rock type, rock type magnesium carbonate, and a mixed type of rock brucite chrysotile asbestos deposit four kinds .
(2) Industrial types of deposits
Serpentine can be divided according to its use in industry:
1, made with calcium and magnesium phosphate fertilizer serpentine DEPOSIT
2. Serpentine deposit for smelting flux
3. Serpentine deposit for sintering furnace slagging agent
4. Serpentine deposits for building materials and crafts
(3) Distribution of minerals
China's serpentine is rich in resources and has a good texture. The main mineral deposits include Donggou County, Donghai County, Jiangsu Province, Ganyang Geyang Yushudun, Henan Xinyang Crouching Tiger, Shaanxi Ningqiang County Heimulin, Lueyang County Jianchaling and Qixian Anzishan. Table 1 lists the ore components of the main serpentine mines in China.
Table 1 Ore composition of major serpentine mines in China
Mine name | chemical composition(%) | ||||||
MgO | SiO 2 | CaO | Fe 2 O 3 | Al 2 O 3 | NiO | Loss on ignition | |
Jiangsu Donghai | 39.60 | 38.20 | 0.56 | 7.21 | 1.20 | 0.28 | 14.78 |
Peng County, Sichuan | 37.21 | 36.41 | 1.24 | 8.85 | 0.36 | 0.23 | 14.60 |
Jiangxi Goyang | 39.12 | 36.76 | 0.26 | 8.12 | 1.14 | 0.31 | 12.87 |
Fujian Jianxi | 37.45 | 41.35 | 1.25 | 6.61 | 0.81 | 0.24 | 11.34 |
Henan Xinyang | 33.95 | 39.86 | 2.75 | 8.35 | 2.35 | 0.24 | 11.75 |
Shandong Penglai | 39.61 | 40.90 | 3.45 | 4.15 | 1.66 | ||
Hubei Hunchun | 37.38 | 36.64 | 1.94 | 12.24 | 2.70 | ||
Dandong, Liaoning | 36.62 | 28.90 | 11.45 | 1.47 | 0.21 | ||
Third, the main industrial indicators of the deposit
Table 2 General industrial requirements for serpentine deposits
use | ingredient(%) | other | |||
MgO | CaO | SiO 2 | MgO/ SiO 2 | ||
Calcium magnesium phosphate | ≥32 | <5 | Not specified but to ascertain the content | ||
Alkaline refractory | >40 | <0.8 | >1.1 | R2O3<10%, refractoriness>1750°C | |
Smelting flux | ≥38 | Not specified but to ascertain the content | Al2O3≤1.6%Ni≤0.5% S≤0.26% P≤0.05% | ||
Fourth, the nature of the ore
(1) Mineral composition of ore
Serpentine is a metamorphic rock mainly composed of serpentine. It is a metamorphic rock with moderate or low temperature metamorphism or metamorphism in the middle and low regions, which causes the olivine and pyroxene in the rock to undergo serpentinization . of.
Serpentine is a magnesium-rich silicate rock formed by the deformation of ultrabasic rocks by high temperature hydrothermal fluid. The main mineral composition as antigorite, chrysotile, lizardite, etc., followed by a magnetite, titanium, iron ore, chrome ore, brucite, magnesium carbonate, iron, sometimes contains a small amount of tremolite , mica, talc.
(2) Characteristics of the target mine
Serpentine is a high-magnesium mineral with a chemical formula of Mg6[Si4O10](OH)8, which contains 43.6% MgO, 43.3% SiO2, 13.1% H2O, and sometimes a small amount of FeO, Fe2O3, NiO and other components. In mineralogy, serpentine is a general term for serpentine minerals. This group of minerals includes:
1. Serpentine: The structural layer is flat and monoclinic.
2. Fiber serpentine: The structural layer is bent into a tubular shape, which is a monoclinic or orthorhombic system.
3, leaf serpentine: its structural layer undulating as a leaf-like, monoclinic system.
Serpentine is a layered silicate mineral whose structural layer is a double layer composed of a layer of silicon oxytetrahedron and a layer of hydrated octahedron. Serpentine is green in various degrees, such as light green, yellow green, dark green and black green, and also grayish white. The color varies with the composition of the impurities. The chlorite contains yellow-green, the pyrite-bearing iron ore, the chromite-colored black, and the limonite-containing brownish red. Dissociation parallel {001} is complete. Blocks have shell-like or staggered breaks. The hardness is 2 to 3.5, the relative density is 2.5 to 2.62, and the relative density of serpentine asbestos is 2.4 to 2.5.
V. Process characteristics and main uses
(I) Process characteristics Serpentine minerals Medium-fibrous serpentine has become one of the most widely used non-metallic minerals in modern industry. It is mostly light-colored, silky lustrous, highly fibrous fiber with a fine tubular structure, and the fiber diameter is 2×10-5mm～5×10-5mm, the texture is soft and elastic, it can be divided and the spinnability is good. High melting point (1500 ° C) and not easy to burn. It has good heat resistance, and its long-term heat-resistant temperature is 500-550 ° C, and the short-time heat-resistant temperature is 700 ° C. The refractive index is 1.5-1.7. Good thermal insulation, thermal conductivity is only 0.1-0.23W / m · K. The tensile strength is as high as 3.16×105 Pa, which greatly exceeds other organic and inorganic fiber materials. The insulation performance is good, and its volume resistivity is generally 3.1×108-5.12×108 Ω·cm, and the surface resistivity is 2.6-6.44×1018 Ω. It also has strong alkali resistance (the amount of alkali corrosion is in the range of 0.3%-0.7%) and low acid resistance (the amount of acid etching is 50%-60%). In addition, the serpentine (also known as Xiuyan jade) with fine texture and apple green is the jade, stone and construction materials carved by the craft.
(II) Main use serpentine minerals have broad application prospects due to their heat resistance, corrosion resistance, wear resistance, heat insulation, sound insulation, good process characteristics and associated beneficial components. Currently, they are mainly used in the following aspects. :
1. Manufacture of chemical fertilizers Serpentine is calcined together with apatite or phosphorite to form calcium magnesium phosphate fertilizer. If serpentine fine powder is applied alone, it also has certain fertilizer effect. Especially for corn, potato, beans and root and tuber crops, the effect is better.
2. As refractory materials For example, Tangshan Iron and Steel Plant uses serpentine to make serpentine coke oven bricks. Chongqing, Taiyuan and other steel mills use serpentine to make magerite bricks. As an alkaline refractory material, the effect is very good.
3. For the pharmaceutical industry Serpentine can be used as a raw material for the manufacture of diarrhea salts.
4. Refining magnesium metal. Magnesium containing magnesium is high. From cobalt, nickel higher serpentinite, the extract may be cobalt and nickel.
5. Extraction of fibrous amorphous silicon Amorphous silicon extracted from serpentinite reacts with carbon at a high temperature to form whiskers, crystal powders and crystals of silicon.
6, engraving materials Bright and transparent, translucent, dense and hard serpentine rock can be used as raw materials for jade crafts. There are more than ten kinds of serpentine jade in China. For example, Xiuyan jade in Liaoning is well-known at home and abroad.
7. Auxiliary raw materials for the production of cast stone or rock wool In the case of cast stone or rock wool furnish, if the MgO is insufficient, serpentinite can be used as an auxiliary material to increase the MgO content and relatively reduce the Al2O3 and CaO content.
Sixth, product quality standards
The industrial technical requirements for serpentine are mainly reflected in the chemical composition and content, and are generally based on the content of MgO and CaO:
(1) Agricultural fertilizers and ingredients MgO<36%, CaO<3~5%.
(2) Smelting flux ingredients
It is required that the serpentinite has MgO≥38%, the harmful component Al2O3≤1.6%, S≤0.26%, Ni≤0.5%, P≤0.05%, and a certain amount of serpentinite is added as a slag-forming agent in the blast furnace and the sintering furnace. The fluidity of the slag can be obviously improved, and the sintered ore can have better structural and structural characteristics and mechanical strength.
(III) As refractory materials It is required that MgO in serpentinite is >40%, CaO<0.8%, Al2O3<1.5%, and refractoriness>1750°C.
(4) The slag-forming agent of the sintering furnace has a MgO of >35%, a particle size of 10 to 30 mm, and a loss on ignition of <1%.
(5) Serpentine for building materials and handicrafts
Appearance: bright and beautiful, compact structure, uniform weathering. Physical properties: a certain degree of block and compressive strength, with honing and processing.
Seven, comprehensive utilization of process technology
(1) Serpentine dressing
Serpentine mines are generally selected for rich ore mining. The original ore is crushed and sieved, and can be sold after reaching a certain blockiness requirement.
In order to explore the separation of serpentine and its associated useful minerals, the study of serpentine flotation characteristics was also carried out. The results showed that both sodium oleate and laurylamine hydrochloride had better harvesting properties for serpentine. It is speculated that the Mg particle on the surface of serpentine is the active point of oleate adsorption, and when floated with the cationic collector dodecylamine salt, the amine is adsorbed on the serpentine surface in a molecular state. Water glass has a strong inhibitory effect on serpentine flotation.
(2) Serpentine as an ingredient to produce calcium magnesium phosphate fertilizer
At present, the domestic enterprises that use serpentine as a batch to produce calcium magnesium phosphate fertilizer mainly include: Guangxi Phosphate Fertilizer Plant, Yunnan Phosphate Fertilizer Plant, and Jiangsu Donghai Phosphate Fertilizer Plant.
(3) Extracting magnesia from serpentine
Serpentine is a high-magnesium mineral. The idea and process of extracting magnesia from serpentine was first proposed in Austria 10 years ago. The method is expected to become the third production method of extracting magnesium from the magnesium oxide addition seawater magnesite and beyond, and compared with the extracted from seawater, sodium hydroxide produced the Act soluble boron-free coke Object. The process of extracting magnesium oxide from serpentine is as follows:
Serpentine | Acid leaching | Soluble part | Purification | Spray calcination | Magnesium oxide products |
Insoluble part | Purification | dry | Porous silica products |
In the multi-stage linked leaching device, serpentine particles of 0 to 1 mm were leached at 105 ° C in 20% hydrochloric acid. The serpentine particles have a residence time of 2.5 hours in hydrochloric acid. The leaching solution is purified to remove impurities such as iron, and then spray-fired to obtain a magnesium oxide product having a purity of 99% or more. The leaching residue was porous silica having a pore size ranging from 0 to 2 mm and a specific surface area of ​​150 m 2 /g. This leaching slag has been successfully applied in papermaking, brewing and soil purification.
Using the above process, an average of 380 kg of high quality magnesia and 250 kg of silica can be produced per ton of serpentine.
(IV) Extraction of useful components Australia extracts high-grade magnesium oxide and porous silica from snake serpentine. Porous silica can be used in papermaking, brewing and sewage purification. China has also obtained preliminary results through experiments, and the purity of the extracted magnesia and porous silica is greater than 99.5%. The Institute of Pollution Resources of the Japan Industrial Technology Institute has developed a new technology for extracting amorphous silica (SiO2) from serpentine. The serpentine rock is pulverized into particles of 30 mm in diameter, made into a light gray powder, and then demagnetized. Remove the magnetic substance and then pick it up with a concentration of 10-20% hydrochloric acid or sulfuric acid at 100 ° C to obtain white amorphous silica. Add high-quality carbon black to the amorphous silica at high temperature (about 2000). Under the reaction of °C), silicon carbide single crystal fiber and silicon carbide crystal, silicon carbide (SiC), hardness second only to diamond , melting point up to 2700 ° C, can be used for grinding wheel and advanced refractory material, silicon carbide Single crystals can be used as materials for making advanced radio components.
Eight, development and utilization status and development trend
At present, the development and utilization of serpentine in China is still in its infancy, and the level of development and utilization is very low. Most of the mines rely mainly on the sale of raw lump ore and simple processed crude products. The value is extremely low at tens of yuan per ton, and the benefits are very poor. In view of the current situation of the development and utilization of serpentine in China, we should strengthen the development and research work in the following aspects:
(1) Extracting beneficial components and synthesizing and regenerating new industrial high-grade products. In this respect, Japan, Australia, and the United States have entered the forefront of the world, and China is still in the experimental stage.
(B) producing a composite mineral fertilizers mixed with 10% potassium feldspar raw material, with phosphate rock, serpentine and coke into the furnace after melting, Ca, Mg, P and K can be made, than the production cost of the production of calcium magnesium phosphate A 30% reduction, the use effect is better than calcium magnesium phosphate fertilizer, is a promising fertilizer.
(III) Increasing the utilization rate of tailings resources development is mainly reflected in the comprehensive utilization of tailings short fiber asbestos, residual slag and waste rock, such as the development of tailings to develop new product routes, extracting beneficial elements and tailings. Direct use, preparation of high quality building materials and other aspects. On the one hand, the comprehensive utilization of tailings can turn waste into treasure and increase economic benefits; on the other hand, it can reduce environmental pollution to purify the environment; thirdly, it can also save energy.
(IV) Increasing the degree of comprehensive utilization The dispersed nickel silicate in serpentine is difficult to obtain by general smelting conditions and processes. In the slag after the production of calcium magnesium phosphate fertilizer, nickel is enriched and can be comprehensively recovered. After Donghai County e.g. phosphate fertilizer plant for producing a calcium magnesium phosphate Xugou serpentine, slag nickel, cobalt, chromium 10 to 15 times relative enrichment, but also found PGE, higher grade, worth recycling. The plant recovers nickel from the slag, and the obtained electrolytic nickel contains Ni99.99%, the open furnace nickel contains Ni61.58%, and the cobalt carbonate contains 18.50% of cobalt. Each year, 65 to 70 tons of nickel sulfate can be extracted from the slag, and the price per ton is 6,500 to 7,000 yuan. The platinum group element can be further enriched after the nickel extraction process, but it has not been solved due to the unresolved process.
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