CN112897530B - Method for efficiently dissolving silicate substances and extracting high-purity silicon oxide - Google Patents
Method for efficiently dissolving silicate substances and extracting high-purity silicon oxide Download PDFInfo
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Abstract
The invention discloses a method for efficiently dissolving silicate substances and extracting high-purity silicon oxide, which comprises the steps of placing a powder raw material containing silicon-containing inorganic solid wastes or silicon-containing natural sandy soil into a reaction kettle, adding a mixed acid of inorganic acid X, inorganic acid Y, inorganic acid Z, water-soluble alcohol and water as an extraction solution, heating and reacting under the condition of being more than or equal to 0.1MPa, filtering after the reaction is finished to obtain an acidic mixed solution and filter residues, heating and boiling the acidic mixed solution, collecting silicon-containing volatile components by a collector, and decomposing and depositing the silicon-containing volatile components in the collector; drying the amorphous silicon dioxide decomposed and deposited in the collector to obtain high-purity silicon oxide powder; and washing and drying filter residues to obtain silicon dioxide. The invention does not generate new waste residue and does not increase the waste residue, thereby having remarkable reduction and utilization effects of industrial waste, reducing the pollution of the industrial waste residue to the environment and fully utilizing industrial solid waste and idle natural resources.
Description
Technical Field
The invention relates to the technical fields of resource recycling, chemical industry, materials, minerals, metallurgy and the like. In particular to a method for efficiently dissolving silicate substances containing low-grade silicon, efficiently dissolving silicate substances and extracting high-purity silicon oxide.
Background
High purity silica is an important industrial raw material for the manufacture of optical glass, optical fibers, functional materials, additives and important components of the electronics industry.
At present, a plurality of methods for synthesizing high-purity silicon oxide exist, wherein a gas phase method takes high-purity silicon tetrachloride, silicon tetrafluoride, methyl silicon trichloride and the like as raw materials, and carries out high-temperature hydrolysis in oxyhydrogen flame to generate silicon dioxide particles, and then processes such as quenching, aggregation, separation, deacidification and the like are carried out to obtain the high-purity silicon oxide; the hydration-gelation method for producing high purity silica is a method in which a reactant is decomposed with an acid or an alkali to form a silica sol, the pH value is adjusted with an alkali or an acid, and a silica gel is formed by filtration and purification; adding an acid solution to the water glass solution to obtain a reaction solution, submitting the reaction solution to pH =9-13 with a base to obtain silica sol, and adding an aqueous solution to form silica gel. The reaction solution can also be evaporated or concentrated to prepare silica sol; adding silicon powder into a sodium hydroxide solution at 65 ℃, adding ammonia water to adjust the pH value to 9-10, and preparing silica sol; mixing diluted water glass and dilute sulfuric acid to prepare silica gel; and drying the silica sol to obtain the purified silicon dioxide. In addition, after the micron-sized silicon dioxide, water, hydrochloric acid, fluoride and mineralizer mixed solution reacts for a long time, cooling and filtering are carried out, filtrate is treated by lime water, then deionized water is used for washing until the filtrate is neutral, and drying is carried out, so that purified silicon dioxide is obtained. The above methods all use high-purity secondary raw materials, and have high cost.
On the other hand, industrial wastes discharged from enterprises such as mines, electric power, metallurgy and the like occupy a large amount of land and cause serious environmental pollution, and a resource regeneration method which is efficient, high in added value, low in cost and free of secondary waste is urgently needed to be developed. These inorganic solid wastes and natural sandy soils contain a large amount of silica components, such as fly ash, desert sand, coal gangue, red mud, metal or non-metal tailings, and the like. The extraction of high-purity compounds including silicon oxide from these substances is the development direction of comprehensive utilization of resources, and meets the requirements of constructing an environment-friendly and resource-saving society and protecting ecological environment.
One method for preparing silicon dioxide by utilizing fly ash is to mix the fly ash with Na 2 CO 3 Mixing evenly, fine grinding, reacting at 800-900 ℃, acid leaching the reaction product with hydrochloric acid with the concentration of 3.14mol/L, filtering out the alkali after impurities to convert the sol into gel, filtering again, drying to obtain SiO with the purity of more than 98 percent 2 . Calcining coal gangue powder at 700-900 deg.C, reacting with hydrochloric acid, and reacting the filter residue with HF to obtain SiF 4 Hydrolyzing in ethanol solution to obtain precipitate, and washing to obtain silicon oxide powder (white carbon black). And adding sodium hydroxide solution into the filter residue for continuous reaction, and filtering, salting out, drying and the like to obtain the white carbon black. Calcining quartz ore at high temperature, water quenching, removing impurities, oven drying, grinding into fine powder, mixing with a certain amount of chlorinating agent (carbon tetrachloride, hydrogen chloride, chlorine, ammonium chloride, and trichloroethylene), and calcining at 900 deg.C for 60 min. The chloridized silicon oxide powder is reused by HCl and HNO 3 Soaking HF mixture for over 40 hr, and performing electrodialysisAnd (3) washing the chloridized silicon oxide powder to be neutral by water or deionized water, and drying at 200-900 ℃ to obtain silicon oxide powder. Calcining the ferrosilicon-rich tailing powder dissolved and dealuminized by hydrochloric acid, reacting with excessive dilute hydrochloric acid, filtering, mixing filter residue with NaOH, calcining again, pouring into water, heating, stirring and filtering. Adding NaCl and hydrochloric acid into the filtrate, adjusting the pH value to 8-9, carrying out ultrasonic washing on the flocculent precipitate, and drying to obtain the white carbon black.
In addition, in order to obtain the highest leaching rate of the alumina, the coal ash is leached by adopting a mixed solution of HCl with the concentration of 4.95mol/L and HF with the concentration of 4.93mol/L, the liquid-solid mass ratio is (4.5-5.0) to 1, and the leaching time is 3 hours at the temperature of 90-95 ℃, so that the effect is best. It was found that HF promotes mullite leaching, and also causes leached Al 3+ Aluminum fluoride is generated to reduce Al 2 O 3 Leaching while enlarging the SiO phase of the non-mullite phase 2 Leaching to form SiF 6 2- The environment is burdened and the concentration of HF is therefore tightly controlled by the leaching process.
Therefore, the defects of great consumption of alkaline and acidic substances, difficult recovery, difficult water treatment, great amount of discharged secondary waste residues and new solid waste treatment problem are overcome in the process of extracting silicon oxide from fly ash, coal gangue and iron tailings leached by an acid method and an alkaline method.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for efficiently dissolving silicate substances and extracting high-purity silicon oxide, so as to solve the problems of huge consumption and difficult recovery of alkaline and acidic substances, difficult water treatment, high cost, huge amount of discharged secondary waste residues, new solid waste treatment and the like when extracting silicon oxide from substances with high silicon oxide content such as inorganic solid waste, natural sandy soil and the like, thereby fully utilizing industrial solid waste and natural idle resources, saving mineral resources and protecting ecological environment.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps:
step A: placing a powder raw material containing silicon inorganic solid waste and/or silicon natural sandy soil into a reaction kettle, adding a mixed acid of inorganic acid X, inorganic acid Y, inorganic acid Z, water-soluble alcohol and water as an leaching solution, heating and reacting under the condition of more than or equal to 0.1MPa, and filtering after the reaction is finished to obtain an acidic mixed solution and filter residue;
and B, step B: heating the acidic mixed solution obtained in the step A to boil, collecting silicon-containing volatile components by using a collector, and decomposing and depositing the silicon-containing volatile components in the collector;
and C: drying the amorphous silicon dioxide decomposed and deposited in the collector to obtain high-purity silicon oxide powder;
step D: and C, washing and drying the filter residue obtained in the step A to obtain silicon dioxide.
The method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps: the silicon-containing inorganic solid waste is one or a combination of more of fly ash, coal gangue, red mud, metal tailings and non-metal tailings; the natural sand soil is one or a combination of several substances of desert sand, river sand and clay.
The method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps: the inorganic acid X is hydrochloric acid, the inorganic acid Y is hydrofluoric acid, and the inorganic acid Z is sulfuric acid; the water-soluble alcohol is ethanol. Nitric acid is less acidic than sulfuric acid and hydrochloric acid, and nitric acid is unstable, is easily decomposed by light and heat, and emits nitrogen dioxide (N0) 2 ) Gas, reduce acidity, not easy to liquefy and recover, and cause environmental pollution.
The method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps: the mass ratio of the powder raw material, the inorganic acid X, the inorganic acid Y, the inorganic acid Z, the water-soluble alcohol and the water is (10-15): (25-35): (6-12): (5-10): (5-10): (15-35).
The method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps: the concentration of the used raw material hydrochloric acid is more than or equal to 36wt%, the concentration of the used raw material hydrofluoric acid is more than or equal to 40wt%, the concentration of the used raw material sulfuric acid is more than or equal to 95wt%, and the used raw material ethanol is absolute ethanol, and the content of ethanol is more than or equal to 99wt%.
The method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps: the pressure in the reaction kettle is 0.1-0.3MPa.
The method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps: the reaction temperature is 90-140 ℃.
The method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps: the reaction time is 0.5 to 2 hours.
The method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps: the drying temperature in the step C is 150 ℃.
The method for efficiently dissolving silicate substances and extracting high-purity silicon oxide comprises the following steps: the drying temperature in the step D is 150 ℃.
The process principle of the method is as follows:
the industrial solid waste, natural sandy soil and other substances mainly comprise quartz (crystal and amorphous), mullite, iron titanium oxide, carbonate, magnesium, calcium, potassium, sodium and other alkali metal and alkaline earth metal ions, silicon, aluminum and other feldspar, kaolinite silicate or aluminosilicate with complex structures, and the components are very complex and unstable. The naturally formed quartz also has a small amount of ions such as magnesium, calcium, potassium, sodium, aluminum, iron, etc. dissolved therein. Hydrochloric acid is very aggressive to iron titanium oxides, carbonates and partial silicates and aluminosilicates, and can dissolve out these substances well, but the dissolution rate of these substances is not increased any more after adding hydrochloric acid in a very excessive amount, one of the reasons for this is that hydrochloric acid is very weak in aggressive to quartz and partial silicates such as mullite (aluminosilicate). The addition of hydrofluoric acid has great influence on the dissolution of the powder raw material; the addition of HF can destroy Al-Si bonds in mullite and other compounds, and has certain effect on destroying Si-Si bonds in quartz, so that mullite, quartz and the like can be effectively dissolved. However, excess hydrofluoric acid forms a large number of fluoride ions, fluoroaluminate and fluorosilicate ions which react with free metal ions to formComplex polycomplexes such as CaAlF 5 And CaSiF 5 And fluorides of Al, na, fe, mg, etc., and fluorinated complexes obtained by complexing these fluorides with crystal water. They tend to form precipitates which result in a reduction in the silicon and metal ion content of the solution and a reduction in the purity of the acid leach residue. Therefore, the amount of hydrofluoric acid added is appropriate. In addition, a proper amount of sulfuric acid is added into the mixed acid solution to play a role in the complex action of the polybasic acid, so that the dissolution assisting effect can be obviously played, and the subsequent evaporation and deposition of the amorphous silicon oxide can be well promoted. The concentration of the solution also has a large influence on the dissolution effect and the formation of fluoride, silicon-rich compound precipitates.
The liquid in the reaction kettle can be adjusted by increasing the vapor pressure in order to obtain higher temperature. Stirring, heating and pressurizing also significantly improved the dissolution effect, but too high a temperature also easily caused more silicate precipitate to be generated. Compared with the prior art, the concentration of the hydrochloric acid is relatively high, the concentration of the hydrofluoric acid is relatively low, and particularly, the consumption of the hydrofluoric acid is related to the content of quartz. The good dissolving effect can be generated only under the conditions of reasonable proportion and concentration of the dosage of the hydrochloric acid, the hydrofluoric acid and the sulfuric acid and proper liquid temperature.
Those with lower boiling point, such as H, as the temperature of the acidic mixture increases and even after boiling 2 O、HF、HCl、SiF 4 、SiCl 4 、H 2 SiF 6 And H 2 SiO 3 The components are volatilized or evaporated into a gas. The silicon-containing gas decomposes in the trap to deposit amorphous or crystalline silicon oxide. The amorphous silica is in gel or flocculent precipitate according to the difference of the pressure of the reaction kettle. The larger the air pressure of the reaction kettle is, the higher the speed of airflow entering the collector is, the easier dehydration and decomposition are carried out, and flocculent precipitates tend to be formed; conversely, a colloidal material is formed. The proper amount of ethanol is added, so that the volatilization and evaporation effects of the silicon-containing gas can be improved, and the dehydration and decomposition of the silicon-containing gas can be well promoted. Drying the gel or flocculent precipitate for further dehydration to obtain the silicon oxide powder with the purity higher than 99.8 percent. The hydrogen chloride and the hydrogen fluoride in the gas flow are condensed into salt in the collectorAnd returning the acid and the hydrofluoric acid to the reaction kettle to continuously participate in the reaction.
The undissolved residue residues still exist in the powder raw materials which are soaked by the mixed solution, the silicon oxide purity of the residues is higher than 90.0% after the residues are washed and dried, and the specific components and the residual quantity of the residues are related to the types of dissolved substances and the content of silicon oxide crystals in each powder raw material besides the mixed acid solution.
Because the acid liquor has strong corrosivity, all surfaces of reaction kettles, pipelines, detection instruments and the like which are in contact with the acid liquor need to be subjected to corrosion prevention treatment.
The technical scheme of the invention achieves the following beneficial technical effects:
(1) inorganic solid wastes such as fly ash, coal gangue, metal or nonmetal tailings, red mud and the like, and natural sandy soil such as desert sand, river sand, clay and the like are used as raw materials, and besides high-purity silicon oxide is prepared, silicon oxide with higher purity is further extracted from the silicate substances containing low-grade silicon. The method obviously reduces the quantity of residual slag, has obvious reduction utilization effect on industrial wastes, and reduces the pollution of the industrial waste slag to the environment.
(2) Fully utilizes industrial solid wastes and idle natural resources, saves mineral resources, protects homeland resources and protects ecological environment.
(3) As no strong alkaline substance is added, no other new waste residue is generated, and the waste residue is not increased.
(4) Under the condition of reasonably regulating and controlling the proportion and the temperature of the mixed acid liquid, the dissolution rate of the raw materials is high, and the decrement effect is obvious.
(5) Hydrochloric acid, hydrofluoric acid and sulfuric acid condensed in the collector return to the reaction kettle to continue to react, discharge is not needed, and the environment-friendly effect is good.
(6) The purity of the amorphous silicon oxide powder deposited by evaporation and decomposition is high and reaches more than 99.8 percent; the content of silica in the undissolved residue is also higher than 90.0%, and the specific content and residual amount thereof are related to the species to be dissolved.
(7) The reaction is carried out at 90-140 ℃, high-temperature calcination is not needed, and the energy-saving effect is good.
(8) The tail liquid after extracting silicon oxide can further separate aluminum, iron, magnesium, calcium, titanium and other ions by adopting an electrochemical method to form hydroxides or oxides of the ions, and the waste liquid is precipitated and purified to be a fluorine-containing solution and can also be reused. Finally, the high-efficiency and high-added-value utilization of inorganic solid wastes and natural resources is realized.
Drawings
FIG. 1 amorphous silica vapor deposited according to inventive example 1 morphology (a), composition (b) and phase composition (c);
FIG. 2 morphology (a), composition (b) and phase composition (c) of undissolved residue of example 1 of the present invention;
note: since the chemical and phase compositions of the evaporated deposits and the undissolved residue are relatively close in each example, they are not shown in the following example so as not to be too repeated. It is only given when a particular phenomenon of chemical composition or phase composition occurs.
FIG. 3 shows the morphology (a) of silicon oxide vapor-deposited and undissolved residue in example 2 of the present invention;
FIG. 4 morphology (a) and phase composition (b) of the silicon oxide vapor-deposited and morphology (c) of the undissolved residue slag of example 3 of the present invention;
FIG. 5 shows the morphology of the silicon oxide (a) and the undissolved residue (b) which were vapor-deposited in example 5 of the present invention.
Detailed Description
Example 1
In this example, 200g of fly ash, hydrochloric acid, hydrofluoric acid and sulfuric acid: ethanol: the mass ratio of water is 10:30:12:5:10:35, the concentration of the used raw material hydrochloric acid is more than or equal to 36wt%, the concentration of the used raw material hydrofluoric acid is more than or equal to 40wt%, the concentration of the used raw material sulfuric acid is more than or equal to 95wt%, the used raw material ethanol is absolute ethanol, and the ethanol content is more than or equal to 99wt%. Adding the above raw materials into a reaction kettle, maintaining the temperature at 100 deg.C, stirring under vapor pressure of 0.1MPa (equivalent to 1 atmosphere) for reaction for 1.5 hr to obtain silica gel, drying at 150 deg.C to obtain 99.85% purity silica gel; the undissolved residue was washed with water and dried at 150 ℃ to give a residue of 46.3g, having a silica content of 91.16%.
FIG. 1 shows the morphology (a), composition (b) and phase composition (c) of the amorphous silica vapor-deposited in the present example, and FIG. 2 shows the morphology (a), composition (b) and phase composition (c) of the undissolved residue. As can be seen from the figure, the evaporative deposits are colloidal structures, the main component is silica, but contain trace impurities, and the deposits are amorphous silica; and residue after acid liquor 23510 soaking is granular, mainly contains silicon oxide components, but contains more impurity elements, and the granular residue is silicon oxide crystals.
Example 2
In the present example, 200g of desert sand fine powder is used, and the desert sand powder comprises hydrochloric acid, hydrofluoric acid and sulfuric acid: ethanol: the mass ratio of water is 15:25:9:10:5:15, the concentration of the used raw material hydrochloric acid is more than or equal to 36wt%, the concentration of the used raw material hydrofluoric acid is more than or equal to 40wt%, the concentration of the used raw material sulfuric acid is more than or equal to 95wt%, the used raw material ethanol is absolute ethanol, and the ethanol content is more than or equal to 99wt%. Adding the above raw materials into a reaction kettle, maintaining the temperature at 90 deg.C, stirring under vapor pressure of 0.1MPa, reacting for 2 hr to obtain colloidal silicon oxide, drying at 150 deg.C to obtain 99.82% pure silica; the undissolved residue was washed with water and dried at 150 ℃ to give a residual amount of 128.5g, with a silica content of 92.63%. As shown in fig. 3, the undissolved portion is granular and substantially in the phase of the silicon oxide crystal.
Example 3
In the embodiment, 200g of iron tailing grinding powder is used, and the iron tailing powder comprises hydrochloric acid, hydrofluoric acid and sulfuric acid: ethanol: the mass ratio of water is 15:35:11:7:8:20, the concentration of the used raw material hydrochloric acid is more than or equal to 36wt%, the concentration of the used raw material hydrofluoric acid is more than or equal to 40wt%, the concentration of the used raw material sulfuric acid is more than or equal to 95wt%, the used raw material ethanol is absolute ethanol, and the ethanol content is more than or equal to 99wt%. Adding the above raw materials into a reaction kettle, maintaining the temperature at 140 deg.C, stirring under vapor pressure of 0.3MPa, reacting for 0.5 hr to obtain silicon oxide flocculent, drying at 150 deg.C to obtain 99.86% pure silicon; the undissolved residue was washed with water and dried at 150 ℃ to give a residue of 86.5g, having a silica content of 92.87%. As shown in fig. 4, the deposit has a cluster structure with crystal phases therein, each of which is a silicon oxide component.
Example 4
In the present example, 200g of red mud fine powder was used, and the weight ratio of red mud fine powder to hydrochloric acid to hydrofluoric acid to sulfuric acid: ethanol: the mass ratio of water is 10:33:6:8:6:25, the concentration of the used raw material hydrochloric acid is more than or equal to 36wt%, the concentration of the used raw material hydrofluoric acid is more than or equal to 40wt%, the concentration of the used raw material sulfuric acid is more than or equal to 95wt%, and the used raw material ethanol is absolute ethanol and the ethanol content is more than or equal to 99wt%. Adding the above raw materials into a reaction kettle, maintaining the temperature at 100 deg.C, stirring under vapor pressure of 0.1MPa, reacting for 1.5 hr to obtain silicon oxide flocculent and colloidal, and drying at 150 deg.C to obtain silicon oxide with purity of 99.85%; the undissolved residue was washed with water and dried at 150 ℃ to give a residue of 75.2g, having a silica content of 91.9%.
Example 5
200g of coal gangue fine powder, hydrochloric acid, hydrofluoric acid, sulfuric acid and ethanol: the mass ratio of water is 12:32:10:5:5:30, the concentration of the used raw material hydrochloric acid is more than or equal to 36wt%, the concentration of the used raw material hydrofluoric acid is more than or equal to 40wt%, the concentration of the used raw material sulfuric acid is more than or equal to 95wt%, and the used raw material ethanol is absolute ethanol and the ethanol content is more than or equal to 99wt%. Adding the above raw materials into a reaction kettle, maintaining the temperature at 120 deg.C, stirring under vapor pressure of 0.2MPa, reacting for 1 hr to obtain silicon oxide flocculent, drying at 150 deg.C to obtain a purity of 99.80%; the undissolved residue was washed with water and dried at 150 ℃ to give a residual amount of 103.6g, and the silica content was 92.3%. As shown in fig. 5, the deposit was mainly of a floc structure with a small amount of crystalline phase, which was determined to be the silicon oxide component.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.
Claims (3)
1. A method for efficiently dissolving silicate substances and extracting high-purity silicon oxide is characterized by comprising the following steps:
step A: placing a powder raw material containing silicon inorganic solid waste and/or silicon natural sandy soil into a reaction kettle, adding a mixed acid composed of inorganic acid X, inorganic acid Y, inorganic acid Z, water-soluble alcohol and water as an leaching solution, heating and reacting under the condition of more than or equal to 0.1MPa, and filtering after the reaction is finished to obtain an acidic mixed solution and filter residue;
and B: heating the acidic mixed solution obtained in the step A to boil, collecting silicon-containing volatile components by using a collector, and decomposing and depositing the silicon-containing volatile components in the collector;
and C: drying the amorphous silicon dioxide decomposed and deposited in the collector to obtain high-purity silicon oxide powder;
step D: washing and drying the filter residue obtained in the step A to obtain silicon dioxide;
in step a: the silicon-containing inorganic solid waste is one or a combination of more of fly ash, coal gangue, red mud, metal tailings and non-metal tailings; the natural sand soil is one or a combination of several substances in desert sand, river sand and clay;
in step a: the inorganic acid X is hydrochloric acid, the inorganic acid Y is hydrofluoric acid, and the inorganic acid Z is sulfuric acid; the water-soluble alcohol is ethanol; the mass ratio of the powder raw material, the inorganic acid X, the inorganic acid Y, the inorganic acid Z, the water-soluble alcohol and the water is (10-15): (25-35): (6-12): (5-10): (15-35);
in step a: the concentration of the used raw material hydrochloric acid is more than or equal to 36wt%, the concentration of the used raw material hydrofluoric acid is more than or equal to 40wt%, the concentration of the used raw material sulfuric acid is more than or equal to 95wt%, and the used raw material ethanol is absolute ethanol, and the content of ethanol is more than or equal to 99wt%;
in step a: the pressure intensity in the reaction kettle is 0.1-0.3MPa; the reaction temperature in the reaction kettle is 90-140 ℃; the reaction time is 0.5 to 2 hours.
2. The method for dissolving silicate materials and extracting high purity silica with high efficiency as claimed in claim 1, wherein said drying temperature in step C is 150 ℃.
3. The method for dissolving silicate substances and extracting high purity silica with high efficiency as claimed in claim 2, wherein the drying temperature in step D is 150 ℃.
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| CN100383041C (en) * | 2006-09-01 | 2008-04-23 | 上海大学 | Method of preparing nanometer SiO2 from ophiolite |
| CN101774584B (en) * | 2009-01-09 | 2011-12-21 | 华南师范大学 | method for purifying solar-grade silicon |
| CN102897771B (en) * | 2012-10-26 | 2014-04-02 | 张韵 | Silicate ore acid leaching extraction method |
| CN104773739B (en) * | 2015-01-14 | 2017-10-27 | 南阳东方应用化工研究所 | A kind of decomposition method of flyash |
| CN105585032B (en) * | 2015-09-09 | 2017-10-20 | 洛阳国兴矿业科技有限公司 | The method that fluorine resource is reclaimed from low product bauxite waste gas decomposition |
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