CN102557033B - Process for recovering molybdenum-silicon heteropoly acid from waste molybdenum disilicide - Google Patents
Process for recovering molybdenum-silicon heteropoly acid from waste molybdenum disilicide Download PDFInfo
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Abstract
The invention discloses a process for recovering molybdenum-silicon heteropoly acid from waste molybdenum disilicide, belonging to the technical field of recycling of solid wastes. The process comprises the steps: crushing the waste molybdenum disilicide into powder, then transferring the waste molybdenum disilicide powder into a porcelain boat, roasting at certain temperature to obtain mixed powder of oxides of molybdenum and silicon, and mixing the oxidized powder with deionized water to prepare slurry; adding solid NaOH into the slurry, stirring by means of magnetic force, cooling, filtering, directly pouring the filtered solution into hydrochloric acid, stirring, placing in a water bath kettle, heating, and continuously stirring until silica gel precipitates, filtering the silica gel, adding n-butyl alcohol into filtrate for extraction, and carrying out reduced-pressure distillation to obtain a rough product of the molybdenum-silicon heteropoly acid; and dissolving by using the deionized water and adding little nitric acid, filtering and washing to remove residual n-butyl alcohol organic matters, and drying to obtain the molybdenum-silicon heteropoly acid. The process has the advantages of realizing the reutilization of molybdenum in the waste molybdenum disilicide, saving raw materials and realizing recycling of resources.
Description
Technical field
The invention belongs to the recovery and utilization technology field of solid waste, especially relate to a kind of technique that reclaims molybdenum sila polyacid from waste and old molybdenum disilicide.
Background technology
Molybdenum is a kind of rare noble metal.Molybdenum standing stock on earth are less, and its content only takes up an area 0.001% of shell weight, and whole world molybdenum ore mainly is distributed in the states such as the U.S., China, Chile, Russia, Canada.China has verified 8,400,000 tons of molybdenum reserves, occupies the second place of the world, and the molybdenum product production occupies the third place in the world, accounts for 24%～25% of World Molybdenum ultimate production.
The coefficient of expansion of molybdenum is little, and electric conductivity is large, good heat conductivity, be not subjected at normal temperatures the erosion of air, with hydrochloric acid, hydrofluoric acid and the equal Fails To Respond of alkaline solution, be only soluble among nitric acid, chloroazotic acid or the vitriol oil, to also quite stable of most of liquid metals, nonmetal slag and melten glass.Therefore, Mo and Mo alloys has a wide range of applications and good prospect at industrial circles such as iron and steel, electronics, aerospace, nuclear energy technology, stress metal processing, chemistry, becomes a kind of important raw material and irreplaceable strategic material in national economy.
Along with the continuous expansion of molybdenum resource Application Areas in defence and military and national economy, the demand of molybdenum and compound thereof is improved constantly.Only rely on and extract molybdenum and compound can not satisfy the needs of production development from contain the molybdenum ore deposit, and as a kind of limited resources, unconfined exploitation are also impossible, therefore, from strategic angle, must realize the molybdenum resource circulation utilization, the reclaiming that foundation contains the molybdenum secondary resource utilizes system, what exploitation was advanced reclaims molybdenum and the Technology of producing molybdenum product from various containing the molybdenum secondary resource, increase the cyclic utilization rate of molybdenum, impels the Sustainable development of molybdenum industry.
Molybdenum disilicide (MoSi
2) with excellent properties such as its high fusing point, lower density, good high-temperature oxidation resistance and a series of mechanics, electricity and be subject to aerospace and the great attention of military project department, be hopeful high temperature oxidation field for 1200～1600 ℃ as a kind of potential high-temperature structural material.
At present, MoSi
2Using the most widely is as the electric furnace Heating element.MoSi
2Heating element is by Sweden Kanthal company invention, and Kanthal company had obtained MoSi in 1956
2First business patent of Heating element, its representative products are Kanthal and the Kanthal-Super that Kanthal company produces, and early 1990s Kanthal brings up to 1900 ℃ to the temperature of Heating element.China carries out MoSi from early 1960s
2The research of Heating element has realized the industrial production of molybdenum silicide heating element the eighties in 20th century.MoSi
2Heating element has been used on large scale industry electric furnace and small-size laboratory electric furnace, is one of major equipment of the industries such as metallurgy, electronics, glass, pottery and magneticsubstance.
At present, global MoSi
2Heating element output surpasses 600 ton/years, and China's output also surpasses 300 ton/years, but the waste and old molybdenum disilicide Heating element does not cause people's enough attention.Thereby there is more than 300 tons of molybdenum disilicide waste materials abandoned or idle every year in China.Approximately contain more than 190 tons of molybdenums (being worth nearly hundred million yuans) every year in more than 300 tons of molybdenum silicide heating elements in China; if these waste materials are recycled; the cyclic utilization rate of molybdenum will greatly be strengthened; Sustainable development and environment protection to molybdenum industry produce important meaning, can also bring good economic benefit.
Summary of the invention
The object of the present invention is to provide a kind of technique that reclaims molybdenum sila polyacid from waste and old molybdenum disilicide, solved the recycle problem of molybdenum disilicide, and method is simple, effective, saving resource.
Processing step of the present invention is as follows:
(1) waste and old molybdenum disilicide is ground into is of a size of the powder of 2～15 microns;
(2) material that obtains after pulverizing changes porcelain boat over to, is placed in the chamber type electric resistance furnace roasting, and maturing temperature is 400～600 ℃, and roasting time is 4～10h, obtains the mixture of molybdenum and Si oxide;
(3) powder and the deionized water that obtains after oxidation was configured to the mixture slurry in 1: 10～1: 5 according to weight ratio;
(4) add solid NaOH in the mixture slurry of the powder after the oxidation and deionized water, the mass ratio of NaOH and powder is 0.5～1.2; 60～90 ℃ of magnetic agitation 1～2h, cooled and filtered is got filtering solution;
(5) adding in advance massfraction in beaker is 37.5% concentrated hydrochloric acid, and concentrated hydrochloric acid is 1: 8～1: 15 with the ratio of liquor capacity, solution is slowly poured in concentrated hydrochloric acid, and stirred;
(6) solution of step (5) is put into 40～80 ℃ of heating of water-bath, and constantly stirred until there is silica gel to separate out, get its solution after filtration;
(7) add isopyknic propyl carbinol to extract in the solution of step (6), through three extractions, front twice standing 10～30min, separatory after last standing 20～40min is got top butanol solution after separatory;
(8) butanol solution that obtains after three extractions is mixed, then the saturated aqueous solution with propyl carbinol washs three times, and the butanol solution after washing is carried out underpressure distillation, obtains molybdenum sila polyacid product;
(9) with molybdenum sila polyacid product again with adding a small amount of nitric acid after deionized water dissolving, filter and wash away remaining propyl carbinol organism, drying obtains molybdenum sila polyacid product.
Compared with the prior art, the present invention can realize the recycling again of rare noble metal molybdenum and semiconductor alloy silicon in waste and old molybdenum disilicide, realizes the resource circulation utilization strategy, has synthesized a kind of novel material by the present invention---molybdenum sila polyacid.This technique is with strong points, effective, has practicality widely aspect the recycle of waste silicon molybdenum rod and molybdenum silicon goods.
Description of drawings
Fig. 1 is the X ray diffracting spectrum that the present invention obtains product, can find out, can access molybdenum sila polyacid according to the present invention.
Fig. 2 is the macro morphology of the molybdenum sila polyacid for preparing of the present invention.
Embodiment
Embodiment 1: waste and old molybdenum disilicide is ground into the powder of 2 microns, then be placed in electric furnace at 600 ℃ of lower roasting 10h, the powder and the deionized water that obtain after roasting are configured to the mixture slurry according to weight ratio at 1: 10, then add solid NaOH, the mass ratio of NaOH and powder is 0.5,60 ℃ of magnetic agitation 2h, cooled and filtered, filtrate is poured in concentrated hydrochloric acid, and concentrated hydrochloric acid is 1: 8 with the ratio of liquor capacity, stirs; Solution is put into water-bath, 40 ℃ of heating, and constantly stir until there is silica gel to separate out, get its solution after filtration; Add isopyknic propyl carbinol to extract in solution, through three grades of extractions, front twice standing 10min, separatory after last standing 20min with the saturated aqueous solution washing of propyl carbinol, then carries out underpressure distillation, gets the heteropolyacid product; With adding a small amount of nitric acid after deionized water dissolving, to filter and wash away remaining propyl carbinol organism, drying obtains molybdenum sila polyacid.
Embodiment 2: waste and old molybdenum disilicide is ground into the powder of 15 microns, then be placed in electric furnace at 400 ℃ of lower roasting 8h, the powder and the deionized water that obtain after roasting are configured to the mixture slurry according to weight ratio at 1: 8, then add solid NaOH, the mass ratio of NaOH and powder is 0.7,70 ℃ of magnetic agitation 1.7h, cooled and filtered, filtrate is poured in concentrated hydrochloric acid, and concentrated hydrochloric acid is 1: 10 with the ratio of liquor capacity, stirs; Solution is put into water-bath, 60 ℃ of heating, and constantly stir until there is silica gel to separate out, get its solution after filtration; Add isopyknic propyl carbinol to extract in solution, through three grades of extractions, front twice standing 15min, separatory after last standing 25min with the saturated aqueous solution washing of propyl carbinol, then carries out underpressure distillation, gets the heteropolyacid product; With adding a small amount of nitric acid after deionized water dissolving, to filter and wash away remaining propyl carbinol organism, drying obtains molybdenum sila polyacid.
Embodiment 3. is ground into waste and old molybdenum disilicide in the powder of 12 microns, then be placed in electric furnace at 500 ℃ of lower roasting 4h, the powder and the deionized water that obtain after roasting are configured to the mixture slurry according to weight ratio at 1: 7, then add solid NaOH, the mass ratio of NaOH and powder is 0.8,80 ℃ of magnetic agitation 1.5h, cooled and filtered, filtrate is poured in concentrated hydrochloric acid, and concentrated hydrochloric acid is 1: 12 with the ratio of liquor capacity, stirs; Solution is put into water-bath, 70 ℃ of heating, and constantly stir until there is silica gel to separate out, get its solution after filtration; Add isopyknic propyl carbinol to extract in solution, through three grades of extractions, front twice standing 20min, separatory after last standing 30min with the saturated aqueous solution washing of propyl carbinol, then carries out underpressure distillation, gets the heteropolyacid product; With adding a small amount of nitric acid after deionized water dissolving, to filter and wash away remaining propyl carbinol organism, drying obtains molybdenum sila polyacid.
Embodiment 4. is ground into waste and old molybdenum disilicide in the powder of 9 microns, then be placed in electric furnace at 450 ℃ of lower roasting 6h, the powder and the deionized water that obtain after roasting are configured to the mixture slurry according to weight ratio at 1: 6, then add solid NaOH, the mass ratio of NaOH and powder is 1.0,85 ℃ of magnetic agitation 1.2h, cooled and filtered, filtrate is poured in concentrated hydrochloric acid, and concentrated hydrochloric acid is 1: 13 with the ratio of liquor capacity, stirs; Solution is put into water-bath, 50 ℃ of heating, and constantly stir until there is silica gel to separate out, get its solution after filtration; Add isopyknic propyl carbinol to extract in solution, through three grades of extractions, front twice standing 25min, separatory after last standing 35min with the saturated aqueous solution washing of propyl carbinol, then carries out underpressure distillation, gets the heteropolyacid product; With adding a small amount of nitric acid after deionized water dissolving, to filter and wash away remaining propyl carbinol organism, drying obtains molybdenum sila polyacid.
Claims (1)
1. a technique that reclaims molybdenum sila polyacid from waste and old molybdenum disilicide, is characterized in that; Processing step is as follows:
(1) waste and old molybdenum disilicide is ground into is of a size of the powder of 2～15 microns;
(2) material that obtains after pulverizing changes porcelain boat over to, is placed in the chamber type electric resistance furnace roasting, and maturing temperature is 400～600 ℃, and roasting time is 4～10h, obtains the mixture of molybdenum and Si oxide;
(3) powder and the deionized water that obtains after oxidation is configured to the mixture slurry according to weight ratio 1:10～1:5;
(4) add solid NaOH in the mixture slurry of the powder after the oxidation and deionized water, the mass ratio of NaOH and powder is 0.5 ~ 1.2,60～90 ℃ of magnetic agitation 1～2h, and cooled and filtered is got filtering solution;
(5) adding in advance massfraction in beaker is 37.5% concentrated hydrochloric acid, and concentrated hydrochloric acid is 1:8 ~ 1:15 with the ratio of liquor capacity, solution is slowly poured in concentrated hydrochloric acid, and stirred;
(6) solution of step (5) is put into 40～80 ℃ of heating of water-bath, and constantly stirred until there is silica gel to separate out, get its solution after filtration;
(7) add isopyknic propyl carbinol to extract in the solution of step (6), through three extractions, front twice standing 10～30min, separatory after last standing 20～40min is got top butanol solution after separatory;
(8) butanol solution that obtains after three extractions is mixed, then the saturated aqueous solution with propyl carbinol washs three times, and the butanol solution after washing is carried out underpressure distillation, obtains molybdenum sila polyacid crude product;
(9) with molybdenum sila polyacid crude product again with adding a small amount of nitric acid after deionized water dissolving, filter and wash away remaining propyl carbinol organism, drying obtains molybdenum sila polyacid product.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101456590A (en) * | 2009-01-09 | 2009-06-17 | 中国矿业大学 | Recovery process of waste and old molybdenum disilicide |
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| CN101456590A (en) * | 2009-01-09 | 2009-06-17 | 中国矿业大学 | Recovery process of waste and old molybdenum disilicide |
Non-Patent Citations (4)
| Title |
|---|
| Keggin结构钼磷和钼硅杂多酸盐热稳定性研究;王恩波等;《无机化学学报》;19941231;第10卷(第4期);352-357 * |
| 张帅等.钼资源回收工艺现状及展望.《无机盐工业》.2011,第43卷(第12期),12-15. |
| 王恩波等.Keggin结构钼磷和钼硅杂多酸盐热稳定性研究.《无机化学学报》.1994,第10卷(第4期),352-357. |
| 钼资源回收工艺现状及展望;张帅等;《无机盐工业》;20111231;第43卷(第12期);12-15 * |
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