CN102674377B - Quartz crystal type conversion metal element gasification integration purification method - Google Patents
Quartz crystal type conversion metal element gasification integration purification method Download PDFInfo
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Abstract
The invention relates to a quartz crystal type conversion metal element gasification integration purification method. The quartz crystal type conversion metal element gasification integration purification method is characterized by including the following steps: high temperature gasification reaction is performed on vein quartz sand and a specific mixed gas for 60-180 minutes at the temperature in a range of 1400-1700 DEG C, and the specific mixed gas is a mixed gas of HC1 and C12 according to a volume ratio of 1:1-9:1 or a mixed gas of C12 and N2 according to a volume ratio of 1:1-9:1. The quartz crystal type conversion metal element gasification integration purification method can achieve conversion of alpha-quartz to beta-cristobalite, further gasifies and reduces impurity metal element content in a quartz crystal lattice, and achieves the cristobalite with ultra-low metal elements.
Description
Technical field
The invention belongs to inorganic materials class field, particularly the integrated method of purification of a kind of quartzy crystal formation conversion metallic element gasification.
Background technology
Quartz is the essential mineral of siliceous resource.Quartz comprises the low quartz (alpha-quartz) of trigonal system and the high quartz (β-cristobalite) of hexagonal system, and general alleged quartz refers to that all low quartz is alpha-quartz.
Natural vein quartz is as a kind of siliceous resource of high-quality, and its mineral composition is all almost quartzy, SiO
2Content can reach 97% ~ 99%.The day by day exhausted present situation of Crystal Resances substitutes ultra-pure vein quartz when unmodifiable to substitute crystal be a kind of inevitable development trend.Traditional vein quartz processing technology is the operations such as fragmentation, high-temperature roasting, shrend, ore grinding, magnetic separation, electric separation, flotation, chemical purification, the quartzy SiO that obtains
2Content can reach 99.95% 99.99% left and right even, but the impurity metallic elements total amount is mostly at 50 ~ 100ppm, is difficult to meet some quartzy specific end use as prepared solar energy polycrystalline silicon, silicon single crystal with the requirement to quartz raw material such as crucible level quartz material.
Present quartzy crystal formation heat conversion method can only realize the purpose of single crystal form conversion, and to products obtained therefrom purity improve and the reduction of foreign metal content without obvious effect.If can study a kind of can reaching when realizing crystal formation conversion, reduce foreign metal content, improve the method for quartzy product purity, efficient utilization and purification for the vein quartz resource will have great importance, the quartzy product for preparing thus is ultra-pure quartz, therefore can meet modern high technology some specific end use requirements to quartz.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, to provide a kind of quartzy crystal formation conversion metallic element gasification integrated method of purification.It can further reduce the metallic impurity elements content in quartz when realizing changing β-cristobalite into by alpha-quartz, reach the purpose of ultralow metallic element cristobalite.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
The integrated method of purification of a kind of quartzy crystal formation conversion metallic element gasification, is characterized in that, it comprises the following steps:
Vein quartz sand and specific blend gas are carried out to high-temperature gasification reaction 60 ~ 180min in 1400 ~ 1700 ℃ of scopes, described specific blend gas is HCl and Cl
2Be the mixed gas of 1:1 ~ 9:1 by volume, or be Cl
2With N
2Be the mixed gas of 1:1 ~ 9:1 by volume.
Press such scheme, described vein quartz sand adopts and adds continuously mode or fixed time interval mode to add.
Press such scheme, described specific blend gas adds vein quartz sand again system first to be vacuumized afterwards and adds in system.
Press such scheme, described specific blend gas passes in temperature-rise period with the form of gas stream, and the flow of described specific blend gas is 200 ~ 4000ml/min.
Press such scheme, described specific blend gas passes into when being warming up to 500-900 ℃, and insulation 0.5-2h, then continues to be warming up to target temperature, carries out the high-temperature gasification reaction.
Press such scheme, during described high-temperature gasification reaction, the control system pressure is >=0.1MPa.
Press such scheme, the integrated method of purification of described quartzy crystal formation conversion metallic element gasification also is included in after the high-temperature gasification reaction completes the nitrogen that stops passing into specific blend gas and pass into 100～300ml/min, and the product after then cooling being come out of the stove washs, dry post-processing step.
Press such scheme, the integrated method of purification of described quartzy crystal formation conversion metallic element gasification also comprises carries out high-temperature gasification reaction re-treatment again by the reacted product of high-temperature gasification.
Press such scheme, described vein quartz sand is SiO
2Content>=99.99wt%, impurity metallic elements total amount ﹤ 30ppm, granularity is the glass sand of 96 ~ 250 μ m.It can directly be bought and obtains or adopt following method of purification to obtain:
(1) select materials
Choose the vein quartz sand of 96 ~ 250 μ m, described vein quartz sand meets 100/mm of fluid inclusion quantity ﹤
2, impurity metallic elements total amount ﹤ 100ppm;
(2) calcining-water quenching or ultrasonication are removed inclusion;
(3) chemical purification
Product after above-mentioned steps (2) is processed is placed in mixing acid and carries out the chemical oxidation reaction purification, and temperature of reaction is 20～100 ℃, and the reaction times is 5～15 hours, and described mixing acid is HF, HNO
3, HCl mixing solutions, in described mixing solutions, the content of HF is 2.5wt%～4wt%, HNO
3Content 2.5wt%～4wt%, content 20wt%～40wt% of HCl;
(4) chelating
Product after above-mentioned steps (3) is processed reacted 5～15 hours in ° C chelating liquid of 50 ° of C～100, wherein said chelating liquid is oxalic acid solution;
(5) will leach through the quartz sand of above-mentioned chelating liquid reaction, be washed to neutrality, dry and get final product.
Press such scheme, the vein quartz sand of described 96 ~ 250 μ m obtains the vein quartz raw ore through selection, fragmentation, ore grinding, high intensity magnetic separation, classification, SiO in described vein quartz raw ore
2Content>=98.5wt%.
Press such scheme, described fluid inclusion number can obtain according to following measuring method: 1. the vein quartz raw ore is made to otpical leaf; 2. otpical leaf is placed under transmission microscopy and observes; 3. choose at random a plurality of 1mm under thin slice
2Zone, statistics fluid inclusion number, finally get its average.
Press such scheme, the calcining-water quenching in described step (2) is: get the vein quartz sand of above-mentioned 96 ~ 250 μ m under 300～500 ℃, roasting 1h～5h, then be placed in frozen water shrend, filtration, oven dry.
Press such scheme, the supersound process in described step (2) is: the vein quartz sand of getting above-mentioned 96 ~ 250 μ m is modulated into ore pulp, the ultrasonication 10～30min take ultrasonic power as 1-2Kw, filtration, oven dry.
Press such scheme, described pulp density is 20wt%-40wt%.
Press such scheme, the product quality ratio after the mixing acid in described step (3) and step (2) are processed is 1～2:1.
Press such scheme, the mass percent of the oxalic acid solution mesoxalic acid in described step (4) is 2.5wt%～4.5wt%.
Press such scheme, the mass ratio of the product after the oxalic acid solution in described step (4) and step (3) are processed is 1～2:1.
Press such scheme, the washing of described step (5), for first using organic solvent washing, is removed the organism of quartz sand surface absorption, then washs with the mixing solutions of organic solvent and water, and is finally extremely neutral with deionized water wash.
Alpha-quartz changes β-quartz at 573 ° of C under normal pressure, continues to heat to 870 ° of C to change β-tridymite into, then continues to heat to 1470 ° of C and change β-cristobalite (β-cristobalite) into.The present invention is by controlling reaction conditions, what temperature of reaction rose to 1700 ° of C, be subjected to thermal process, quartzy can the variation by three crystal formations of generation, on vein quartz sand surface, crack, simultaneously, the impurity metallic elements that is present in quartz crystal in the isomorph mode can react with specific blend gas wherein and gasify effusion, can reach thus part and remove impurity metallic elements, realize the polymorphic transformation of crystalline structure, namely by alpha-quartz, change β-cristobalite into, further reduce the metal content in vein quartz, reach the purpose of purification.In this quartz crystal formation conversion and purge process, impurity metallic elements can play mineralizer simultaneously, promotes the transformation of quartzy crystal formation.
Beneficial effect of the present invention:
(1) the present invention is by controlling vein quartz sand and specific blend gas gasification reaction conditions at high temperature, the purpose that realizes when quartzy crystal formation is changed removing the fluid impurity in vein quartz sand crystal body and reduce impurity metallic elements content, realized ultralow metallic element cristobalite.It is SiO that the present invention preferably selects pan feeding
2The glass sand of>=99.995wt%, foreign matter content ﹤ 30ppm, the ultra-pure quartz sand impurity metallic elements content for preparing even can reach the requirement lower than 20ppm, meets some quartzy specific end use as prepared the requirement to quartz raw material such as solar energy polycrystalline silicon, silicon single crystal crucible level quartz material, crystalline silicon, electronic material, opticglass, laser glass, high temp glass, crystal level fused quartz, aerospacecraft sight glass, senior trombone slide glass, radiation shielding glass.
(2) the method technique is easily controlled, and the quartz sand purity that makes is high, and metal element content is low.
Embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate summary of the invention of the present invention, but content of the present invention not only is confined to the following examples; Should not be considered as limitation of the present invention yet.
Vein quartz sandy plain material in embodiment 1-4 is prepared by following methods:
(1) select materials
The vein quartz raw ore is prepared into the vein quartz sand of 96 ~ 250 μ m through selection, fragmentation, ore grinding, high intensity magnetic separation, classification, described vein quartz sand meets the quantity of fluid inclusion<100/mm
2, SiO
2Content>=98.5wt%, impurity metallic elements total amount 50ppm.
(2) calcining-water quenching
The vein quartz sand of getting 96 ~ 250 μ m that above-mentioned classification obtains in the retort furnace of 500 ℃ after roasting 2h, is placed in the frozen water Water Quenching to quartz sand and frozen water constant temperature, precipitation, filtration, oven dry.
(3) chemical purification
The shrend product was reacted 15 hours in 60 ° of C mixing acid, described mixing acid is HF, HNO
3, HCl mixing solutions, in described mixing solutions, the content of HF is 4wt%, HNO
3Content be that the content of 2.5wt%, HCl is 35wt%, the mass ratio of described mixing acid and shrend product is 1:1.
(4) chelating
Product after above-mentioned steps (3) Ore Leaching is transferred in 70 ° of C oxalic acid solutions that mass percentage concentration is 3wt% and reacted 7 hours, and the mass ratio that described oxalic acid solution and above-mentioned steps (3) obtain product is 2:1.
(5) will leach through the reacted quartz sand of above-mentioned oxalic acid solution, and with organic solvent, clean 5 times, then wash 3 times with the mixing solutions of organic solvent and deionized water, finally extremely neutral with deionized water wash, oven dry, obtain.The quartz specimen that this technique obtains is through ICP total analysis test, and major impurity metal element content and metallic element total amount are as shown in table 1.
Vein quartz sand in embodiment 5 is purchased from Pacific Ocean quartz ware company limited, and model is PQC, and purity is 99.99wt%, impurity metallic elements total amount<30ppm, granularity 96 ~ 250 μ m.Impurity metallic elements total amount and major impurity metallic element index are in Table 2.
Vein quartz sand in embodiment 6 reaches quartzy company limited and provides by Jiangsu is triumphant, and purity is 99.99%, impurity metallic elements content<50ppm, granularity 96 ~ 250 μ m.Impurity metallic elements total amount and major impurity metallic element index are in Table 3.
Vein quartz sand in embodiment 7 reaches quartzy company limited and provides by Jiangsu is triumphant, and purity is 99.9wt%, impurity metallic elements content<200ppm, granularity 96 ~ 250 μ m.Impurity metallic elements total amount and major impurity metallic element index are in Table 4.
Vein quartz sandy plain material in embodiment 8 is prepared by following methods:
(1) select materials
The vein quartz raw ore is prepared into the vein quartz sand of 96 ~ 250 μ m through selection, fragmentation, ore grinding, high intensity magnetic separation, classification, described vein quartz sand meets the quantity of fluid inclusion<100/mm
2, SiO
2Content>=98.5wt%, impurity metallic elements total amount ﹤ 100ppm.
(2) calcining-water quenching
The vein quartz sand of getting 96 ~ 250 μ m that above-mentioned classification obtains in the retort furnace of 400 ℃ after roasting 1h, is placed in the frozen water Water Quenching to quartz sand and frozen water constant temperature, precipitation, filtration, oven dry.
(3) chemical purification
The shrend product was reacted 5 hours in 30 ° of C mixing acid, described mixing acid is HF, HNO
3, HCl mixing solutions, in described mixing solutions, the content of HF is 3wt%, HNO
3Content be that the content of 4wt%, HCl is 30wt%.
(4) chelating
Product after above-mentioned steps (3) Ore Leaching is transferred in 80 ° of C oxalic acid solutions and reacted 10 hours.
(5) will leach through the reacted quartz sand of above-mentioned oxalic acid solution, and be washed to neutrality, oven dry, obtain.The quartz specimen that this technique obtains is through ICP total analysis test, and impurity metallic elements total amount and major impurity metallic element index are as shown in table 5.
Vein quartz sandy plain material in embodiment 9 is prepared by following methods:
(1) select materials
Choose the quantity of fluid inclusion<100/mm
2, SiO
2Content>=98.5wt%, the vein quartz sand of impurity metallic elements total amount 70ppm.(2) ultrasonication is removed inclusion
Getting 96 ~ 250 μ m quartz sand furnishing concentration that above-mentioned classification obtains is the ore pulp of 40wt%, with the ultrasonication 30min of ultrasonic power 1.5Kw, filters drying.
(3) chemical purification
Product after ultrasonication was reacted 5 hours in 60 ° of C mixing acid, described mixing acid is HF, HNO
3, HCl mixing solutions, in described mixing solutions, the content of HF is 3wt%, HNO
3Content be that the content of 3wt%, HCl is 35wt%, described mixing acid is 2:1 with the mass ratio of product after ultrasonication.
(4) chelating
Product after above-mentioned steps (3) Ore Leaching is transferred in 60 ° of C oxalic acid solutions that mass percentage concentration is 4wt% and reacted 5 hours, and the mass ratio that described oxalic acid solution and above-mentioned steps (3) obtain product is 2:1.
(5) will leach through the reacted quartz sand of above-mentioned oxalic acid solution, washing is to neutral, and oven dry, obtain.The quartz specimen that this technique obtains is through ICP total analysis test, and impurity metallic elements total amount and major impurity metallic element index are as shown in table 5.
Vein quartz sandy plain material in embodiment 10 is prepared by following methods:
(1) select materials
The vein quartz raw ore is prepared into the vein quartz sand of 96 ~ 250 μ m through selection, fragmentation, ore grinding, high intensity magnetic separation, classification, described vein quartz sand meets the quantity of fluid inclusion<100/mm
2, SiO
2Content>=98.5wt%, impurity metallic elements total amount 42ppm.
(2) calcining-water quenching
The vein quartz sand of getting 96 ~ 250 μ m that above-mentioned classification obtains in the retort furnace of 300 ℃ after roasting 5h, is placed in the frozen water Water Quenching to quartz sand and frozen water constant temperature, precipitation, filtration, oven dry.
(3) chemical purification
The shrend product was reacted 8 hours in 90 ° of C mixing acid, described mixing acid is HF, HNO
3, HCl mixing solutions, in described mixing solutions, the content of HF is 4wt%, HNO
3Content be that the content of 4wt%, HCl is 30wt%, the mass ratio of described mixing acid and shrend product is 1:1.
(4) chelating
Product after above-mentioned steps (3) Ore Leaching is transferred in 80 ° of C oxalic acid solutions that mass percentage concentration is 3wt% and reacted 8 hours, and the mass ratio that described oxalic acid solution and above-mentioned steps (3) obtain product is 2:1.
(5) will leach through the reacted quartz sand of above-mentioned oxalic acid solution, and with organic solvent, clean 5 times, then use 10%(V/V) the mixing solutions washing of organic solvent+90% (V/V) deionized water 3 times, finally with deionized water wash to neutral, oven dry, obtain.The quartz specimen that this technique obtains is through ICP total analysis test, and impurity metallic elements total amount and major impurity metallic element index are as shown in table 5.
Embodiment 1:
Take a certain amount of above-mentioned SiO for preparing
2The glass sand sample of>=99.99wt%, impurity metallic elements total amount<30ppm, put into the vacuum high-temperature tube-type atmosphere furnace, adds after quartz sand to start pre-heating temperature elevation, take out in reaction tubes vacuum to≤1.0 p
aAnd passing into cooling circulating water, the flow with 1500ml/min when system temperature reaches 600 ℃ passes into mixed gas, wherein HCl and Cl
2Volume ratio is 4:1, insulation 1h, then continue to be warming up to 1700 ℃, pressure is 0.3Mpa, after gasification reaction 180min, stop the nitrogen that passes into mixed gas and pass into 100ml/min after stopped heating, after being down to room temperature, take out quartz specimen, deionized water fully washs, and drying is ultra-pure cristobalite.
The sample metallic element tests and calculates SiO with ICP
2Content, the variation of quartzy lattice XRD phenetic analysis.
Wherein quartzy crystal formation turnover ratio is by the diffracted intensity I of vein quartz and cristobalite in the XRD figure spectrum
Q, I
CR, by formula C
CR=I
CR/ (I
CR+ 0.61I
Q) calculate SiO
2Content, impurity metallic elements total amount and major impurity metallic element index through ICP total analysis test, obtain, result is as shown in table 1.
Embodiment 2:
Take a certain amount of above-mentioned SiO for preparing
2The glass sand sample of>=99.99wt%, impurity metallic elements total amount<30ppm, 96 ~ 250 μ m, put into reactor, add after quartz sand to start pre-heating temperature elevation, vacuumize, the flow with 4000ml/min when system temperature reaches 900 ℃ passes into mixed gas, wherein HCl and Cl
2Volume ratio is 1:1, insulation 0.5h, then continue to be warming up to 1500 ℃, pressure is 0.5Mpa, after gasification reaction 130min, stop the nitrogen that passes into mixed gas and pass into 200ml/min after stopped heating, after being down to room temperature, take out quartz specimen, deionized water fully washs, and drying is ultra-pure cristobalite.
The sample metallic element tests and calculates SiO with ICP
2Content, the variation of lattice XRD phenetic analysis.Quartzy crystal formation turnover ratio, SiO
2Content, impurity metallic elements total amount and major impurity metallic element index as shown in table 1.
Embodiment 3:
Take a certain amount of above-mentioned SiO for preparing
2The glass sand sample of>=99.99wt%, impurity metallic elements total amount<30ppm, 96 ~ 250 μ m, put into the vacuum high-temperature tube-type atmosphere furnace, add after quartz sand to start pre-heating temperature elevation, vacuumize, the flow with 2500ml/min when system temperature reaches 500 ℃ passes into mixed gas, wherein Cl
2With N
2Volume ratio is 5:1, insulation 1h, then continue to be warming up to 1600 ℃, pressure is 0.35Mpa, after gasification reaction 60min, stop the nitrogen that passes into mixed gas and pass into 100ml/min after stopped heating, after being down to room temperature, take out quartz specimen, deionized water fully washs, and drying is ultra-pure cristobalite.
The sample metallic element tests and calculates SiO with ICP
2Content, the variation of lattice XRD phenetic analysis.Quartzy crystal formation turnover ratio, SiO
2Content, impurity metallic elements total amount and major impurity metallic element index as shown in table 1.
Embodiment 4:
Take a certain amount of above-mentioned SiO for preparing
2The glass sand sample of>=99.99wt%, impurity metallic elements total amount<30ppm, 96 ~ 250 μ m, put into reactor, add after quartz sand to start pre-heating temperature elevation, vacuumize, when system temperature reaches 800 ℃, pass into the 300ml/min mixed gas, wherein HCl and Cl
2Volume ratio is 5:1, and insulation 1h, then continue to be warming up to 1400 ℃, and pressure is 0.1Mpa, and after gasification reaction 150min, cooling is come out of the stove, and deionized water fully washs, and drying is ultra-pure cristobalite.
The sample metallic element tests and calculates SiO with ICP
2Content, the variation of lattice XRD phenetic analysis.Quartzy crystal formation turnover ratio, SiO
2Content, impurity metallic elements total amount and major impurity metallic element index as shown in table 1.
Table 1
Embodiment 5:
Take the glass sand that a certain amount of Pacific Ocean quartz ware company limited produces, wherein SiO
2>=99.99wt%, impurity metallic elements total amount<30ppm, granularity 96 ~ 250 μ m, put into reactor, add after quartz sand start pre-heating temperature elevation, the flow with 500ml/min when system temperature reaches 700 ℃ passes into mixed gas, wherein HCl and Cl
2Volume ratio is 9:1, insulation 1h, then continue to be warming up to 1400 ℃, pressure is 0.15Mpa, after gasification reaction 180min, stop the nitrogen that passes into mixed gas and pass into 200ml/min after stopped heating, after being down to room temperature, take out quartz specimen, deionized water fully washs, and drying is ultra-pure cristobalite.
The sample metallic element tests and calculates SiO with ICP
2Content, the variation of lattice XRD phenetic analysis.Quartzy crystal formation turnover ratio, SiO
2Content, impurity metallic elements total amount and major impurity metallic element index as shown in table 2.
Table 2
Embodiment 6:
Take the triumphant glass sand that quartzy company limited produces, the wherein SiO of reaching in a certain amount of Jiangsu
2>=99.99wt%, impurity metallic elements total amount 40 ~ 50ppm, granularity 96 ~ 250 μ m, put into reactor, add after quartz sand to start pre-heating temperature elevation, vacuumize, and be warming up to gradually 1400 ℃, flow with 500ml/min in temperature-rise period passes into mixed gas, wherein Cl
2With N
2Volume ratio is 9:1, and pressure is 0.15Mpa, after gasification reaction 180min, stops the nitrogen that passes into mixed gas and pass into 100ml/min after stopped heating, after being down to room temperature, takes out quartz specimen, and deionized water fully washs, and drying is ultra-pure cristobalite.
The sample metallic element tests and calculates SiO with ICP
2Content, the variation of lattice XRD phenetic analysis.Quartzy crystal formation turnover ratio, SiO
2Content, impurity metallic elements total amount and major impurity metallic element index as shown in table 3.
Table 3
Embodiment 7:
Take the triumphant glass sand that quartzy company limited produces, the wherein SiO of reaching in a certain amount of Jiangsu
2>=99.9wt%, impurity metallic elements total amount<200ppm, granularity 96 ~ 250 μ m, put into reactor, adds after quartz sand to start pre-heating temperature elevation, vacuumize, and the flow with 1500ml/min when system temperature reaches 700 ℃ passes into mixed gas, wherein Cl
2With N
2Volume ratio is 1:1, insulation 2h, then continue to be warming up to 1600 ℃, pressure is 0.15Mpa, after gasification reaction 150min, stop the nitrogen that passes into mixed gas and pass into 250ml/min after stopped heating, after being down to room temperature, take out quartz specimen, deionized water fully washs, and drying is ultra-pure cristobalite.
The sample metallic element tests and calculates SiO with ICP
2Content, the variation of lattice XRD phenetic analysis.Quartzy crystal formation turnover ratio, SiO
2Content, impurity metallic elements total amount and major impurity metallic element index as shown in table 4.
Table 4
Embodiment 8:
Take a certain amount of above-mentioned SiO for preparing
2The glass sand sample of>=99.99wt%, impurity metallic elements total amount<30ppm, granularity 96 ~ 250 μ m (the impurity metallic elements total amount of this glass sand sample raw material and each major impurity metallic element index are as shown in table 5), put into reactor, add after quartz sand and start pre-heating temperature elevation, vacuumize, flow with 300ml/min when system temperature reaches 700 ℃ passes into mixed gas, wherein HCl and Cl
2Volume ratio is 5:1, insulation 2h, then continue to be warming up to 1400 ℃, pressure is 0.1Mpa, after gasification reaction 150min, stop the nitrogen that passes into mixed gas and pass into 150ml/min after stopped heating, after being down to room temperature, take out quartz specimen, deionized water fully washs, and drying is ultra-pure cristobalite.
Embodiment 9:
Take a certain amount of above-mentioned SiO for preparing
2The glass sand sample of>=99.99wt%, impurity metallic elements total amount<30ppm, granularity 96 ~ 250 μ m (the impurity metallic elements total amount of this glass sand sample raw material and each major impurity metallic element index are as shown in table 5), put into reactor, add after quartz sand and start pre-heating temperature elevation, vacuumize, when system temperature reaches 700 ℃ with the flow mixed gas of 2500ml/min, wherein HCl and Cl
2Volume ratio is 5:1, insulation 2h, then continue to be warming up to 1600 ℃, pressure is 0.35Mpa, after gasification reaction 60min, stop the nitrogen that passes into mixed gas and pass into 200ml/min after stopped heating, after being down to room temperature, take out quartz specimen, deionized water fully washs, and drying is ultra-pure cristobalite.
Embodiment 10:
Take a certain amount of above-mentioned SiO for preparing
2The glass sand sample of>=99.99wt%, impurity metallic elements total amount<30ppm, granularity 96 ~ 250 μ m (the impurity metallic elements total amount of this glass sand sample raw material and each major impurity metallic element index are as shown in table 5), put into reactor, add after quartz sand and start pre-heating temperature elevation, vacuumize, flow with 500ml/min when system temperature reaches 700 ℃ passes into mixed gas, wherein HCl and Cl
2Volume ratio is 9:1, insulation 2h, then continue to be warming up to 1400 ℃, pressure is 0.2Mpa, after gasification reaction 180min, stop the nitrogen that passes into mixed gas and pass into 100ml/min after stopped heating, after being down to room temperature, take out quartz specimen, deionized water fully washs, and drying is ultra-pure cristobalite.
Table 5
Each concrete raw material that the present invention is cited, and the bound of each raw material, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention, at this, do not enumerate embodiment.
Claims (11)
1. the integrated method of purification of quartzy crystal formation conversion metallic element gasification, is characterized in that, it comprises the following steps:
Vein quartz sand and specific blend gas are carried out to high-temperature gasification reaction 60 ~ 180min in 1400 ~ 1700 ℃ of scopes, described specific blend gas is HCl and Cl
2Be the mixed gas of 1:1 ~ 9:1 by volume, or be Cl
2With N
2Be the mixed gas of 1:1 ~ 9:1 by volume; Described vein quartz sand is SiO
2Content>=99.99wt%, impurity metallic elements total amount ﹤ 30ppm, granularity is the glass sand of 96 ~ 250 μ m.
2. quartzy crystal formation according to claim 1 is changed the integrated method of purification of metallic element gasification, it is characterized in that: described vein quartz sand adopts and adds continuously mode or fixed time interval mode to add.
3. quartzy crystal formation according to claim 1 is changed the integrated method of purification of metallic element gasification, and it is characterized in that: described specific blend gas adds after in system, adding vein quartz sand then system to be vacuumized.
4. quartzy crystal formation according to claim 1 is changed the integrated method of purification of metallic element gasification, it is characterized in that: described specific blend gas passes in temperature-rise period with the form of gas stream, and the flow of described specific blend gas is 200 ~ 4000ml/min.
5. quartzy crystal formation according to claim 1 is changed the integrated method of purification of metallic element gasification, it is characterized in that: described specific blend gas passes into when being warming up to 500-900 ℃, and insulation 0.5-2h, then continue to be warming up to target temperature, carry out the high-temperature gasification reaction.
6. quartzy crystal formation according to claim 1 is changed the integrated method of purification of metallic element gasification, it is characterized in that: during described high-temperature gasification reaction, controlling system pressure is >=0.1MPa.
7. quartzy crystal formation according to claim 1 is changed the integrated method of purification of metallic element gasification, it is characterized in that: the integrated method of purification of described quartzy crystal formation conversion metallic element gasification also is included in after the high-temperature gasification reaction completes the nitrogen that stops passing into specific blend gas and pass into 100～300ml/min, and the product after then cooling being come out of the stove washs, dry post-processing step.
8. quartzy crystal formation according to claim 1 is changed the integrated method of purification of metallic element gasification, it is characterized in that: the integrated method of purification of described quartzy crystal formation conversion metallic element gasification also comprises carries out high-temperature gasification reaction re-treatment again by the reacted product of high-temperature gasification.
9. quartzy crystal formation according to claim 1 is changed the integrated method of purification of metallic element gasification, and it is characterized in that: described vein quartz sand can adopt following method of purification to obtain:
(1) select materials
Choose the vein quartz sand of 96 ~ 250 μ m, described vein quartz sand meets 100/mm of fluid inclusion quantity ﹤
2, impurity metallic elements total amount ﹤ 100ppm;
(2) calcining-water quenching or ultrasonication are removed inclusion;
(3) chemical purification
Product after above-mentioned steps (2) is processed is placed in mixing acid and carries out the chemical oxidation reaction purification, and temperature of reaction is 20～100 ℃, and the reaction times is 5～15 hours, and described mixing acid is HF, HNO
3, HCl mixing solutions, in described mixing solutions, the content of HF is 2.5wt%～4wt%, HNO
3Content 2.5wt%～4wt%, content 20wt%～40wt% of HCl;
(4) chelating
Product after above-mentioned steps (3) is processed reacted 5～15 hours in ° C chelating liquid of 50 ° of C～100, wherein said chelating liquid is oxalic acid solution;
(5) will leach through the quartz sand of above-mentioned chelating liquid reaction, be washed to neutrality, dry and get final product.
10. quartzy crystal formation according to claim 9 is changed the integrated method of purification of metallic element gasification, it is characterized in that: the calcining-water quenching in described step (2) is: get the vein quartz sand of above-mentioned 96 ~ 250 μ m under 300～500 ℃, roasting 1h～5h, then be placed in frozen water shrend, filtration, oven dry.
11. the integrated method of purification of quartzy crystal formation conversion metallic element gasification according to claim 9, it is characterized in that: the supersound process in described step (2) is: the vein quartz sand of getting above-mentioned 96 ~ 250 μ m is modulated into ore pulp, the ultrasonication 10～30min take ultrasonic power as 1-2Kw, filtration, oven dry.
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| CN105936509A (en) * | 2016-06-01 | 2016-09-14 | 安徽晶晶石英科技有限公司 | Purifying method of ultralow-metal element highly pure quartz |
| CN109574020A (en) * | 2019-01-03 | 2019-04-05 | 湖北省通发矿业有限责任公司 | A method of for large-scale production quartz sand except iron removal of impurities |
| CN112520987B (en) * | 2020-12-03 | 2022-01-28 | 东海县奥兰石英科技有限公司 | Preparation method for producing large-diameter quartz tube by multi-stage continuous melting integration method |
| CN112551532B (en) * | 2020-12-03 | 2022-03-08 | 东海县奥兰石英科技有限公司 | Process for removing impurities in quartz powder by continuous melting high-temperature thermal state method |
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Address after: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122 Patentee after: WUHAN University OF TECHNOLOGY Patentee after: JIANGSU KAIDA SILICA Co.,Ltd. Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122 Patentee before: WUHAN University OF TECHNOLOGY Patentee before: JIANGSU KAIDA SILICA Co.,Ltd. |
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