CN109399914A - Ultrapure no color spot top grade all-transparent quartz material of one kind and its preparation method and application - Google Patents
Ultrapure no color spot top grade all-transparent quartz material of one kind and its preparation method and application Download PDFInfo
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- CN109399914A CN109399914A CN201811165438.XA CN201811165438A CN109399914A CN 109399914 A CN109399914 A CN 109399914A CN 201811165438 A CN201811165438 A CN 201811165438A CN 109399914 A CN109399914 A CN 109399914A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/02—Pretreated ingredients
- C03C1/022—Purification of silica sand or other minerals
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
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Abstract
The invention discloses a kind of ultrapure no color spot top grade all-transparent quartz materials and its preparation method and application, after the present invention carries out purification processes to domestic quartzy silicon mine by processing steps such as selected quartzy silicon mine, water quenching, " chloroazotic acid " impurity elimination, esterification, flotation, magnetic separation, high-temperature vacuum processing, ultrasonic wave purifications, preparation can get without color spot top grade all-transparent silica glass ingot super pure silica material.The requirement of present invention combination commercial production scale; further perfect microwave treatment produces the process conditions of ultrapure no color spot top grade all-transparent quartz material; in particular for the ultrapure quartz sand raw material sources in China; conscientiously the manufacturing condition for being determined that domestic quartzy silicon mine produces ultrapure quartz sand raw material is provided; mature, reasonable, technical effect is stablized, and provides technical support for large-scale production, the real production cost preparation for reducing super pure silica glass ingot of super pure silica glass ingot.
Description
Technical field
The present invention relates to super pure silica technical field of material, high-grade complete more particularly, to a kind of ultrapure no color spot
Clear quartz material and its preparation method and application.
Background technique
In recent years with dust PM2.5, CO that manufacturing industry and building industry generate2、SO2Form haze, greenhouse effects and acid
Rain etc., seriously pollutes environment.It is reduced without reproducible disposable traditional fossil energy resource, finds the new energy and green energy
Source technology becomes current worldwide key subjects.Such as solar energy, it is the first choice of current new energy development, it is high in photovoltaic industry
Shelves quartz material is essential.With high-tech development, high-grade all-transparent quartz material demand is continuously increased, and natural water
Brilliant but exhausted, the eighties in last century, people get only the substitute of water detection crystalline substance, start to explore silicon ore instead of crystal
Deep refining research.
High-grade all-transparent silica glass ingot is SiO2Single content is up to 99.99% or more extraordinary quartz material, has
Chemical stabilization, all-transparent, impurity content are low, spectral transmission is wide, heat shock resistance is (when can be repeatedly long under 1420 DEG C of hot environments
Between using indeformable), resistance to x ray irradiation x, ultraviolet light penetrate entirely, devitrification resistance can strong, hardness up to seven grades of Mohs, the coefficient of expansion it is small,
The superior physical chemistry such as resistance to thermal shock is strong, electrical insulating property is good, the resistance to corrosion of nearly all acid in addition to hydrofluoric acid and hot phosphoric acid
Energy.
Currently, the whole world possesses the production for producing the core technology for the super pure silica material that SiO2 content reaches 99.99%
Producer is very few, and wherein the Unimin Corp. (US) (UNIMIN) in the U.S. and General Electric Co. Limited (GE) have almost monopolized entire ultrapure
Quartz sand material supply market.Either foreign enterprise or Chinese Enterprise are all using external import quartz silicon mine conduct mostly
Raw material carry out purification and prepare ultrapure no color spot top grade all-transparent quartz material, such as Madagascar, Norway's import quartz silicon
Mine, since the hydroxyl in external quartzy silicon mine, gas liquid inclusion content are lower than hydroxyl, gas liquid inclusion content in level-one crystal,
Also an order of magnitude lower than China's quartz silicon mine simultaneously, therefore conveniently by purification as substitution crystal material.But import resources
It is expensive, and limited by exported country and the exchange rate influences, this gives ultrapure no color spot top grade all-transparent quartz material material inlet
Source brings very big limitation, while also improving production cost.
Although China's quartz silicon ore resources deposit very abundant, cheap, hydroxyl, gas in domestic quartz silicon mine
Liquid inclusion enclave impurity content is much higher than external import quartz silicon mine, can not prepare ultrapure colourless spot top grade all-transparent quartz material with it
Material is distributed in mine containing the gas liquid inclusions such as B, P, methane, ethane are relatively uniform simultaneously the reason is that hydroxy radical content is high,
The ultrapure quartz sand of right quartz material again can not be unlimited levigate, and it is high-grade complete that this gives domestic quartzy silicon mine to prepare ultrapure no color spot
Clear quartz material brings technical difficulty, seriously limits the popularization and application of domestic quartzy silicon ore resources, and often
It is only used for preparing the quartz sand product of some low sides, can not be used to prepare the high-end products such as quartzy heavy stone used as an anchor.
The prior art pass through in domestic quartzy silicon mine preparation quartz sand in hydroxyl, B, P content be much higher than chalazie, and
And the gas liquid inclusion content in the quartz sand of domestic mine preparation is rejected not exclusively, the silica glass ingot prepared is often with indigo plant
Spot, which has limited the ultrapure no color spot top grade all-transparent quartz material substitution chalazies of common silicon ore purification to prepare quartz material,
And China substitutes the bottleneck that crystal prepares silica glass ingot material with silicon ore.
Since current technique limits, the quartz sand SiO of domestic quartz silicon mine production2Content can only at most reach 99.96%,
Technology stability is bad, and gained quartz sand quality is not high, and technology stability is bad, the silica glass ingot prepared often internal layer
Opaque or contain color spot, the transparency is not good enough.It is high-grade to ultrapure no color spot complete with the needs that China's high-tech technology develops
The demand of clear quartz material will be increasing, therefore, in order to break the external technical monopoly long-term in the field, sufficiently sends out
China natural resources advantage is waved, needs to realize domestic ultrapure no color spot top grade all-transparent quartz material industrialized production.
Summary of the invention
The technical problem to be solved by the present invention is to for hydroxy radical content and B, P impurity content in existing domestic quartz sand
Height causes the silica glass ingot of preparation the deficiency of locus coeruleus occur, provides the ultrapure no color spot height that a kind of hydroxy radical content is low, impurity is few
Shelves all-transparent quartz material.
Another technical problem to be solved by the present invention is that for ultrapure no color spot top grade all-transparent quartz material in the prior art
Material preparation process can not reject the deficiency of hydroxyl, provide and a kind of prepare silica glass ingot with ultrapure using common domestic quartzy silicon mine
Ultrapure no color spot top grade all-transparent quartz may be implemented in purifying technique without color spot top grade all-transparent quartz material, the process
Material (quartz sand) industrial-scale production uses domestic raw material completely, and at low cost, technical effect is stablized.
A present invention also technical problems to be solved are to provide the ultrapure no color spot top grade all-transparent quartz material application
In silica glass ingot, elevated temperature vessel field.
Ultrapure no color spot top grade all-transparent quartz material partial size provided by the invention is 90~220 mesh, in quartz material
SiO2Content is greater than 99.999%, hydroxy radical content < 6mg/kg, total content < 5mg/kg of P and B.
The ultrapure quartz sand of selection appropriate particle size not only contributes to the purification of quartz sand, and another party can also ensure subsequent top grade
The high-quality of all-transparent product.It is difficult to remove the impurity such as gas liquid inclusion in the excessive purification process of partial size while influencing to melt, grain
The too small one side of diameter destroys the lattice structure of quartz sand, while while quenching powdered particle is waved and flies to cause to waste, and waves winged
Fine dust is crossed it is also possible to setting off an explosion.
Specifically specifically include following preparation step:
S1.. selected quartzy silicon mine: the domestic common quartzy silicon mines in multiple areas are subjected to repeatedly icp analysis and are compared, are screened
Then domestic ordinary silicon mine needed for being suitble to this research out is soaked with low concentration acid solution with clean the surface impurity, then use deionization
Water is got express developed, and quartzy silicon mine crude product is obtained；
S2. water quenching: will heat after quartzy silicon mine crude product acidleach obtained by step S1, then quickly burst to the cold into the water,
A large amount of gas liquid inclusion is removed, crude product particle is obtained；
S3. acidleach: by crude product particle obtained by step S2 through Raymond mill, sieving, " chloroazotic acid " impregnates, and removal metal is miscellaneous
Matter, then rinsed with deionized water to get quartz sand crude product；
S4. it is esterified: the quartz sand crude product that step S4 is obtained being soaked in the ether containing acid anhydrides, and is connected with protection gas
Under conditions of body, magnetic agitation, quartz sand surface hydroxyl is esterified；
S5. flotation: flotation in flotation solvent is added in esterification quartz sand crude product obtained by step S4 and eliminates non-quartz sand
Grain；
S6. magnetic separation: the quartz sand crude product after step S5 flotation is rinsed with deionized water, after drying, then uses magnet separator magnetic
Choosing；
S7. high-temperature vacuum is handled: the step S6 quartz sand particle magneticly elected is placed under high temperature, vacuum condition and is kept the temperature,
Lead to chlorine treatment, superconduction purification after cooling again；
S8. ultrasonication: quartz sand particle obtained by step S7 is high-grade to get ultrapure no color spot by ultrasonication
All-transparent quartz material.
Further, it is low for 300~400mg/kg, gas liquid inclusion total content that alkali metal total content is filtered out in step S1
It is lower than the quartzy silicon mine of 38mg/kg in 2600mg/kg, B and P total content.
Preferably, the alkali metal total content filtered out in step S1 is 320~380mg/kg, gas liquid inclusion total content is
The quartzy silicon mine of 2000~2400mg/kg；B and P total content is lower than the quartzy silicon mine of 22mg/kg.
Further, acid solution described in step S1 is one or more of oxalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, the acid
Solution concentration is 1~10%.
Acid solution used excludes most strong using former corrosivity completely and can generate permanent damage to environment, generate forever simultaneously
Can not far wither away F-1HF acid.
Preferably, acid solution described in step S1 is one or more of hydrochloric acid, phosphoric acid, and the acid solutions are
3%.
Acid concentration is too low, and reaction is slow, and time-consuming, and impurity-eliminating effect is poor；Acid concentration is excessively high volatile, causes cost inclined
Height, while environment is polluted, it on the other hand can corrode container and SiO2；The too low reaction rate of acidleach temperature is slow, reaction is not thorough, temperature
It is volatile to spend peracid, concentration easily reduces, therefore, suitable acidleach concentration and acidleach temperature not only on properties of product influence compared with
Greatly, while also it will affect cost control.
Further, it is 60~120min that the time is embathed described in step S1, and embathing temperature is 60~72 DEG C.
Further, heating temperature described in step S2 is 600~700 DEG C；It is described to burst 5~20s into the water.
Preferably, heating temperature described in step S2 is 630~680 DEG C, described to burst 8s into the water.
Further, the sieve mesh number that pulverizes and sieves described in step S3 is 90~220 mesh, " chloroazotic acid " and quartzy silicon mine crude product
Granular mass ratio is 1:0.5~4, and soaking time is 10~15h, and soaking temperature is 30~50 DEG C, and described crush uses Raymond mill,
It is high density quartz ball that thunder used, which covers ball,.
The present invention can avoid crushing the new metal impurities of friction introducing using high density quartz ball.
Further, anhydride concentration described in step S4 be 0.03~0.5mol/L, magnetic agitation 3~7 hours.
Further, flotation solvent described in step S5 is prodan, dodecyl sodium sulfate, pentadecanoic acid, oxidation stone
Wax soap, N- (2- aminoethyl)-lauramide, N, one or more of N- dimethyl lauryl amine.
Further, high-temperature temperature described in step S7 is 850~980 DEG C, keeps the temperature 50~90min；Surpass described in step S8
Sonication power is 33~50kw, and sonication treatment time is 30~90min, is ultrasonically treated 35~55 DEG C of temperature.
Further, the ultrapure no color spot top grade all-transparent quartz material partial size is 90~220 mesh, and purity is greater than
99.999%.
Beneficial effects of the present invention:
The present invention controls reaction temperature by rationally designing processing step, by easily neutralize the acid not strong with corrosivity and
Its rational proportion, by reasonable process, the especially industrial microwave use condition found out repeatedly of application, effectively remove
The gas liquid inclusions such as hydroxyl, P, B, methane, ethane in quartzy silicon mine, at the same can also reject with existing for complex form other
Impurity (CH4, C2H6, NaCl etc.) can get high-purity no color spot top grade all-transparent quartz ingot of ultrapure quartz sand preparation, can be by stone
Locus coeruleus in English ingot is thoroughly eradicated.To realize the purification of domestic quartzy silicon mine, it is prepared and can be used for silica glass ingot
Ultrapure no locus coeruleus quartz material, prepared quartz material have chemical stabilization, all-transparent, impurity content is low, spectrum is saturating
Wide, heat shock resistance (can be under 1420 DEG C of hot environments repeatedly for a long time using indeformable), resistance to x ray irradiation x, ultraviolet light are worn entirely
Thoroughly, anti-crystallization is strong, hardness up to seven grades of Mohs, the coefficient of expansion is small, resistance to thermal shock is strong, electrical insulating property is good, resistance to removes hydrofluoric acid and hot phosphoric acid
The superior physical and chemical performances such as the outer corrosion of nearly all acid.
The present invention prepare ultrapure no color spot top grade all-transparent quartz material process it is easy to operate environmental protection, technique it is steady
Fixed, the ultrapure no color spot top grade all-transparent quartz material purity of gained can reach 99.999%.It will be further appreciated that work of the present invention
The ultrapure no color spot top grade all-transparent quartz material amount of process single treatment is big, and simple process is stablized, and can be advantageously applied to
Industrialized production.Present invention process method can break the external long-term technology in the field and monopolize, and reach china natural resources advantage
It gives full play to, the development for high-tech technology provides support.
The requirement of present invention combination commercial production scale, has carried out special tune to the process route of laboratory research of the present invention
Whole, further perfect domestic quartzy silicon mine prepares the process conditions of ultrapure no color spot top grade all-transparent quartz material, sums up
It is suitable for the industrial process conditions of domestic mine, is that the scale of domestic quartzy silicon mine uses, really reduces ultrapure no color spot
The production cost of high-grade all-transparent quartz material makes offer technical support.Change China to be chronically at import, supply and cannot fill
Code insurance is demonstrate,proved, material quality is difficult to ensure, high-end quartz material problem of industry status outstanding, cracks engineering challenge, thoroughly
It abolishes China's high-technology industry related with the world and develops unfavorable bottleneck, raising China's quartz silicon ore resource pair is value added comprehensively,
Technological Economy is double good with social benefit, and China's industry international status can be improved.
Specific embodiment
It is explained further and illustrates combined with specific embodiments below, but specific embodiment does not have any form to the present invention
Restriction.Unless otherwise specified, method and apparatus used in embodiment be conventional method in that art and equipment, it is raw materials used
For conventional commercial raw material.Following embodiment is using Heilungkiang quartz silicon mine, Xinjiang quartz silicon mine as silicon mine raw material.
Embodiment 1 prepares ultrapure no color spot top grade all-transparent quartz material
S1. selected quartzy silicon mine: domestic quartzy silicon mine is subjected to repeatedly icp analysis and is compared, alkali metal total content is filtered out
It is lower than the quartzy silicon mine of 38mg/kg lower than 2000mg/kg, B and P total content lower than 320mg/kg, gas liquid inclusion total content, uses
The hydrochloric acid that concentration is 1% impregnates quartzy silicon mine 2h under the conditions of 60 DEG C, then is got express developed with a large amount of deionized waters, obtains quartzy silicon
Mine crude product；
S2. water quenching: 600 DEG C will be heated to after quartzy silicon mine crude product acidleach obtained by step S1, then quickly met into the water
It is cold to burst 5S, a large amount of gas liquid inclusions are removed, crude product particle is obtained；
S3. by crude product particle obtained by step S2 through Raymond mill, 90 meshes, under the conditions of 30 DEG C, " chloroazotic acid " acidleach: are crossed
In mass ratio it is that 1:1 impregnates 15h with quartzy silicon mine crude product particle, removes metal impurities, then rinsed to get quartz with deionized water
Sand crude product；
S4. it is esterified: the quartz sand crude product that step S3 is obtained is soaked in the ether of anhydride concentration 0.03mol/L, and
It is connected under conditions of argon gas, magnetic agitation 3h, quartz sand surface hydroxyl is esterified；
S5. dodecyl sodium sulfate and N, N- dimethyl lauryl amine flotation: is added in the quartz sand being esterified obtained by step S4
Concentration rejects non-quartz sand particle than flotation in the solvent for 1:1；
S6. magnetic separation: the quartz sand crude product after step S5 flotation is rinsed with deionized water, after drying, with magnetic separator magnetic separation；
S7. high-temperature vacuum is handled: step S6 being magneticly elected the quartz sand particle come and is placed under 850 DEG C of high temperature, vacuum conditions
90min is kept the temperature, leads to chlorine treatment, superconduction purification after cooling again；
S8. ultrasonication: the ultrasound for being 33kw by power under the conditions of 35 DEG C by quartz sand particle obtained by step S7
Wave handles 90min to get ultrapure no color spot top grade all-transparent quartz material.
Embodiment 2 prepares ultrapure no color spot top grade all-transparent quartz material
S1. selected quartzy silicon mine: domestic quartzy silicon mine is subjected to repeatedly icp analysis and is compared, alkali metal total content is filtered out
It is the quartzy silicon mine that 2310mg/kg, B and P total content are 21mg/kg for 350mg/kg, gas liquid inclusion total content, is with concentration
2% hydrochloric acid impregnates quartzy silicon mine 2h under the conditions of 60 DEG C, then is got express developed with a large amount of deionized waters, and it is thick to obtain quartzy silicon mine
Product；
S2. water quenching: 630 DEG C will be heated to after quartzy silicon mine crude product acidleach obtained by step S1, then quickly met into the water
It is cold to burst 5S, a large amount of gas liquid inclusions are removed, crude product particle is obtained；
S3. acidleach: by crude product particle obtained by step S2 through Raymond mill, sieving with 100 mesh sieve, under the conditions of 30 DEG C, " king
Water " and quartzy silicon mine crude product particle are that 1:0.5 impregnates 15h in mass ratio, remove metal impurities, then rinsed with deionized water, i.e.,
Obtain quartz sand crude product；
S4. it is esterified: the quartz sand crude product that step S3 is obtained is soaked in the ether of anhydride concentration 0.04mol/L, and
It is connected under conditions of argon gas, magnetic agitation 5h, quartz sand surface hydroxyl is esterified；
S5. pentadecanoic acid, oxidized paraffin wax soap, N- (2- the aminoethyl)-moon flotation: is added in the quartz sand being esterified obtained by step S4
Osmanthus amide concentration rejects non-quartz sand particle than flotation in the solvent for 1:1:1；
S6. magnetic separation: the quartz sand crude product after step S5 flotation is rinsed with deionized water, after drying, with magnetic separator magnetic separation；
S7. high-temperature vacuum is handled: step S6 being magneticly elected the quartz sand particle come and is placed under 880 DEG C of high temperature, vacuum conditions
62min is kept the temperature, leads to chlorine treatment, superconduction purification after cooling again；
S8. ultrasonication: the ultrasound for being 35kw by power under the conditions of 38 DEG C by quartz sand particle obtained by step S7
Wave handles 90min to get ultrapure no color spot top grade all-transparent quartz material.
Embodiment 3 prepares ultrapure no color spot top grade all-transparent quartz material
S1. selected quartzy silicon mine: domestic quartzy silicon mine is subjected to repeatedly icp analysis and is compared, alkali metal total content is filtered out
It is the quartzy silicon mine that 2256mg/kg, B and P total content are 21.6mg/kg for 354mg/kg, gas liquid inclusion total content, uses concentration
Quartzy silicon mine 1h is impregnated under the conditions of 70 DEG C for 3% phosphoric acid, then is got express developed with a large amount of deionized waters, and it is thick to obtain quartzy silicon mine
Product；
S2. water quenching: 650 DEG C will be heated to after quartzy silicon mine crude product acidleach obtained by step S1, then quickly met into the water
It is cold to burst 8S, a large amount of gas liquid inclusions are removed, crude product particle is obtained；
S3. by crude product particle obtained by step S2 through Raymond mill, 150 meshes, under the conditions of 40 DEG C, " king acidleach: are crossed
Water " and quartzy silicon mine crude product particle are that 2:1 impregnates 12h in mass ratio, remove metal impurities, then with deionized water rinse to get
Quartz sand crude product；
S4. it is esterified: the quartz sand crude product that step S3 is obtained is soaked in the ether of anhydride concentration 0.04mol/L, and
It is connected under conditions of argon gas, magnetic agitation 5h, quartz sand surface hydroxyl is esterified；
S5. dodecyl sodium sulfate and N, N- dimethyl lauryl amine flotation: is added in the quartz sand being esterified obtained by step S4
Concentration rejects non-quartz sand particle than flotation in the solvent for 1:1；
S6. magnetic separation: the quartz sand crude product after step S5 flotation is rinsed with deionized water, after drying, with magnetic separator magnetic separation；
S7. high-temperature vacuum is handled: step S6 being magneticly elected the quartz sand particle come and is placed under 900 DEG C of high temperature, vacuum conditions
75min is kept the temperature, leads to chlorine treatment, superconduction purification after cooling again；
S8. ultrasonication: the ultrasound for being 40kw by power under the conditions of 35 DEG C by quartz sand particle obtained by step S7
Wave handles 58min to get ultrapure no color spot top grade all-transparent quartz material.
Embodiment 4 prepares ultrapure no color spot top grade all-transparent quartz material
S1. selected quartzy silicon mine: domestic quartzy silicon mine is subjected to repeatedly icp analysis and is compared, alkali metal total content is filtered out
It is 367mg/kg, gas liquid inclusion total content lower than the quartzy silicon mine that 2451mg/kg, B and P total content are 8mg/kg, uses concentration
Quartzy silicon mine 1.5h is impregnated under the conditions of 70 DEG C for 3% hydrochloric acid, then is got express developed with a large amount of deionized waters, and quartzy silicon mine is obtained
Crude product；
S2. water quenching: 680 DEG C will be heated to after quartzy silicon mine crude product acidleach obtained by step S1, then quickly met into the water
It is cold to burst 8S, a large amount of gas liquid inclusions are removed, crude product particle is obtained；
S3. by crude product particle obtained by step S2 through Raymond mill, 200 meshes, under the conditions of 46 DEG C, " king acidleach: are crossed
Water " and quartzy silicon mine crude product particle are that 1:3 impregnates 13h in mass ratio, remove metal impurities, then with deionized water rinse to get
Quartz sand crude product；
S4. it is esterified: the quartz sand crude product that step S3 is obtained is soaked in the ether of anhydride concentration 0.04mol/L, and
It is connected under conditions of argon gas, magnetic agitation 5h, quartz sand surface hydroxyl is esterified；
S5. dodecyl sodium sulfate and N, N- dimethyl lauryl amine flotation: is added in the quartz sand being esterified obtained by step S4
Concentration rejects non-quartz sand particle than flotation in the solvent for 1:0.5；
S6. magnetic separation: the quartz sand crude product after step S5 flotation is rinsed with deionized water, after drying, with magnetic separator magnetic separation；
S7. high-temperature vacuum is handled: step S6 being magneticly elected the quartz sand particle come and is placed under 920 DEG C of high temperature, vacuum conditions
82min is kept the temperature, leads to chlorine treatment, superconduction purification after cooling again；
S8. ultrasonication: the ultrasound for being 48kw by power under the conditions of 45 DEG C by quartz sand particle obtained by step S7
Wave handles 80min to get ultrapure no color spot top grade all-transparent quartz material.
Embodiment 5 prepares ultrapure no color spot top grade all-transparent quartz material
S1. selected quartzy silicon mine: domestic quartzy silicon mine is subjected to repeatedly icp analysis and is compared, alkali metal total content is filtered out
It is the quartzy silicon mine that 2400mg/kg, B and P total content are 11mg/kg for 380mg/kg, gas liquid inclusion total content, is with concentration
10% hydrochloric acid impregnates quartzy silicon mine 1h under the conditions of 72 DEG C, then is got express developed with a large amount of deionized waters, and it is thick to obtain quartzy silicon mine
Product；
S2. water quenching: 700 DEG C will be heated to after quartzy silicon mine crude product acidleach obtained by step S1, then quickly met into the water
It is cold to burst 20S, a large amount of gas liquid inclusions are removed, crude product particle is obtained；
S3. by crude product particle obtained by step S2 through Raymond mill, 220 meshes, under the conditions of 50 DEG C, " king acidleach: are crossed
Water " and quartzy silicon mine crude product particle are that 1:4 impregnates 10h in mass ratio, remove metal impurities, then with deionized water rinse to get
Quartz sand crude product；
S4. it is esterified: the quartz sand crude product that step S3 is obtained is soaked in the ether of anhydride concentration 0.05mol/L, and
It is connected under conditions of argon gas, magnetic agitation 7h, quartz sand surface hydroxyl is esterified；
S5. flotation: dodecyl sodium sulfate and N, N- dimethyl 12 will be added in the quartz sand being esterified obtained by step S4
Amine concentration rejects non-quartz sand particle than flotation in the solvent for 0.5:1；
S6. magnetic separation: the quartz sand crude product after step S5 flotation is rinsed with deionized water, after drying, then uses magnet separator magnetic
Choosing；
S7. high-temperature vacuum is handled: step S6 being magneticly elected the quartz sand particle come and is placed under 980 DEG C of high temperature, vacuum conditions
50min is kept the temperature, leads to chlorine treatment, superconduction purification after cooling again；
S8. ultrasonication: the ultrasound for being 50kw by power under the conditions of 55 DEG C by quartz sand particle obtained by step S7
Wave handles 30min to get ultrapure no color spot top grade all-transparent quartz material.
Comparative example 1 prepares ultrapure no color spot top grade all-transparent quartz material
S1. selected quartzy silicon mine: Madagascar's quartz silicon mine is subjected to repeatedly icp analysis and is compared, alkali metal is filtered out
Total content is lower than the quartz of 11mg/kg lower than 300mg/kg, gas liquid inclusion total content lower than 2200mg/kg, B and P total content
Silicon mine is impregnated with the hydrofluoric acid dips quartz silicon mine that concentration is 3%, is got express developed with a large amount of deionized waters, obtain quartzy silicon mine
Crude product；
S2. water quenching: 1000 DEG C will be heated to after quartzy silicon mine crude product acidleach obtained by step S1, then quickly fried into the water
10S is split, a large amount of gas liquid inclusions are removed, obtains crude product particle；
S3. by crude product particle obtained by step S2 through Raymond mill, 150 meshes, under the conditions of 40 DEG C, " king acidleach: are crossed
Water " and quartzy silicon mine are that 2:1 impregnates 12h in mass ratio, remove metal impurities, then thick to get quartz sand with deionized water flushing
Product；
S4. flotation: quartz sand crude product obtained by step S3 is added in dodecyl sodium sulfate solvent and floatingly selects non-quartz sand
Particle；
S5. magnetic separation: the quartz sand crude product after step S4 flotation is added in the mixed acid of 3% phosphoric acid and 3% hydrochloric acid
Then acidleach is rinsed with deionized water, screened after drying by reciprocating sieve, then passes through magnetic separator magnetic separation；
S6. high-temperature vacuum is handled: step S5 is magneticly elected the quartz sand particle come and is placed under high temperature, vacuum condition and is reacted,
Lead to chlorine treatment, superconduction purification after cooling again；
S7. ultrasonication: the ultrasound for being 21kw by power under the conditions of 35 DEG C by quartz sand particle obtained by step S6
Wave handles 58min to get ultrapure no color spot top grade all-transparent quartz material.
Comparative example 2 prepares ultrapure no color spot top grade all-transparent quartz material
Step is same as Example 3, the difference is that being 450 DEG C by heating temperature in step S2.
Comparative example 3 prepares ultrapure no color spot top grade all-transparent quartz material
Step is same as Example 3, the difference is that step S7 high-temperature vacuum processing high temperature temperature is 650 DEG C.
Comparative example 4 prepares ultrapure no color spot top grade all-transparent quartz material
Step is same as Example 3, the difference is that ultrasonication power is 20kw in step S8.
Comparative example 5 prepares ultrapure no color spot top grade all-transparent quartz material
Step is same as Example 3, the difference is that being esterified without step S4, directly by quartz sand crude product after acidleach
Flotation.
Domestic quartz silicon mine used in the present invention is set forth through present invention process condition gas-liquid packet before and after the processing in table 1~4
The content experimental result of body content and B, P, hydroxyl is wrapped up in, it is as shown in the table for specific testing result.As seen from table, the present invention by adjusting
Technological parameter and preparation step can effectively improve the purity of ultrapure no color spot top grade all-transparent quartz material, reduce quartz material
The content of middle gaseous impurity and B, P, hydroxyl.
The quartzy silicon mine-gas liquid Fluid Inclusion Compositions content (unit: mg/kg) of table 1
Table 2 be the no color spot top grade all-transparent quartz material gas liquid inclusion component content of be prepared ultrapure (unit:
mg/kg)
Other impurities content (unit: mg/kg) in each quartzy silicon mine of table 3
| Sample | P | B | Hydroxyl |
| Domestic quartz silicon mine | 11.2 | 9.3 | 612.3 |
| Madagascar's quartz silicon mine | 0.2 | 0.8 | 56.9 |
Each component content in ultrapure no color spot top grade all-transparent quartz material after the purification of table 4
The quartz material that embodiment and comparative example is prepared is observed into its light transmission rate using 721 spectrophotometers, it is real
The light transmittance for applying 1~embodiment of example 5 has reached 94~96%, and the light transmittance highest of embodiment 3, has reached 96.9%, colourless
Spot；The light transmittance of comparative example 1 is 92.3%, and the light transmittance of 2~comparative example of comparative example 5 is below 80%, and has a small amount of indigo plant
Color spot exists.The ultrapure no color spot all-transparent quartz material light transmittance that the present invention is prepared is substantially better than comparative example, and does not have
There is color spot.
Detailed process equipment and process flow of the invention that the present invention is explained by the above embodiments, but the present invention is not
It is confined to above-mentioned detailed process equipment and process flow, that is, does not mean that the present invention must rely on above-mentioned detailed process equipment and work
Skill process could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, to product of the present invention
The equivalence replacement of each raw material and addition, the selection of concrete mode of auxiliary element etc., all fall within protection scope of the present invention and public affairs
Within the scope of opening.
Claims (10)
1. a kind of ultrapure no color spot top grade all-transparent quartz material, which is characterized in that the ultrapure no color spot top grade full impregnated alum
English material particle size is 90 ~ 220 mesh, SiO in quartz material2Content is greater than 99.999%, and hydroxy radical content < 6mg/kg, P and B's always contains
Amount < 5mg/kg.
2. a kind of preparation method of ultrapure no color spot top grade all-transparent quartz material, which comprises the following steps:
S1. selected quartzy silicon mine: icp analysis is repeated in the domestic quartzy silicon mines in multiple areas and is compared, screens, then, uses
Low concentration acid solution embathes surface impurity, then is got express developed with deionized water, obtains quartzy silicon mine crude product；
S2. water quenching: then quartzy silicon mine crude product heating obtained by step S1 is quickly burst, removal is a large amount of to the cold into the water
Gas liquid inclusion obtains crude product particle；
S3. acidleach: by crude product particle obtained by step S2 through Raymond mill, sieving, " chloroazotic acid " impregnates, and removes metal impurities, then
It is rinsed with deionized water to get quartz sand crude product；
S4. it is esterified: the quartz sand crude product that step S4 is obtained being soaked in the ether containing acid anhydrides, and is connected with protective gas
Under the conditions of, magnetic agitation, quartz sand surface hydroxyl is esterified；
S5. flotation: flotation in flotation solvent is added in esterification quartz sand crude product obtained by step S4 and rejects non-quartz sand particle；
S6. magnetic separation: the quartz sand crude product after step S5 flotation is rinsed with deionized water, after drying, then with magnetic separator magnetic separation；
S7. high-temperature vacuum is handled: the step S6 quartz sand particle magneticly elected being placed under high temperature, vacuum condition and is kept the temperature, is cooled down
Lead to chlorine treatment, superconduction purification again afterwards；
S8. ultrasonication: by quartz sand particle obtained by step S7 by ultrasonication to get ultrapure no color spot top grade full impregnated
Bright quartz material.
3. the preparation method of ultrapure no color spot top grade all-transparent quartz material according to claim 2, which is characterized in that step
Acid solution described in rapid S1 is one or more of oxalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, and the acid solutions are 1 ~ 10%；Sieve
The alkali metal total content selected is 300 ~ 400mg/kg, gas liquid inclusion total content is lower than the quartzy silicon mine of 2600mg/kg.
4. the preparation method of ultrapure no color spot top grade all-transparent quartz material according to claim 2, which is characterized in that step
It is 60 ~ 120min that the time is embathed described in rapid S1, and embathing temperature is 60 ~ 72 DEG C.
5. the preparation method of ultrapure no color spot top grade all-transparent quartz material according to claim 2, which is characterized in that step
Heating temperature described in rapid S2 is 600 ~ 700 DEG C；5 ~ 20s is burst into the water.
6. the preparation method of ultrapure no color spot top grade all-transparent quartz material according to claim 2, which is characterized in that step
The sieve mesh number that pulverizes and sieves described in rapid S3 is 90 ~ 220 mesh, and " chloroazotic acid " and quartzy silicon mine crude product granular mass ratio are 1:0.5 ~ 4,
Soaking time is 10 ~ 15h, and soaking temperature is 30 ~ 50 DEG C, and it is high density quartz ball that thunder used in the Raymond mill, which covers ball,.
7. the preparation method of ultrapure no color spot top grade all-transparent quartz material according to claim 2, which is characterized in that its
In, anhydride concentration described in step S4 be 0.03~0.5mol/L, magnetic agitation 3~7 hours.
8. the preparation method of ultrapure no color spot top grade all-transparent quartz material according to claim 2, which is characterized in that step
Flotation solvent described in rapid S5 is prodan, dodecyl sodium sulfate, pentadecanoic acid, oxidized paraffin wax soap, N- (2- the aminoethyl)-moon
Osmanthus amide, N, one or more of N- dimethyl lauryl amine.
9. the preparation method of ultrapure no color spot top grade all-transparent quartz material according to claim 2, which is characterized in that step
High-temperature temperature described in rapid S7 is 850 ~ 980 DEG C, keeps the temperature 50 ~ 90min；Sonification power described in step S8 is 33 ~ 50kw, is surpassed
The sonication time is 30 ~ 90min, is ultrasonically treated 35 ~ 55 DEG C of temperature.
10. as the described in any item ultrapure no color spot top grade all-transparent quartz materials of claim 1 ~ 9 are applied to high-grade quartzy glass
Glass ingot.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357470A (en) * | 2019-06-28 | 2019-10-22 | 黄冈师范学院 | A kind of high pressure acidleach removes the process of blue illite particulate matter in quartz sand |
| CN111393022A (en) * | 2020-03-23 | 2020-07-10 | 黄冈师范学院 | Preparation method of high-purity low-hydroxyl quartz glass raw material |
-
2018
- 2018-09-30 CN CN201811165438.XA patent/CN109399914A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357470A (en) * | 2019-06-28 | 2019-10-22 | 黄冈师范学院 | A kind of high pressure acidleach removes the process of blue illite particulate matter in quartz sand |
| CN110357470B (en) * | 2019-06-28 | 2022-01-14 | 黄冈师范学院 | Process method for removing blue illite particles in quartz sand through high-pressure acid leaching |
| CN111393022A (en) * | 2020-03-23 | 2020-07-10 | 黄冈师范学院 | Preparation method of high-purity low-hydroxyl quartz glass raw material |
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