CN209685571U

CN209685571U - A kind of special equipment producing devitrified glass

Info

Publication number: CN209685571U
Application number: CN201920236937.7U
Authority: CN
Inventors: 陈福; 续芯如; 冯建业; 闫亚琼
Original assignee: Qinhuangdao Glass Industry Research And Design Institute Co Ltd
Current assignee: Qinhuangdao Glass Industry Research And Design Institute Co Ltd
Priority date: 2019-02-25
Filing date: 2019-02-25
Publication date: 2019-11-26
Anticipated expiration: 2029-02-25

Abstract

The utility model discloses a kind of special equipments for producing devitrified glass, including sequentially connected glass melter, cooling bay, device for shaping glass and annealing kiln, the device for shaping glass is molding molten tin bath, is also successively arranged coring molten tin bath and crystallization molten tin bath between molding molten tin bath and the annealing kiln.The devitrified glass bubble that the utility model special equipment obtains is few, intensity is high, and yield rate and final product quality all have a big promotion；And idle Ta Nb tailings are utilized in production in itself, have saved resource.

Description

A kind of special equipment producing devitrified glass

Technical field

The utility model relates to the processing technique field of glass, produces the dedicated of devitrified glass more particularly to a kind of and set It is standby.

Background technique

Devitrified glass, using certain controlled coring and crystallization process, is passed through using natural inorganic material as primary raw material A kind of glass of special crystallite crystal phase is precipitated in the glass metal of special composition, basis is shown in Table 1.

The basis of 1 devitrified glass of table

Ingredient	CaO	Al₂O₃	SiO₂	Sb₂O₃	ZnO+MgO	Na₂O
							Content/%	16-22	3-10	50-70	1-3	4-9	1-6

Devitrified glass has the advantages that the triple of glass, ceramics and lithotome, such as with the optics passability and table of glass Face optical property, mechanical and surface crystallization performance, the surface anisotropic with lithotome and dicoration etc. with ceramics, It is better than lithotome and ceramics again simultaneously, performance is relatively shown in Table 2.

The properties of 2 devitrified glass of table and ceramics, lithotome compare

From Table 2, it can be seen that devitrified glass (is reflected, because of water absorption rate and heat expansion in dimensional stability with water absorption rate Coefficient is related, the big material of water absorption rate is easily deformed, i.e., coefficient of thermal expansion is big, poor dimensional stability), frost resistance, glossiness hold Long property (i.e. the weatherability and durability of material is embodied by acid resistance, the alkali resistance in table 2), intensity (flexural strength, pressure resistance Degree) etc. be superior to ceramics, natural marble and granite.Therefore, devitrified glass can be used as the inner-outer wall and ground of all kinds of buildings Plate ornament materials, the ideal material of platen of even more washing one's face, hygienic platen.Devitrified glass is in addition to can be used as external wall and indoor height Shelves decoration, can also do mechanical structure, such as the insulating materials on electronics, electrician, baseboard material, the micro-wave oven of large scale integrated circuit Flameproof ware, chemical industry and anti-corrosion material and mine wear-resistant material etc., purposes is extremely wide.

The production technology of existing devitrified glass is mainly sintering process, and through molten sintering twice.Sintering process includes melting water Particle at small particle, is then attached to by sintering process of quenching and direct sintering, melt water quenching sintering process by water quenching after glass melting Carry out coring and crystallization in mold, specific process include: mixture preparation → glass smelting → water quenching prepare pellet → molding → Dominated crystallization → cold working etc.；The process of direct sintering include: mixture preparation → grinding mixing → forming and sintering → cold plus Work etc..

As Publication No. CN 1868946A Chinese patent application in disclose a kind of waste residue microcrystal glass and its preparation side Method.The preparation method of the devitrified glass is the melt water quenching sintering process in sintering process.Not only production energy consumption occupies height not to this method Under, it can also make the devitrified glass superficial layer densification depths (the microcrystalline coating thickness formed) of production 2nm more shallow than direct sintering Left and right, microcrystalline coating thickness is thinner, illustrates that controlled micro crystallization degree is insufficient, and obtained devitrified glass properties are poorer, glass particle Between bubble be difficult to exclude, lead to that rough surface, the porosity are high, are also easy to produce deformation, the fireproof die used when to subsequent forming High temperature resistant, pressure-resistant performance and to be not easy deformation nature requirement high, it is also necessary to the processes such as secondary operation are carried out to devitrified glass surface, Because secondary operation can further result in the production energy consumption and cost raising of devitrified glass again.While due to magnesia and calcium oxide It is advantageous using the adjustment for capableing of viscosity and temperature performance to glass, and magnesia is not used in the devitrified glass, use height The calcium oxide of content, this can make glass embrittlement, then adjust glass melting temperature using the relatively high boron oxide of price, promote Into the fusing of devitrified glass, the production cost of devitrified glass can be promoted again in this way.

Direct sintering crystal phase ratio when preparing devitrified glass depends on the whole crystallization ability of parent glass, this just leads Crystallization Process is caused to be difficult to control, and whole crystallization time length, production efficiency and yield rate are low.

Rolling process can also be used to production devitrified glass at present, such as the Chinese patent application of Publication No. CN 106746681A In disclose it is a kind of using trade waste prepare wear-resistant glass-ceramics.The devitrified glass is prepared through rolling process, system Standby process includes mixture preparation → glass smelting → calendering formation → annealing → nucleus crystallization → cold working etc..Rolling process is to adopt Rotate pressed glass molding forward with double roller, glass waits have contraction at the time of molding, simultaneously because roller table surface is coarse, can all make It is rough at glass surface, therefore also need to be processed by shot blasting after forming, process flow is increased, yield rate is reduced, is mentioned High cost.Contain copper sulphate, nickel sulfide, magnesium diboride in the raw material composition of the devitrified glass, and is used to the Nucleating Agent of crystallization What is selected is chrome green；Wherein, copper sulphate can make glass coloration au bleu, Cr₂O₃Middle Cr³⁺It is to belong to heavy metal ion, It can generate pollution of chromium and intoxicating phenomenon, it is dangerous, not environmentally, use should be avoided in industry.

Utility model content

The purpose of this utility model is to provide a kind of above-mentioned crystallite glass of production for technological deficiency existing in the prior art The special equipment of glass, including it is sequentially connected

For by glass raw material mix be melting into glass metal and carry out clear glass melter,

For the glass metal after clarification is homogenized and is cooled down cooling bay,

Device for shaping glass and

For eliminating the annealing kiln of glass tape stress, which is characterized in that

The device for shaping glass is for forming glass metal float glass process to the molding for being loaded with soldering tin of glass tape Molten tin bath,

It is described molding molten tin bath and annealing kiln between be also successively arranged be loaded with soldering tin, be used to glass tape carry out core The coring molten tin bath of change and for glass tape carry out crystallization crystallization molten tin bath.

It is equipped between the molding molten tin bath and coring molten tin bath and is used to adjust glass tape temperature and be transported to coring molten tin bath First Transition roller tables.

It is equipped between the coring molten tin bath and crystallization molten tin bath and is used to adjust glass tape temperature and be transported to crystallization molten tin bath The second transition roller table.

The two sides of the molding molten tin bath are also equipped with multipair symmetrical edge machine in pairs.

The edge machine is arranged 6-12 pairs.

The coring molten tin bath and crystallization molten tin bath two sides are not provided with edge machine.

The molding molten tin bath, coring molten tin bath are equipped with for fill the nitrogen and hydrogen that prevent tin liquor oxidation in crystallization molten tin bath Inflating port.

Roller in the First Transition roller tables and the second transition roller table is Quartz Ceramic Roller.

The glass melter is oxy-fuel combustion glass melting furnace.

5-8 is equipped in the glass melter to all-oxygen combustion spray gun.

Compared with prior art, the utility model prepares devitrified glass, impact strength, resistance to pressure using float apparatus The indexs such as degree, water absorption rate (i.e. dimensional stability) are superior to the devitrified glass of current sintering process preparation, and physicochemical property and decoration The devitrified glass that effect can reach current sintering process preparation is horizontal, is conducive to application.It is built simultaneously using Ta Nb tailings preparation The comprehensive utilization effect that Ta Nb tailings are improved to the exploitation of the blindness of lithotome can be greatly reduced by building decoration devitrified glass Rate turns waste into wealth.

Glass raw material is melt by glass metal using oxy-fuel combustion glass melting furnace in the special equipment of the utility model, can be added Fast glass metal fusing and clear process, advantageously reduce the generation of the bubble, striped plethora of glass, reduce glass inside and The defect on surface.

In addition, the special equipment of the utility model uses secondary forming process at the time of molding, first make glass metal in molten tin bath Molding carries out temperature to transitional product outside molten tin bath to plate glass transitional product uniform, smooth, with certain thickness and width Molten tin bath is again introduced into after degree adjustment and carries out nucleus crystallization, and obtained devitrified glass bubble is few, intensity is high, yield rate and final product quality All have a big promotion；And idle Ta Nb tailings are utilized in production in itself, have saved resource, have contained in Ta Nb tailings K₂O、Na₂O、Rb₂O、PbO、Li₂The meltable oxide such as O generates eutectic effect, reduces fusion temperature, reduces crystallite glass Energy consumption when glass produces, is effectively protected resource environment.

Detailed description of the invention

Fig. 1 show the profilograph of the special equipment structure of the utility model production devitrified glass；

Fig. 2 show the structure top view of the special equipment of the utility model production devitrified glass；

1 glass melter, 2 glass metals, 3 cooling bays, 4 upper spaces, 5 molding molten tin baths, 6 glass tapes, 7 First Transition roller tables, 8 Roller, 9 coring molten tin baths, 10 second transition roller tables, 11 crystallization molten tin baths, 12 check aprons, 13 annealing kilns, 14 all-oxygen combustion spray guns, 15 meltings Tin liquor, 16 edge machines.

Specific embodiment

Yichuan Ta Nb tailings be from the lithium spectra containing tantalum niobium rare metal, after selected tantalum niobium remaining tail Ore in sand form., in the future can be increasingly severe to the pollution of environment if Ta Nb tailings are not utilized rationally, be for local government Urgent need to solve the problem.Hair is also all indicated from " economizing energy law ", " environment impact assessment ordinance " and " Renewable Energy Law " etc. Open up the requirement of circular economy related fields.

Local raw material and geographical advantage can be made full use of by preparing devitrified glass using Ta Nb tailings, for enterprise and be worked as Ground government forms new productivity growth point.Through Al in ore dressing analysis Ta Nb tailings sample₂O₃It is higher, therefore building can be introduced into The decoration preparation of devitrified glass, provides Al needed for preparing devitrified glass₂O₃；Least a portion of Na can be also introduced simultaneously₂O is to subtract Few soda ash dosage；The P of introducing portion₂O₅, ZrO₂, fluoride and TiO₂It can be used as Nucleating Agent, to reduce the dosage of Nucleating Agent, have Conducive to the production cost for reducing glass, by determining that the chemical component in Ta Nb tailings is shown in Table 3 after beneficiation test.

Ta Nb tailings sample chemical component after 3 beneficiation test of table

By largely testing the devitrified glass produced with research repeatedly, final selected the utility model special equipment Basis composition includes SiO₂、Al₂O₃、CaO、MgO、Na₂O、K₂O and ZnO etc..It is mainly formed in glass and in high strength micro-crystalline glass Played in effect it is as follows:

Silica SiO₂It is the main body that glass forms skeleton, the SiO in soda lime glass₂The heat of glass can be reduced The coefficient of expansion improves thermal stability, chemical stability, softening temperature, hardness and the mechanical strength of glass.

Aluminium oxide Al₂O₃Belong to the intermediate oxide of glass, the crystallization tendency of glass can be reduced, improve the chemistry of glass Stability, thermal stability, mechanical strength, hardness and refractive index mitigate erosion of the glass to refractory material.The utility model production Devitrified glass in Al₂O₃Content is 10.2%-16%, and Al in general devitrified glass₂O₃Content is no more than 10%, this is Because when alumina content is high, devitrified glass can have [AlO₄] and [AlO₆] two kinds of structures, glassware directly applies and carries out It is low to environmental parameter requirement when deep processing, and facilitate glass and carry out chemical tempering, be conducive to being widely applied and answering for product With.

Sodium oxide molybdena Na₂O is glass network modifier oxides, can reduce the viscosity of glass, and glass is made to be easy to melt, and is glass The good fluxing agent of glass.Na₂O can increase the thermal expansion coefficient of glass, reduce thermal stability, chemical stability and the machinery of glass Intensity.

Potassium oxide K₂O is also glass network modifier oxides, its effect and Na in glass₂O is similar.Potassium ion (K⁺) Radius ratio sodium ion (Na⁺) it is big, the viscosity of potash glass is bigger than soda-lime glass, can reduce the tendency towards devitrification of glass, increases glass Transparency and gloss etc., can also be with Na₂O generates mixed alkali effect, is conducive to the fusing of glass.

Calcium oxide CaO is the glass network modifier oxides of divalent.Its main function is stabilizer, that is, increases the change of glass Learn stability and mechanical strength.When content is high, the crystallization tendency of glass will increase.

Magnesia MgO is network modifying oxide in soda lime glass.It is replaced in glass with 10% MgO below Part CaO can make the setting rate of glass slack-off, reduce the tendency towards devitrification of glass, improve the chemical stability and machine of glass Tool intensity.

Barium monoxide BaO is also glass network modifier oxides, can increase refractive index, density gloss and the chemical stabilization of glass Property, also the material of glass can be made elongated, a small amount of barium monoxide can also accelerate fusing and the crystallization of glass.

Zinc oxide ZnO is glass intermediate oxide, keeps glass structure finer and close, can reduce the thermal expansion system of glass Number, improves thermal stability, the chemical stability of glass, increases the refractive index of glass, while can speed up glass at high temperature Fusing, split-phase and crystallization.

Phosphorus pentoxide P₂O₅It is network former, it is with phosphorus oxygen tetrahedron [PO₄] formed phosphate glass structure Network improves glass abbe number and the ability by ultraviolet light, can be as the Nucleating Agent in devitrified glass preparation process.

Zirconium dioxide ZrO₂It is intermediate oxide, viscosity, hardness, elasticity, refractive index, the chemical stabilization of glass can be improved Property, the thermal expansion coefficient of glass is reduced, can be used as the nucleating agent of devitrified glass.

Fluoride is common fluxing agent and opacifiers in glass industry, also can be used as the Nucleating Agent of devitrified glass, mainly Select CaF₂And Na₂SiF₆。

Titanium dioxide TiO₂It is intermediate oxide, the refractive index and chemical stability of glass can be improved, increases and absorb X The ability of ray and ultraviolet light can be used as the Nucleating Agent of Aluminous Silicate Glass-Ceramics.

In glass melting process, since a large amount of gas can be precipitated in the decomposition and the volatilization of Volatile Colstituent etc. of batch each component Body.Until still have small part of gas that cannot escape completely from glass metal after glass forming process finishes, it is residual in the form of bubbles It stays in glass metal.Therefore, in order to obtain pure uniform high-quality glass metal, three oxidations two are added in glass batch Antimony (Sb₂O₃) and nitrate (generally sodium nitrate and potassium nitrate) be used as clarifying agent, to promote the exclusion of bubble in glass metal.Phase Than in sulfate clarifying agent, the utility model selects Sb₂O₃The secondary bubble of sulfate will not be generated as clarifying agent with nitrate, Pollutant SO will not be generated in flue gas simultaneously₂, be conducive to mitigate flue gas desulfurization and denitrification load, reduce the production of devitrified glass Cost.Nano-titanium dioxide (TiO is added in glass raw material simultaneously₂), phosphorus pentoxide (P₂O₅), fluoride and nano-silica Change zirconium (ZrO₂) it is used as Nucleating Agent, accelerate coring and the crystallization process of glass, accelerate the generation of crystallite and grow up, is i.e. acceleration glass Body, can be by particle aggregation small around together, to promote the discharge of bubble in glass metal to the process of crystalline transformation.

The utility model uses Ta Nb tailings for primary raw material, the devitrified glass produced using floating process, resists The indexs such as impact strength, compressive resistance are superior to the devitrified glass that sintering process obtains.However the crystallite glass of the utility model production Glass is because of Al in itself glass ingredient₂O₃Content is higher, there is both sides technical problem with float process: first is that glass melting Temperature is high, and clarifying and homogenizing is difficult；Second is that controlled micro crystallization control is difficult, this is because producing devitrified glass, fusing using floating process The temperature difference between temperature and forming temperature is big, while coring and crystallization temperature are also different, is difficult to be controlled in molten tin bath.For The special equipment of problem one, the utility model uses pure oxygen combustion technology, reduces the viscosity of glass metal, solves clarifying and homogenizing Difficult problem, can also reduce bubble, blub and the striped in glass metal.For problem two, the utility model passes through in tantalum niobium P is added in tailing₂O₅, ZrO₂, fluoride and TiO₂Equal Nucleating Agents, and tin groove forming is first carried out to glass metal, it is left after molding Molten tin bath to transition roller table is again introduced into the production method that molten tin bath carries out coring and crystallization after adjusting temperature, so that glass-ceramic process can Control, prevents the generation of defect, guarantees the stabilization of crystallization process, realizes that continuous production, high-efficient, at low cost target obtain product The Expectation of Glass-Ceramics Used as Decorated Materials of matter qualification.

Although the utility model produces devitrified glass using float apparatus, not similar with float process simple glass. Float process simple glass is that the glass metal after fusing is made to flow into tin groove forming, cooling by transition roller table after molding, then into Enter annealing kiln annealing.

And the utility model using float apparatus production devitrified glass be the glass metal that will melt flow into form molten tin bath into Row molding, enters coring molten tin bath after molding and crystallization molten tin bath carries out coring and crystallization respectively, after gradually cooling down in crystallization molten tin bath It anneals into annealing kiln, to eliminate the stress of glass.When annealing, glass tape is heated by certain temperature curve, soaking, Heat preservation, Xu Leng and rapid cooling etc. make to form the inner-stress value reduction generated in cooling procedure, meet cutting and quality requirement to reach Standard.

The devitrified glass of the utility model due to using float apparatus and floating process to prepare, also referred to as float glass process Devitrified glass is to be made with natural inorganic material through processes such as crushing, ingredient, fusing, float glass process molding, crystallization, annealing.It should The good characteristic of devitrified glass that there is float glass process devitrified glass sintering process to obtain: such as without radiate, do not absorb water, not burn into do not aoxidize, Colour-fast, no color differnece, indeformable, intensity is high, glossiness is high etc.；In addition, also additionally having, bubble-free, decorative pattern are naturally beautiful, manage Change performance is more preferable, product specification can ultra-thin ultra-wide, imporosity is easy to clean, yield is big, high yield rate, it is at low cost the advantages that.This is floating Method devitrified glass can be used as senior building ornament materials, with extraordinary flatness, surface gloss and excellent physico Performance is learned, alternative natural granite is for the inner-outer wall of various buildings, ground and table top decoration.The popularization of float glass process devitrified glass Using new growth engines will be will form, gone to the world with the advantage of high-performance mass, low production cost, large-scale production. Furthermore primary raw material (such as: Ta Nb tailings, gold ore tailing) can be done using industrial residue in the production of float glass process devitrified glass, belonged to The preferred new product that environment-friendly type project and float glass enterprise adjustment structure are increased economic efficiency.

The utility model prepares float glass process devitrified glass as raw material using Ta Nb tailings, and the glass properties of preparation is stablized, answered With extensive, be conducive to the application of the kind devitrified glass, and can accelerate to promote Ta Nb tailings comprehensive utilization, reduces to environment Pollution.

Below in conjunction with specific embodiment, the content of the utility model is further illustrated, and the utility model is made into one Step illustrates, but these embodiments absolutely not limit the utility model.

Batch is formed into uniform, bubble-free by high-temperature heating and meets the process of the glass metal of forming requirements, is claimed For being melted for glass.Glass melting process is the important link in glass production.Many defects (such as bubble, calculus, the item of glass Line etc.) be all the glass metal in melting process it is uneven caused by.The yield and quality of glass, qualification rate, production cost, combustion Material consumption and melted tank furnace service life etc. all have substantial connection with the melted of glass.Therefore, reasonable glass smelting is carried out, is Entire production process is smooth, and efficiently produces the important guarantee of high-quality glassware.

Ta Nb tailings are used to produce Expectation of Glass-Ceramics Used as Decorated Materials by the utility model by largely having determined, should The raw material composition of devitrified glass presses mass percentage, comprising: SiO₂43%-49.8%, Al₂O₃10.2%-16%, CaO 5.5%-9.9%, MgO 1.2%-9.8%, Na₂O 3.1%-6.5%, K₂O 2.3%-7.7%, BaO 4.2%-8.8%, ZnO 4.5%-10%, Sb₂O₃0.2%-2%, nitrate 0.8%-8%, P₂O₅0.3%-1.8%, ZrO₂0.2%- 1.5%, fluoride 0.1%-0.7%, TiO₂0.7%-3.5%；Wherein P₂O₅, ZrO₂, fluoride and TiO₂As compound nucleus Agent；

It is preferred that:

SiO₂45%-47%, Al₂O₃11%-14%, CaO 6%-8%, MgO 3%-8%, Na₂O 4%-5%, K₂O 3%-6%, BaO 5%-7%, ZnO 5%-8%, Sb₂O₃0.5%-1.5%, nitrate 2%-6%, P₂O₅0.6%- 1.5%, ZrO₂0.5%-1.1%, fluoride 0.2%-0.5%, TiO₂1.2%-2.9%.

It is more preferable:

SiO₂46%, Al₂O₃12.5%, CaO 7%, MgO 5.5%, Na₂O 4.5%, K₂O 4.5%, BaO 6%, ZnO 6.5%, Sb₂O₃0.8%, nitrate 2.8%, P₂O₅0.8%, ZrO₂0.7%, fluoride 0.4%, TiO₂2%.

In the raw material of production devitrified glass, the best introducing mass percentage of Ta Nb tailings is glass raw material gross mass 25%-40%, preferably 30%-35%, more preferable 33%.The introducing ratio is guaranteeing that devitrified glass forms stable situation Under, Ta Nb tailings can be maximally utilised, while being contained in tailing part microelement such as Li₂O、Rb₂O, PbO, NiO etc., Also help the fusing and clarification of glass.

The utility model provides a kind of special equipment for producing above-mentioned devitrified glass, and structure is as depicted in figs. 1 and 2, including Sequentially connected glass melter 1, cooling bay 3, molding molten tin bath 5, First Transition roller tables 7, coring molten tin bath 9, the second transition roller table 10, Crystallization molten tin bath 11 and annealing kiln 13.Wherein:

Glass melter 1 is used to mixed glass raw material being melting into glass metal 2, and removes the visible bubble in bubble in glass metal. The process of removal visible bubble in bubble is known as the clarification of glass metal, i.e. the clarification of glass raw material being melted with glass metal is molten in glass It is carried out in kiln 1.

Cooling bay 3 is used to that the glass metal after clarification is homogenized and is cooled down, and adjusts the viscosity of glass metal, it may be assumed that makes to melt The glass raw material melted is uniformly mixed, adjusts the viscosity of glass metal and be cooled to forming temperature, and the molding for subsequent glass metal provides Guarantee；

Molding molten tin bath 5 is used to the uniformly mixed glass metal of melting pulling into the glassware with fixed geometry, Molding molten tin bath 5 includes the symmetrical 6-12 that is arranged in pairs of two sides to edge machine 16, and glass metal 2 floats after entering molding molten tin bath 5 In the tin liquor 15 of melting, under the pulling force of the molding symmetrically arranged edge machine 16 in 5 two sides of molten tin bath, glass metal 2 is pulled into glass Band 6 completes molding.

First Transition roller tables 7 is used to adjust the temperature of glass tape 6 after molding to 600-660 DEG C, is then conveyed To coring molten tin bath 9；Roller 8 in First Transition roller tables 7 is made of quartz-ceramics.

The tin liquor 15 of melting is loaded in coring molten tin bath 9, glass tape 6 floats on 15 surface of tin liquor of melting, melting after entering Tin liquor 15 temperature of glass tape 6 is adjusted to 580-640 DEG C of progress coring；Coring molten tin bath 9 and the difference of molding molten tin bath are Two sides are not provided with edge machine 16.

Second transition roller table 10 is used to adjust the temperature of the glass tape 6 after coring to 740-950 DEG C, is then conveyed To crystallization molten tin bath 11；Roller 8 in second transition roller table 10 is made of quartz-ceramics.

The tin liquor 15 of melting is loaded in crystallization molten tin bath 11, glass tape 6 floats on 15 surface of tin liquor of melting, melting after entering Tin liquor 15 temperature of glass tape 6 is adjusted to 730-940 DEG C of progress crystallization；Crystallization molten tin bath 11 and the difference of molding molten tin bath are Two sides are not provided with edge machine 16.

It forms and fills nitrogen and hydrogen in the upper space 4 of molten tin bath, coring molten tin bath, crystallization molten tin bath, prevent tin liquor from aoxidizing；Glass The coring of glass and crystallization are all to adjust glass to a certain temperature range is just automatic to occur, Nucleating Agent when glass raw material is added just It is uniformly mixed with other raw materials, when fusing is evenly distributed on again at high temperature in the glass metal of melting, reaches coring and crystallization Temperature after, Nucleating Agent promotes the formation of nucleus in glass, and crystal is made to grow up, and forms devitrified glass.

Annealing kiln 13 is in order to eliminate the stress after molding in certain thickness glass tape 6, by the temperature of glass tape Degree is continuously down to 100 DEG C or less；It is separated between annealing kiln 13 and crystallization molten tin bath 11 by check apron 12.

The production method of above-mentioned devitrified glass, process flow include the pretreatment of Ta Nb tailings, the mixing of raw material, glass Melted and clarification, the homogenizing of glass metal, tin groove forming, a transition cooling and coring, secondary transition heating and the crystallization of liquid are moved back Fire and etc.；Each step carries out in the special equipment of above-mentioned production devitrified glass, specifically:

1), the pretreatment of Ta Nb tailings:

Ta Nb tailings are passed sequentially through into the processes such as classification, scouring, magnetic separation, pickling and obtain the tantalum niobium for being suitble to production devitrified glass Tailing sample, Fe in Ta Nb tailings sample₂O₃Content less than 0.01% (100ppm), partial size 0.1-1.5mm, water content is small In 5%.

2), the mixing of raw material:

After detecting the chemical composition in Ta Nb tailings sample, by calculating, by SiO₂、Al₂O₃、CaO、MgO、Na₂O、K₂O、 B₂O₃、ZnO、Li₂It is one or more of in O and MnO to be mixed with the Ta Nb tailings sample that step 1) obtains, it obtains comprising SiO₂ 43%-49.8%, Al₂O₃10.2%-16%, CaO 5.5%-9.9%, MgO 1.2%-9.8%, Na₂O 3.1%- 6.5%, K₂O 2.3%-7.7%, BaO 4.2%-8.8%, ZnO 4.5%-10%, Sb₂O₃0.2%-2%, nitrate 0.8%-8%, P₂O₅0.3%-1.8%, ZrO₂0.2%-1.5%, fluoride 0.1%-0.7%, TiO₂0.7%-3.5% Glass raw material；In general industry production, SiO₂From silica sand, Al₂O₃Come from feldspar, CaO from lime stone, MgO From in magnesite, Na₂O is from soda ash, K₂O is from potassium carbonate.

Preferably contain SiO in glass raw material₂45%-47%, Al₂O₃11%-14%, CaO 6%-8%, MgO 3%- 8%, Na₂O 4%-5%, K₂O 3%-6%, BaO 5%-7%, ZnO 5%-8%, Sb₂O₃0.5%-1.5%, nitrate 2%-6%, P₂O₅0.6%-1.5%, ZrO₂0.5%-1.1%, fluoride 0.2%-0.5%, TiO₂1.2%-2.9%； More preferably contain SiO₂46%, Al₂O₃12.5%, CaO 7%, MgO 5.5%, Na₂O 4.5%, K₂O 4.5%, BaO 6%, ZnO 6.5%, Sb₂O₃0.8%, nitrate 2.8%, P₂O₅0.8%, ZrO₂0.7%, fluoride 0.4%, TiO₂2%.

3), the melted and clarification of glass metal:

The glass raw material that step 2) mixes is melted into glass metal at 1600-1660 DEG C, is generally required left for 24 hours It is right；When obtained glass metal emerges there is no bubble and (12-25h or so generally required, to carry out enough clarifications), clarification is tied Beam；

4), the homogenizing and cooling of glass metal:

Temperature of glass liquid after clarification is maintained at 1620-1670 DEG C, until each section of glass metal reaches in chemical composition To uniformity (generally requiring 7-16h), homogenizing terminates, and homogenizing is to eliminate the striped and heterogeneous body in glass metal；Glass Glass liquid is cooled down during flow forward, is cooled to 1350-1400 DEG C；

5), tin groove forming:

Step 4) homogenizing and glass metal after cooling, which enter in molten tin bath, to be formed, and makes glass molding is uniform, smooth to have The plate glass transitional product of certain thickness and width, with a thickness of 2-15mm, width is generally wide with molten tin bath, the entrance of molten tin bath Temperature is 1250-1320 DEG C (forming temperature in existing method is 1050-1100 DEG C), and molten tin bath temperature is 750- after the completion of molding 930℃。

6), a transition cooling and coring:

Transitional product after molding enter First Transition roller tables adjust temperature to after 600-660 DEG C, be again introduced into molten tin bath into Row coring, nucleation temperature are 580-640 DEG C, nucleation time 30min-3h, obtain a transitional product.

7), secondary transition heating and crystallization:

A transitional product after coring enters the second transition roller table and adjusts temperature to after 740-950 DEG C, is again introduced into tin Slot carries out crystallization, and crystallization temperature is 730-940 DEG C, and crystallization time 2-8.5h obtains secondary transitional product.

8) it, anneals:

Secondary transitional product after crystallization used at 600-700 DEG C continuation mode annealing 2-8h or to 100 DEG C hereinafter, with The stress for eliminating glass, obtains devitrified glass.

It is micro- according to producing above using the special equipment of the above production devitrified glass and containing the glass raw material of Ta Nb tailings The devitrified glass of embodiment 1- embodiment 7 is prepared in the method for crystal glass.The devitrified glass of production example 1- embodiment 7 Parameter and raw material composition are shown in Table 4.

The raw material of the devitrified glass of 4 embodiment 1- embodiment 7 of table forms and manufacturing parameter

Experiment:

The bending strength for the glass that measurement embodiment 1-7 and comparative example 1-4 is obtained, by glass specimen through cutting, grinding, throwing The strip of 80 × 10 × 10mm is made after light, using three-point bending method, test equipment is DKZ-5000 type electric bending testing Machine.The performance test results are shown in Table 5.

The performance test results of table 5 embodiment 1-7 and comparative example 1-4 glass

As it can be seen that the devitrified glass of the utility model production has higher intensity compared with the devitrified glass that sintering process obtains, fit Cooperation is requires high-intensitive building decoration materials, while machining property is good, can be widely applied.

The above is only the preferred embodiment of the utility model, it is noted that for the general of the art For logical technical staff, without departing from the principle of this utility model, several improvements and modifications can also be made, these change Into the content that also should be regarded as the utility model with retouching.

Claims

1. a kind of special equipment for producing devitrified glass, including it is sequentially connected

Device for shaping glass and

The device for shaping glass be for forming glass metal float glass process to the molding molten tin bath for being loaded with soldering tin of glass tape,

Also be successively arranged between the molding molten tin bath and annealing kiln be loaded with soldering tin, for carrying out coring to glass tape Coring molten tin bath and for glass tape carry out crystallization crystallization molten tin bath.

2. special equipment according to claim 1, which is characterized in that be equipped with and be used between the molding molten tin bath and coring molten tin bath Adjustment glass tape temperature and the First Transition roller tables for being transported to coring molten tin bath.

3. special equipment according to claim 2, which is characterized in that be equipped with and be used between the coring molten tin bath and crystallization molten tin bath Adjustment glass tape temperature and the second transition roller table for being transported to crystallization molten tin bath.

4. special equipment according to claim 3, which is characterized in that the two sides of the molding molten tin bath are also equipped with a multipair left side in pairs Right symmetrical edge machine.

5. special equipment according to claim 4, which is characterized in that the edge machine is arranged 6-12 pairs.

6. special equipment according to claim 1, which is characterized in that the coring molten tin bath and crystallization molten tin bath two sides are not provided with drawing Side machine.

7. according to the special equipment of claim 5 or 6, which is characterized in that the molding molten tin bath, coring molten tin bath, crystallization molten tin bath In be equipped with for fill prevent tin liquor oxidation nitrogen and hydrogen inflating port.

8. special equipment according to claim 7, which is characterized in that in the First Transition roller tables and the second transition roller table Roller is Quartz Ceramic Roller.

9. special equipment according to claim 8, which is characterized in that the glass melter is oxy-fuel combustion glass melting furnace.

10. special equipment according to claim 9, which is characterized in that be equipped with 5-8 in the glass melter and sprayed to all-oxygen combustion Rifle.