CN100528781C - Microcrystal glass made from titanium-containing magnetic iron are tailings - Google Patents
Microcrystal glass made from titanium-containing magnetic iron are tailings Download PDFInfo
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- CN100528781C CN100528781C CNB2006100952999A CN200610095299A CN100528781C CN 100528781 C CN100528781 C CN 100528781C CN B2006100952999 A CNB2006100952999 A CN B2006100952999A CN 200610095299 A CN200610095299 A CN 200610095299A CN 100528781 C CN100528781 C CN 100528781C
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- titanium
- mine tailing
- devitrified glass
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- debris
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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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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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
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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Abstract
This invention provides a glass ceramic produced by debris of magnetite that contains titanium. it takes titanium-containing debris as the main raw material, plus quartz sand that SiO2 purity greater than 96% and content of 18% ~ 30%; With further increase feldspar that content of 2% to 5% as additives; the weight percentage of above glass ceramic composition: SiO2: 55 ~ 65, Al2O3: 4 to 10, CaO: 10 ~ 20, MgO: 3-7, TiO2: 4 to 7, Fe2O3: 4.0 ~ 9.5, ZrO2: 0 ~ 1.5 , K2O - Na2O: 4 to 9. This invention can comprehensive utilize of titanium containing vanadium and titanium magnetite debris, can effectively solve the problem of environmental and safety issues caused by the long-term accumulation of debris, and reduce production costs.
Description
Technical field
The present invention relates to the titaniferous mine tailing of vanadium titano-magnetite is applied to building and ornament materials, make the technology of devitrified glass, be specifically related to the devitrified glass that a kind of titanium-containing magnet ore deposit mine tailing is made.
Background technology
Devitrified glass is a kind of intensity (bending resistance, resistance to compression) of manually developing in recent decades, hardness, erosion resistance (acidproof, alkaline-resisting) and all very high type material such as wear-resisting, is called granolith (or marble) again.Be mainly used in industry and departments such as building decoration, metallurgy, chemical industry, machinery, pottery, medical science, astronomical telescope.When using, have the texture close with lithotome as building and ornament materials, elegance attractive in appearance, atmospheric corrosion resistance, quality is light, easily processing.In addition, can produce the more inner, external wall finishing material of horn of plenty of color flower face by toning and combination.And can utilize the high characteristics of transparency, in be equipped with light, be used for edge list, wall etc., more apparent gorgeous elegance.Along with the fast development of national economy and the rapid raising of living standards of the people, increasing to the demand of this high-grade finishing material of devitrified glass.
The main raw material of devitrified glass (base-material) adopts and contains silicon-dioxide (SiO
2) higher raw material, as making such as blast furnace slag, converter slag, flyash, metal tailings, non-ferrous metal slag, for example Chinese patent 03111105.X disclosed " compound fly ash building manufacture method of glass-ceramic ".Different with the general sheet glass of production is, the production of devitrified glass also will be added many other additives, in heat treatment process, separate out small grains (about 0.5～1.0 micron of grain-size) to satisfy when devitrified glass is made, reach performance requriementss such as high strength; And satisfied requirement of producing the devitrified glass kind of various patterns and texture.Up to the present, make existing at home more research, Chinese patent 200410058079.X disclosed " containing devitrified glass and method that the molybdenum mine tailing is made " and 200410058045.0 disclosed " devitrified glass and the methods of high iron tailings manufacturing " etc. for another example aspect the devitrified glasses utilizing mine tailing such as iron-containing tailing, non-ferro metals debris etc.; Some researchs are abroad also arranged.But do main raw material making Research of Glass-ceramics at titaniferous magnetite mine tailing specially and yet there are no relevant bibliographical information.
Very abundant v-ti magnetite ore resources is being contained in the Flos Bombacis Malabarici in China southwest--area, Xichang, and the reserves of verifying surpass 10,000,000,000 tons, and 33.88 hundred million tons of retained reserves are the domestic important iron ore deposits that is only second to saddle this area.The vanadium titano-magnetite of what is more important Panxi Diqu still is world-famous compound mineral intergrowth, and its vanadium and titanium resources has not only occupied absolute status at home, also cans be counted on one's fingers in the world.Its iron reserves account for 20% of China; TiO
2Account for more than 90% of China; V
2O
5Account for 80% of China.The Flos Bombacis Malabarici vanadium titano-magnetite mainly is by ore dressing, obtains iron ore concentrate earlier and is used for ironmaking and STEELMAKING PRODUCTION steel product, contains the vanadium of part titanium and higher proportion in iron ore concentrate; Select the mine tailing master titanium-containing iron ore behind the iron, it is mainly used in and selects titanium, and the titanium production line that selects that has built up at present can only select titanium to handle to the part iron selection tailings; Select the mine tailing behind the titanium also to contain a considerable amount of titaniums.The comprehensive mine tailing that does not select the mine tailing of titanium and selected titanium contains the titanium dioxide of higher proportion, and makes Flos Bombacis Malabarici vanadium titano-magnetite mine tailing become the iron tailings that has than high titanium content in mine tailing, the roughly content of its mine tailing chemical ingredients sees Table 1.
Table 1 titaniferous mine tailing main component table (wt%)
At present, serve as to calculate the basis with the raw ore of exploiting, the rate of recovery of each element that in product, embodies, iron is approximately 73.40%; Vanadium is approximately 26.28%; Titanium is approximately 3.11%.Other useful element residues in smelting process to be become in the steel the alloying element, does not have special extraction and application.
Go into operation from first blast furnace of Panzhihua Iron 1970,1971 first block converters reborn produce since, up to the present, Panzhihua Iron has been produced 30 years.Handle 1,350 ten thousand tons/year in raw ore by annual exploitation, over more than 30 year, the titaniferous mine tailing has accumulated very big quantity.The accumulation of mine tailing has produced relatively serious environmental and safety problem, and the potentially dangerous of polluting Jinsha jiang River is arranged, and has dam break to have the problem of potential safety hazard.Therefore, the extensive comprehensive utilization of carrying out Flos Bombacis Malabarici titaniferous vanadium titano-magnetite mine tailing has crucial meaning.
Summary of the invention
At the prior art above shortcomings, the purpose of this invention is to provide a kind of effective development and use Flos Bombacis Malabarici titanium-containing magnet ore deposit mine tailing resource, the titaniferous mine tailing of vanadium titano-magnetite is applied to building and ornament materials and devitrified glass that a kind of titanium-containing magnet ore deposit mine tailing of providing is made.
The object of the present invention is achieved like this: the devitrified glass that titanium-containing magnet ore deposit mine tailing is made is characterized in that: with the titaniferous mine tailing as main raw material, with addition of SiO
2Purity is 18%～30% quartz sand greater than 96% content; Be that 2%～5% feldspar can be made the good tailing microcrystal glass of obtained performance as additive with addition of content again.
The weight percent of described devitrified glass composition is: SiO
2Be 55～65, Al
2O
3Be 4～10, CaO is 10～20, and MgO is 3～7, TiO
2Be 4～7, Fe
2O
3Be 4.0～9.5, ZrO
2Be 0～1.5, K
2O-Na
2O is 4～9.
The titaniferous mine tailing that the present invention adopts is made devitrified glass, and under the situation of crystallization temperature (about 810-860 ℃), the processing method of its making devitrified glass is identical with the manufacture craft of common wollastonite devitrified glass, cinder microcrystalline glass etc.
The invention has the beneficial effects as follows:
1, can mass-producing fully utilize the titaniferous vanadium titano-magnetite mine tailing of Flos Bombacis Malabarici, can effectively solve the environmental pollution and the safety problem of the long-term accumulation generation of mine tailing, and can reduce production costs;
2, owing to adopt the technology and the method for existing making devitrified glass, can build the production line that titanium-containing magnet ore deposit mine tailing is made devitrified glass fully, be mainly used in the devitrified glass of making as high-grade finishing material;
3, formulating of recipe is reasonable, and it is definite to carry out actual test by the crystallization temperature when making devitrified glass, adopts conventional manufacture craft can produce superior in quality devitrified glass.
4, in the preparation of devitrified glass, TiO
2Be a kind of important nucleus agent and make toner.Owing to contain the TiO of some amount
2, can add TiO less
2With the nucleus agent of other kind, thereby can save cost, the additional proportion of titaniferous mine tailing can be higher.
Description of drawings
Fig. 1 is the parent glass DSC curve of No.4 sample
Fig. 2 is the parent glass DSC curve of No.6 sample
Fig. 3 is the metallographic structure (400X) of No.4 sample
Fig. 4 is the metallographic structure (400X) of No.6 sample
Embodiment
At the development and use of the titanium-containing magnet ore deposit mine tailing of Flos Bombacis Malabarici, the present invention is according to the composition characteristic of vanadium titano-magnetite mine tailing, directly with it as the raw material of producing devitrified glass, high-load TiO
2Be the nucleus agent and the fusing assistant of excellent property, CaO, MgO, Al in the glass ingredient
2O
3, Fe
2O
3Mainly introduce, do not add substantially by mine tailing; Add SiO in addition
2To reduce the relative content of CaO, MgO, improve the crystallization property of glass, because SiO
2Being glass network former, is main component, and content can not be too low; But can not be too high, too high glass viscosity increases.
Flos Bombacis Malabarici titanium-containing magnet ore deposit mine tailing is made devitrified glass, and its key is with mine tailing as main raw material, is 18%～30% quartz sand SiO again greater than 96% content with addition of purity
2Can make the good tailing microcrystal glass of obtained performance with addition of a spot of feldspar (about 2%～5%) as additive more in addition.As nucleus agent, ZrO
2Can not add or add less.
Table 2 is design composition tables that Flos Bombacis Malabarici titanium-containing magnet ore deposit mine tailing is made devitrified glass.
Table 2 design glass ingredient table (Wt%)
Al
2O
3Content want suitably.Al
2O
3Can significantly reduce the crystallization ability of glass, wollastonite crystalline recrystallization temperature is with Al in the glass
2O
3The increase of content and raising, its crystallization speed then decreases.And the recrystallization temperature of devitrified glass is low, when speed of separating out is too fast, the sintering process of product is difficult to fine carrying out, it is closely knit that product is difficult to, the void content height.So for to guarantee that product has good sintering and crystallization property, Al in the parent glass
2O
3Content must reach certain value, but can not be too high.
CaO content is wanted suitably, can not be too low, and too low devitrification of glass speed is little, and the crystalline phase amount is few, is difficult to guarantee that product has the ideal physical and chemical performance; But if greater than 20% o'clock, the mobile variation of glass then, the discharging difficulty, and crystallization speed is big.
The content of MgO can be adjusted the crystallization property of material property and goods at 3～7% o'clock.But can not be too high, the too high crystalline phase that may make becomes complicated, can not guarantee the performance of goods.
Suitably add Na
2O, K
2Oxide compounds such as O can satisfy the requirement of material property and manufacturing process, R
2The content of O can not be less than 4%, otherwise the mobile variation between glass particle, but if greater than 9% o'clock, the softening temperature of goods is low excessively.
Carried out the experiment of the concrete prescription of group surplus in the of 10 by the formula range of table 2, wherein 4# and 6# prescription sees Table 3.
Table 3 experiment glass ingredient table (wt%)
Annotate: Fe in table
2O
3Content all be 4.56%, TiO
2Content is 3.53% all, excludes.
Carried out the parent glass crystallization tracing analysis of the DSC of each prescription with the heat analysis, wherein the DSC curve of 4# and 6# as depicted in figs. 1 and 2.Promptly represented the crystallization temperature of devitrified glass among the figure at the heat peak value more than 800 ℃.No matter be preparation method's (sintering process, rolling process etc.) of the sort of devitrified glass, should be higher than this thermal spike in the recrystallization temperature of the original material matrix of thermal treatment control devitrified glass.
And the titanium-containing magnet ore deposit mine tailing that the present invention relates to is made devitrified glass, because the devitrified glass that its ore deposit phase composite and other mine tailings and slag etc. are made may be different, the temperature the when height of its crystallization temperature may have certain difference, the melting of employing sintering process is difference to some extent also; But the method (sintering process, rolling process etc. are based on sintering process) of the making devitrified glass that adopts is identical with the manufacture craft of common wollastonite devitrified glass, cinder microcrystalline glass etc.
Therefore, the titaniferous mine tailing that the present invention adopts is made the prescription of devitrified glass, measuring by thermal analyzer and clear and definite the making under the situation of the data such as crystallization temperature (DSC peak of curve) in the devitrified glass, the manufacture craft of the processing method of its making devitrified glass and common wollastonite devitrified glass, cinder microcrystalline glass etc. is identical.
Can work out the heat treating regime of devitrified glass according to the DSC curve of testing the parent glass that obtains.For 4# and 6# devitrified glass parent glass prescription, obtained the good devitrified glass sample of hardness after the thermal treatment, its tissue is seen Fig. 3 and Fig. 4.Test shows, the hardness of two kinds of prescription devitrified glasses has reached 620kg/mm respectively
2And 588kg/mm
2About.
Claims (2)
1, the mine tailing devitrified glass made in titanium-containing magnet ore deposit is characterized in that, with the titaniferous mine tailing as main raw material, with addition of SiO
2Purity is 18%～30% quartz sand greater than 96% weight percent; Be that 2%～5% feldspar forms as additive with addition of weight percent again.
2, the devitrified glass of titanium-containing magnet ore deposit mine tailing making according to claim 1 is characterized in that the weight percent of described devitrified glass composition is: SiO
2Be 55%～65%, AL
2O
3Be 4%～10%, CaO is 10%～20%, and MgO is 3%～7%, TiO
2Be 4%～7%, Fe
2O
3Be 4.0%～9.5%, ZrO
2Be 0%～1.5%, K
2O-Na
2O is 4%～9%.
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|---|---|---|---|
| CNB2006100952999A CN100528781C (en) | 2006-12-15 | 2006-12-15 | Microcrystal glass made from titanium-containing magnetic iron are tailings |
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| CN100528781C true CN100528781C (en) | 2009-08-19 |
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| CN102453562B (en) * | 2010-10-27 | 2014-04-30 | 中国石油化工股份有限公司 | Organic amide low-sulfur diesel oil lubrication additive and application thereof |
| CN102079625A (en) * | 2010-12-07 | 2011-06-01 | 淮安乔氏建材发展有限公司 | Microcrystal glass manufactured by using tailing solid waste and manufacturing method thereof |
| CN102775070B (en) * | 2012-08-21 | 2015-09-02 | 何德开 | Crystallizing glass sheet material and preparation method thereof is manufactured with copper tin metal mine tailing |
| CN103073186B (en) * | 2013-01-28 | 2015-05-20 | 吴克诚 | Preparation method for producing calendered crystallite cast stone plate with iron tailings |
| CN104926131B (en) * | 2015-06-05 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of vanadium titano-magnetite tailing microcrystal glass and preparation method thereof |
| CN106116159A (en) * | 2016-06-22 | 2016-11-16 | 河北省沙河玻璃技术研究院 | A kind of imitative Achates devitrified glass |
| CN106082673A (en) * | 2016-06-22 | 2016-11-09 | 河北省沙河玻璃技术研究院 | A kind of imitative Achates devitrified glass production technology |
| CN108455861A (en) * | 2018-04-11 | 2018-08-28 | 四川名微晶科技股份有限公司 | A method of using iron ore tailings be main material production devitrified glass |
| CN108373266A (en) * | 2018-04-11 | 2018-08-07 | 四川名微晶科技股份有限公司 | A method of preparing devitrified glass new material using smelting titanium tailings |
| CN108409142A (en) * | 2018-05-18 | 2018-08-17 | 四川名微晶科技股份有限公司 | R is prepared by raw material of red mud2O-CaO-Al2O3-SiO2-Fe2O3The method of microcrystalline glass in series |
| CN108558217A (en) * | 2018-07-03 | 2018-09-21 | 四川名微晶科技股份有限公司 | A method of devitrified glass is prepared with titanium slag tailings collaboration granite tailing |
| CN109020243B (en) * | 2018-10-18 | 2021-08-31 | 陕西理工大学 | Method for preparing microcrystalline foam glass from vanadium-titanium magnet tailings |
| CN111470777B (en) * | 2020-03-27 | 2022-08-02 | 广东工业大学 | CAS series iron tailing microcrystalline glass material and preparation method and application thereof |
| CN113149443A (en) * | 2021-05-06 | 2021-07-23 | 西南科技大学 | Method for preparing building glass ceramics from granite tailings and high-titanium slag |
| CN114230184B (en) * | 2021-12-30 | 2023-07-14 | 武汉理工大学 | Microcrystalline glass with liquid titanium slag as main raw material and preparation method thereof |
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- 2006-12-15 CN CNB2006100952999A patent/CN100528781C/en not_active Expired - Fee Related
Non-Patent Citations (4)
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| 铁尾矿制备微晶玻璃研究的进展. 陈盛建，陈吉春，高宏亮，余以雄.矿业快报，第总第417期. 2004 |
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