CN104261677A - Method for preparing microcrystalline glass from lithium beryllium tailings - Google Patents

Method for preparing microcrystalline glass from lithium beryllium tailings Download PDF

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Publication number
CN104261677A
CN104261677A CN201410471994.5A CN201410471994A CN104261677A CN 104261677 A CN104261677 A CN 104261677A CN 201410471994 A CN201410471994 A CN 201410471994A CN 104261677 A CN104261677 A CN 104261677A
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China
Prior art keywords
glass
devitrified glass
raw material
lithium beryllium
mine tailing
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CN201410471994.5A
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CN104261677B (en
Inventor
张深根
贾殿赠
刘浪
黄玉代
卜金彪
杨健
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Xinjiang non ferrous metal industry (Group) Co., Ltd.
University of Science and Technology Beijing USTB
Xinjiang University
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University of Science and Technology Beijing USTB
Xinjiang University
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C10/00Devitrified 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
    • C03C10/0063Devitrified 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 containing waste materials, e.g. slags

Abstract

The invention relates to a method for preparing microcrystalline glass from lithium beryllium tailings, which is characterized in that certain amounts of limestone and cupronickel water quenching slag are added to the lithium beryllium tailings used as the main raw material to prepare the microcrystalline glass. The method basically comprises the following steps: drying the raw material, proportioning, mixing, melting, casting, annealing and carrying out heat treatment to obtain the microcrystalline glass. By using the lithium beryllium tailings and cupronickel water quenching slag as the raw materials without adding other chemical raw materials, the microcrystalline glass prepared by a melting process has the characteristics in microcrystal and glass, and has the advantages of favorable mechanical properties, favorable thermal shock performance and favorable chemical stability. The lithium beryllium tailings and cupronickel water quenching slag are coprocessed, thereby lowering the production cost of the microcrystalline glass and having obvious economic and environmental benefits.

Description

A kind of method utilizing lithium beryllium mine tailing to prepare devitrified glass
Technical field
The present invention relates to a kind of method utilizing lithium beryllium mine tailing to prepare devitrified glass, particularly with lithium beryllium mine tailing be main raw material, Wingdale and copper nickel Water Quenching Slag prepare the method for devitrified glass for auxiliary material, belongs to environmental area and field of metallurgy.
Background technology
Lithium beryllium mine tailing is that after the useful component such as lithium, beryllium that comprehensively extracts through the multiple beneficiation method such as gravity treatment, flotation, magnetic separation, electric separation in ore of rare metal ore, the side product from ore dressing of generation, its main component is SiO 2and Al 2o 3.Due to its SiO 2and Al 2o 3content is higher, and its fusing point is more than 1700 DEG C, and melting homogenizing difficulty is large, and in full-bodied situation, a large amount of bubbles existed in system are not easily discharged, for its recycling brings difficulty.Learn according to existing test and evaluation report, end to 2012, in the mine tailing separating plant Tailings Dam of Koktokay mining area, Powdered mine tailing amount is up to 4,000,000 tons.At present, the main Land use systems of lithium beryllium mine tailing reclaims rare metal in mine tailing and non-metallic minerals, fails to realize its direct whole utilization, reclaims the economic benefit that the methods such as mica create not high simultaneously, cause waste to pile up, problem cannot fundamentally solve.
The relevant report adopting mine tailing waste residue to prepare devitrified glass has much, and ([1] application number: 201310137329.8, application name is called " preparation method based on iron tailings being the composite microcrystallite glass of raw material ".[2] application number: 201210496348.5, application title " without Nucleating Agent devitrified glass preparation method ".[3] application number: 201310080423.4, application title " a kind of method utilizing blast furnace slag to prepare devitrified glass ".[4] application number: 201210103590.1, application title " a kind of method utilizing high-titanium blast furnace slag to prepare devitrified glass ".Application number: 201310217525.6, application title " a kind of Pb-Zn tailings prepares the processing method of dark devitrified glass ".[5] application number: 201310181939.8, application title " a kind of devitrified glass and preparation method thereof ".[6] Zhang Yuanzhi. [J] is inquired in the trial-production of slag, ash glass-Ceramics. Anhui chemical industry, 1998, (6): 31-33.[7] Yang Zhijie, Cang great Qiang, Li Yu etc., molten steel slag prepares the experimental study [J] of devitrified glass, New Building Materials, 2011, (7): 52 ~ 65.Above-mentioned relevant report more or less introduces chemical reagent in devitrified glass preparation process, and major part adopts sintering process, and the production cost of devitrified glass is relatively high, and the physical and mechanical properties of devitrified glass is relatively poor.
In sum, when not adding any chemical reagent, introduce Fe with the form of copper nickel Water Quenching Slag 2o 3as main Nucleating Agent, simultaneously there is high-melting-point and composition and the larger lithium beryllium mine tailing of existing cinder microcrystalline glass composition tolerances adopt scorification to prepare devitrified glass as main raw material have not been reported.
Summary of the invention
The object of the invention is the shortcoming overcoming above-mentioned prior art, provide a kind of method utilizing lithium beryllium mine tailing to prepare devitrified glass, prepare devitrified glass raw materials used based on lithium beryllium mine tailing, Wingdale and copper nickel Water Quenching Slag are auxiliary, do not add any chemical reagent, prepared the devitrified glass with excellent mechanical performances, solve the technical difficult problem that the problem of environmental pollution of mine tailing and lithium beryllium mine tailing are difficult to utilize, reduce the production cost of devitrified glass, improve value-added content of product.
First, by levigate for raw material to 40 orders, and it is dried at 120 DEG C.
Then, according to mass percent by the lithium beryllium mine tailing of 30.07% ~ 47.40%, the Wingdale of 43.97% ~ 52.41% and the copper nickel Water Quenching Slag of 5.44% ~ 17.52% mix, and load in High Temperature Furnaces Heating Apparatus.
The raw material mixed is incubated melting 1 ~ 6h at 1400 DEG C ~ 1600 DEG C, and then watered fast by melt and cast from the annealing 30min ~ 180min that is shaped in the mould of 400 DEG C ~ 600 DEG C of preheatings in advance, last furnace cooling obtains parent glass.
Parent glass is heat-treated, is heated to 700 DEG C ~ 900 DEG C insulation 30 ~ 180min with 5 ~ 10 DEG C/min temperature rise rate, the Fe introduced with copper nickel Water Quenching Slag form 2o 3abundant forming core is carried out as main Nucleating Agent.Again with the temperature rise rate of 5 ~ 10 DEG C/min, be warming up to 850 DEG C ~ 1100 DEG C insulation 1 ~ 5h, then furnace cooling can obtain devitrified glass.
Devitrified glass carries out cutting, polish, polishing, can obtain devitrified glass finished product.
Compared with the present invention prepares devitrified glass with sintering process, technique is short, and energy consumption is low, and raw materials cost is low, and waste utilization rate is high.
Accompanying drawing explanation
Fig. 1 is devitrified glass preparation flow figure
Embodiment
Embodiment 1
The first step, carries out composition analysis to raw material, according to composition analysis result, prepares burden to raw material.Raw material and product composition proportioning are in Table-1 and table-2.
The proportioning raw materials (wt.%) of table-1 devitrified glass product
Raw material Lithium beryllium mine tailing Wingdale Copper nickel Water Quenching Slag
Devitrified glass 47.40 47.15 5.45
Table-2 raw materials and product chemical constitution (wt.%)
Component SiO 2 Al 2O 3 CaO Fe 2O 3 Other
Lithium beryllium mine tailing 76.72 13.28 0.18 0.34 9.48
Wingdale 1.10 0.48 54.42 0.32 43.95
Copper nickel Water Quenching Slag 34.95 8.09 2.14 44.02 10.80
Devitrified glass 48.60 8.72 32.40 3.00 7.28
Second step, raw material is dried at 120 DEG C, raw material is mixed by composition proportion, then High Temperature Furnaces Heating Apparatus is put into, rise to 1460 DEG C from room temperature, and melting 2.5h obtains glass melt at 1460 DEG C, glass melt is cast in the mould of 600 DEG C and be shaped, annealing 30min, last furnace cooling finally obtains parent glass.
3rd step, heat-treats parent glass, is heated to 850 DEG C of insulation 60min, the Fe introduced with copper nickel Water Quenching Slag form with 5 DEG C/min temperature rise rate 2o 3as main Nucleating Agent, make the abundant forming core of parent glass; Again with the temperature rise rate of 5 DEG C/min, be warming up to 1100 DEG C of insulation 1h, make its abundant micritization, finally cool to the glass of micritization with the furnace room temperature, described devitrified glass can be obtained.
Embodiment 2
The first step, according to composition analysis result, carries out proportioning to raw material, and raw material and product composition proportioning are in Table-3 and table-4.
The proportioning raw materials (wt.%) of table-3 devitrified glass products
Raw material Lithium beryllium mine tailing Wingdale Copper nickel Water Quenching Slag
Devitrified glass 44.77 46.11 9.12
Table-4 product chemical constitutions (wt.%)
Component CaO SiO 2 Al 2O 3 Fe 2O 3 Other
Devitrified glass 31.60 47.40 8.60 5.00 7.40
Raw material is dried at 120 DEG C, and mix by composition proportion, then High Temperature Furnaces Heating Apparatus is put into, 1500 DEG C are risen to from room temperature, and melting 2.5h obtains glass melt at 1500 DEG C, cast in by glass melt in the mould of 600 DEG C and be shaped, annealing 30min, last furnace cooling finally obtains parent glass.
Parent glass is heat-treated, from room temperature with the temperature rise rate of 5 DEG C/min, is warming up to 860 DEG C of insulation 60min, the Fe introduced with copper nickel Water Quenching Slag form 2o 3as main Nucleating Agent, make its abundant forming core, then with the temperature rise rate of 5 DEG C/min, be warming up to 1100 DEG C of insulation 1h, make its abundant micritization, then cool to room temperature with the furnace, can devitrified glass be obtained.
Embodiment 3
The first step, according to composition analysis result, carries out proportioning to raw material, and raw material and product composition proportioning are in Table-5 and table-6.
The proportioning raw materials (wt.%) of table-5 devitrified glass products
Raw material Lithium beryllium mine tailing Wingdale Copper nickel Water Quenching Slag
Devitrified glass 30.07 52.41 17.52
Table-6 product chemical constitutions (wt.%)
Component SiO 2 CaO Al 2O 3 Fe 2O 3 Other
Devitrified glass 38.24 37.25 7.27 9.80 7.44
Raw material is dried at 120 DEG C, and mix by composition proportion, then High Temperature Furnaces Heating Apparatus is put into, 1600 DEG C are risen to from room temperature, and melting 2.5h obtains glass melt at 1600 DEG C, cast in by glass melt in the mould of 650 DEG C and be shaped, annealing 30min, last furnace cooling finally obtains parent glass.
Parent glass is heat-treated, from room temperature with the temperature rise rate of 5 DEG C/min, is warming up to 800 DEG C of insulation 60min, the Fe introduced with copper nickel Water Quenching Slag form 2o 3as main Nucleating Agent, make its abundant forming core, then with the temperature rise rate of 5 DEG C/min, be warming up to 1000 DEG C of insulation 1h, make its abundant micritization, then cool to room temperature with the furnace, can devitrified glass be obtained.
Aforesaid method is the invention that professional and technical personnel in the field can realize or use; apparent to the multiple amendment of these embodiments concerning those skilled in the art; therefore; the present invention can not be restricted to embodiment illustrated herein, the distortion done of with good grounds this programme or apparent change all among protection scope of the present invention.

Claims (3)

1. utilize lithium beryllium mine tailing to prepare a method for devitrified glass, it is characterized in that, comprise the step preparing parent glass and step parent glass being obtained devitrified glass by thermal treatment:
(1) by levigate for raw material to 40 orders, and it to be dried under 120 ° of C, then by raw material by proportioning Homogeneous phase mixing, and load in High Temperature Furnaces Heating Apparatus, described raw material comprises lithium beryllium mine tailing, Wingdale and copper nickel Water Quenching Slag;
(2) raw material mixed is incubated melting 1 ~ 6h under 1400 ° of C ~ 1600 ° C, obtain melt, then watered fast by melt and cast from advance in the mould of 400 ° of C ~ 600 ° C preheating, be shaped and the 30min ~ 180min that anneals, last furnace cooling obtains parent glass;
(3) parent glass of step (2) is heat-treated, be heated to 700 ° of C ~ 900 ° C with 5 ~ 10 ° of C/min temperature rise rates and be incubated 30min ~ 180min, the Fe introduced with copper nickel Water Quenching Slag form 2o 3carry out abundant forming core as main Nucleating Agent, then with the temperature rise rate of 5 ~ 10 ° of C/min, be warming up to 850 ° of C ~ 1100 ° C and be incubated 1 ~ 5h, then furnace cooling can obtain devitrified glass;
(4) step (3) described devitrified glass is carried out polish, polishing, cutting can obtain devitrified glass finished product.
2. a kind of method utilizing lithium beryllium mine tailing to prepare devitrified glass according to claim 1, it is characterized in that, described method raw materials quality per-cent composition: lithium beryllium mine tailing 30.07% ~ 47.40%, Wingdale 43.97% ~ 52.41%, copper nickel Water Quenching Slag 5.44% ~ 17.52%.
3. a kind of method utilizing lithium beryllium mine tailing to prepare devitrified glass according to claim 1, it is characterized in that, the principal crystalline phase of devitrified glass is wollastonite and gehlenite.
CN201410471994.5A 2014-09-16 2014-09-16 A kind of method utilizing lithium beryllium mine tailing to prepare devitrified glass Expired - Fee Related CN104261677B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105819694A (en) * 2016-04-11 2016-08-03 新疆有色金属工业(集团)有限责任公司 Glass ceramic and preparation method thereof
CN109354416A (en) * 2018-12-07 2019-02-19 李异洪 It is a kind of to utilize the once sintered process for preparing devitrified glass of lithium porcelain stone tailing
CN113149442A (en) * 2021-03-23 2021-07-23 广东昊昌智能装备有限公司 Method for preparing high-temperature-resistant composite crystal by using fly ash

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056857A (en) * 1990-05-26 1991-12-11 中国科学院上海硅酸盐研究所 The manufacturing of black glass ceramic and method
CN101020968A (en) * 2006-12-29 2007-08-22 金川集团有限公司 Process of comprehensively utilizing high temperature nickel smelting slag
CN101439932A (en) * 2008-12-26 2009-05-27 中国地质科学院尾矿利用技术中心 Low-expansion glass-ceramics with lithia ore tailings as principal raw material and manufacturing method thereof
CN102229468A (en) * 2010-07-09 2011-11-02 鞍钢集团矿业公司 Low-expansion micro-crystal glass manufactured from high-silicon iron tailings and preparation method thereof
CN102515553A (en) * 2011-12-13 2012-06-27 淄博钰晶新型材料科技有限公司 Method for producing microcrystalline foam thermal-insulation sheet material through utilizing industrial lithium tailings
CN102531394A (en) * 2011-12-28 2012-07-04 淄博钰晶新型材料科技有限公司 Formula and production process for producing microcrystal panels using lithium tailings
CN102838283A (en) * 2012-10-11 2012-12-26 南京师范大学 Method for producing foam microcrystal glass by utilizing composite industrial residue and product

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056857A (en) * 1990-05-26 1991-12-11 中国科学院上海硅酸盐研究所 The manufacturing of black glass ceramic and method
CN101020968A (en) * 2006-12-29 2007-08-22 金川集团有限公司 Process of comprehensively utilizing high temperature nickel smelting slag
CN101439932A (en) * 2008-12-26 2009-05-27 中国地质科学院尾矿利用技术中心 Low-expansion glass-ceramics with lithia ore tailings as principal raw material and manufacturing method thereof
CN102229468A (en) * 2010-07-09 2011-11-02 鞍钢集团矿业公司 Low-expansion micro-crystal glass manufactured from high-silicon iron tailings and preparation method thereof
CN102515553A (en) * 2011-12-13 2012-06-27 淄博钰晶新型材料科技有限公司 Method for producing microcrystalline foam thermal-insulation sheet material through utilizing industrial lithium tailings
CN102531394A (en) * 2011-12-28 2012-07-04 淄博钰晶新型材料科技有限公司 Formula and production process for producing microcrystal panels using lithium tailings
CN102838283A (en) * 2012-10-11 2012-12-26 南京师范大学 Method for producing foam microcrystal glass by utilizing composite industrial residue and product

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105819694A (en) * 2016-04-11 2016-08-03 新疆有色金属工业(集团)有限责任公司 Glass ceramic and preparation method thereof
CN105819694B (en) * 2016-04-11 2018-04-10 新疆有色金属工业(集团)有限责任公司 Devitrified glass and preparation method thereof
CN109354416A (en) * 2018-12-07 2019-02-19 李异洪 It is a kind of to utilize the once sintered process for preparing devitrified glass of lithium porcelain stone tailing
CN113149442A (en) * 2021-03-23 2021-07-23 广东昊昌智能装备有限公司 Method for preparing high-temperature-resistant composite crystal by using fly ash

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