CN104230169B - A kind of method preparing full solid waste high strength glass pottery for major ingredient with cinder - Google Patents
A kind of method preparing full solid waste high strength glass pottery for major ingredient with cinder Download PDFInfo
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- CN104230169B CN104230169B CN201410469887.9A CN201410469887A CN104230169B CN 104230169 B CN104230169 B CN 104230169B CN 201410469887 A CN201410469887 A CN 201410469887A CN 104230169 B CN104230169 B CN 104230169B
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- cinder
- solid waste
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Abstract
The invention provides a kind of method preparing full solid waste high strength glass pottery for major ingredient with cinder.The method with 50～the titanium slag of the white clay of magnesium slag, 0～15%, 2～10% of the cinder of 95%, 0～45% and 3～10% sodium hypophosphite waste residue as raw material, use high-temperature fusion, moulding by casting and Crystallization method to prepare the glass ceramics of high intensity.The method preparation technology is simple, and utilization rate of solid waste 100%, can efficiently solve cinder, magnesium slag, white clay, titanium slag and the pollution problem to environment of the sodium hypophosphite waste residue solid waste.The rupture strength of the glass ceramics that the present invention prepares is up to more than 300MPa, and its product is wear-resisting, corrosion resistance good, and color and luster is soft, texture good, added value is high, can be used as building and ornament materials, industrial wear-resistant corrosion resistant material and the production of artware, wide market.
Description
Technical field
The invention belongs to new material and environmental technology field, particularly relate to that a kind of to prepare full solid waste with cinder for major ingredient high-strength
The method of degree glass ceramics.
Background technology
Along with the development of China's economic, becoming increasingly dependent on the oil of the title having " industry blood ", according to statistics, China arrives
The year two thousand twenty is up to 2.6 × 10 to the consumption figure of product oil8Ton/year.Crude oil needs just to become product oil, crude oil through refinery
In lay particular stress on oil more, need through sulfide catalytic cracking (FCC) technology to resolve into light oil, and catalytic cracking technology be most important
It it is catalytic cracking catalyst.Due to the increase in demand to product oil, the acceleration that have stimulated catalytic cracking catalyst produces, thus also
Considerably increase and produce the amount discharging solid waste in petroleum catalytic cracking catalyst process.The most conventional catalytic cracking is urged
Agent has unformed aluminium silicate (such as natural clay, synthesis low aluminum silicon acid aluminum, synthesis high aluminum silicate) and crystalline aluminosilicate
(i.e. molecular sieve).In catalytic cracking catalyst production process, the main component of the waste residue (being also called cinder) of discharge has SiO2、
Al2O3、CaO、CeO2And La2O3, remaining impurity has Fe2O3、MgO、Na2O, SrO etc..The stacking of cinder can take substantial amounts of soil,
The cinder dried is powdered, waves with the wind, atmosphere pollution, causes air PM2.5 to raise.The most many producers are buried by cinder
Underground, causes the biggest destruction to surrounding, harmful element meeting polluted underground water, the soil in cinder, eventually results in soil
Ground salinization of soil.
In recent years, China's Smelting magnesium Industry Quick Development, along with increasing year by year of former magnesium and magnesium alloy annual production, give off
The magnesium slag come also gets more and more.Often produce 1t magnesium metal and about discharge the magnesium slag of 8～about 10t, produce with the former magnesium of China in 2009
As a example by measuring 50.18 ten thousand t, produce commercial magnesium slag 5,000,000 about t altogether, be equivalent to the product of the 1 year cement in two daily output 8000t cement plants
Amount.White clay is the waste residue that basic industry emits, and often produces 1t soda, discharges about 10m3Waste liquid, wherein containing waste residue 300～
600kg.At present, whole world soda annual production about 70,000,000 tons, ammonia-soda process alkaline is the main method that our times produces soda,
Soda prepared by ammonia-soda process about 50,000,000 tons, the alkaline residue white clay of generation about 20,000,000 tons.Titanium slag is to produce discharge after titanium dioxide
Waste residue.Sodium hypophosphite waste residue is to produce the solid waste that sodium hypophosphite is discharged, and mainly contains CaHPO3。
The discharge of above-mentioned waste residue, not only takies a large amount of soil, and environment and human health is caused the biggest harm.To mesh
Till before, cinder is mainly used to as construction material and filler, or is used for extracting useful component, synthetic zeolite etc.；Magnesium slag master
Novel wall material to be used as, mineralizer, desulfurizing agent use, or produce building building cement etc..White clay is mainly used to fill out pad
Ground；Titanium slag is mainly used in cement additive, aggregate, lays bricks；Sodium hypophosphite waste residue is mainly used to reclaim phosphorous
Acid；Above-mentioned application majority only has social benefit, does not has economic benefit.
Summary of the invention
It is an object of the invention to provide a kind of method preparing full solid waste high strength glass pottery for major ingredient with cinder, purport
Solving, cinder, magnesium slag, white clay, titanium slag and sodium hypophosphite waste residue waste's reclamation rate are the highest and cause polluting the asking of environment
Topic, reduces the consumption of natural resources simultaneously.
The present invention is achieved in that a kind of method preparing full solid waste high strength glass pottery for major ingredient with cinder, its
Feature is, its raw material and weight ratio thereof be: cinder 50～95%, magnesium slag 0～45%, white clay 0～15%, titanium slag 2～10% and
Sodium hypophosphite waste residue 3～10%.
Optimum ratio: cinder 70%, magnesium slag 10%, white clay 10%, titanium slag 5% and sodium hypophosphite waste residue 5%.
Wherein, cinder is in producing petroleum catalytic cracking agent amorphous silicic aluminum and crystalline aluminosilicate production process
The waste residue produced, main component is as follows, in mass ratio meter: SiO240～60%, Al2O314～22%, CaO 5～11%, CeO2
+La2O33～6%, remaining is possibly together with Fe2O3、MgO、Na2O, SrO etc..Wherein, the main component of described magnesium slag is as follows, by quality
Than meter: CaO 40～50%, SiO220～30%, A12O32～5%, MgO 6～10%, Fe2O38～10%.
The present invention utilizes cinder rare earth elements fining glass liquid, eliminates bubble, promotes the work of glass ceramics compact conformation
With, make the mechanical property of full solid waste glass ceramics increase, such as, rupture strength is up to more than 300Mpa.
The present invention introduces composite nucleating agent (such as the TiO in titanium slag by other waste residue2、ZrO2, BaO and ZnO and hypophosphorous acid
CaHPO in sodium waste residue3、NaH2PO3Deng), flux (Na2O、K2O etc.) and brightener (BaO and ZnO in such as titanium slag) etc.,
Form a kind of compound system with chemiluminescence, not only solve high-melting-point that complicated ingredient brings, crystallize difficulty, face
Color is gloomy waits technical barrier, but also improves the performance of glass ceramics.The present invention composite nucleating agent control by certain proportioning
Crystallize speed processed, has strongly reduced the suppression crystallize effect of cinder rare earth elements, greatly increases glass of the present invention pottery
The crystallization degree of porcelain；Utilize the flux in waste residue, reduce fusing point, raw material can be made to melt at 1350～1380 DEG C of homogeneous temperature
Change (general low-melting glass just can be accomplished), enhance glass ceramics structure, improve mechanical property；Brightener can increase
The glossiness of material, makes material color more bright-coloured bright.
The preparation method of the present invention, specifically includes following steps:
(1) each raw material for standby is taken by weight ratio described above, by cinder, magnesium slag, white clay, titanium slag and sodium hypophosphite waste residue
Put in batch mixer, batch mixing 0.1～0.4h, cross 50～90 mesh sieves, mix homogeneously；
(2) step (1) mixed raw material is loaded crucible, be subsequently placed in high temperature furnace, 1350～1380 DEG C of temperature
Through 3～5h fusings, form improving uniformity of melt；
(3) melt of step (2) is poured in the stainless steel mould of 250 DEG C of constant temperature, in a mold cooling 1～3min
After, regulation temperature is 400～500 DEG C and furnace cooling after keeping 1.5～2h, obtains parent glass；
(4) parent glass after step (3) molding is placed in heat-treatment furnace, at a temperature of 700～800 DEG C be incubated 4～
5h carries out heat of crystallization process, obtains glass ceramics blank after cooling；
(5) the glass ceramics blank that step (4) obtains is carried out rough cutting, essence cutting, corase grind, fine grinding, refines and polish
After obtain glass ceramics finished product.
Compared to existing technology, the method have the advantages that
(1) the whole raw materials needed for the preparation of the glass ceramics of the present invention are solid waste, and cost of material is low, preparation
Method is simple, and beneficially industrialized production is promoted；
(2) cinder peak use rate 95% in the present invention, total waste utilization rate 100%, the most single garbage,
Or the utilization rate of composite wastes, has exceeded the leading level in the world the most.Greatly reduce waste residue and stack cost of land, stockyard
Build and maintenance cost, it is to avoid the waste residue pollution to surrounding ground environment, water source and air, be conducive to economizing the land resource,
Protection environment；
(3) the glass ceramics intensity of the present invention is high, texture is good, it is possible to be well used for producing building and ornament materials, industry
Wear-and corrosion-resistant material and artware, reliable product quality, wide market.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, to the present invention
It is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.Wherein composition and the weight ratio thereof of raw material are as follows:
Cinder: SiO240～60%, Al2O314～22%, CaO 5～11%, CeO2+La2O33～6%；
Magnesium slag: CaO 40～50%, SiO220～30%, A12O32～5%, MgO 6～10%, Fe2O38～10%；
White clay: CaCO330～32%, CaSO42.5～3.5%, Mg (OH)225～31%, SiO28～10%；
Titanium slag: TiO230～40%, SiO220～30%, ZrO23～5%, BaO 1～3%, ZnO 2～4%.
Sodium hypophosphite waste residue: CaHPO344～46%, Ca (OH)214～16%, CaCO326～29%, NaH2PO33～
4%.
Embodiment 1:
(1) by 50% cinder, the magnesium slag of 20%, the white clay of 10%, the titanium slag of 10% and the sodium hypophosphite waste residue of 10%
Put in batch mixer, batch mixing 0.1h, crosses 50 mesh sieves, mix homogeneously；
(2) step (1) mixed raw material is loaded crucible, be placed in high temperature furnace and melt through 3h 1350 DEG C of temperature, formed
Improving uniformity of melt；
(3) melt of step (2) is poured into 250 DEG C of constant temperature, has in the stainless steel mould of definite shape and size,
In a mold after cooling 1min, furnace cooling after regulating temperature 400 DEG C and keeping 1.5h, obtain parent glass；
(4) parent glass after step (3) molding is placed in heat-treatment furnace, at a temperature of 700 DEG C, is incubated 4h analyses
Brilliant heat treatment, obtains glass ceramics blank after cooling；
(5) the glass ceramics blank that step (4) obtains is carried out rough cutting, essence cutting, corase grind, fine grinding, refines and polish
After obtain glass ceramics finished product 1.
Embodiment 2:
(1) the sodium hypophosphite waste residue of cinder, the magnesium slag of 20%, the white clay of 5%, the titanium slag of 10% and 5% of 60% is put
Enter in batch mixer, batch mixing 0.2h, crosses 60 mesh sieves, mix homogeneously；
(2) step (1) mixed raw material is loaded crucible, be placed in high temperature furnace and melt through 4.2h 1360 DEG C of temperature, shape
Uniformly melt；
(3) melt of step (2) is poured into 250 DEG C of constant temperature, has in the stainless steel mould of definite shape and size,
In a mold after cooling 2min, furnace cooling after regulating temperature 410 DEG C and keeping 1.6h, obtain parent glass；
(4) parent glass after step (3) molding is placed in heat-treatment furnace, at a temperature of 710 DEG C, is incubated 4.1h carries out
Heat of crystallization processes, and obtains glass ceramics blank after cooling；
(5) the glass ceramics blank that step (4) obtains is carried out rough cutting, essence cutting, corase grind, fine grinding, refines and polish
After obtain glass ceramics finished product 2.
Embodiment 3:
(1) the sodium hypophosphite waste residue of cinder, the magnesium slag of 10%, the white clay of 10%, the titanium slag of 5% and 5% of 70% is put
Enter in batch mixer, batch mixing 0.3h, crosses 70 mesh sieves, mix homogeneously；
(2) step (1) mixed raw material is loaded crucible, be placed in high temperature furnace and melt through 4.4h 1370 DEG C of temperature, shape
Uniformly melt；
(3) melt of step (2) is poured into 250 DEG C of constant temperature, has in the stainless steel mould of definite shape and size,
In a mold after cooling 3min, furnace cooling after regulating temperature 420 DEG C and keeping 1.7h, obtain parent glass；
(4) parent glass after step (3) molding is placed in heat-treatment furnace, at a temperature of 730 DEG C, is incubated 4.3h carries out
Heat of crystallization processes, and obtains glass ceramics blank after cooling；
(5) the glass ceramics blank that step (4) obtains is carried out rough cutting, essence cutting, corase grind, fine grinding, refines and polish
After obtain glass ceramics finished product 3.
Embodiment 4:
(1) the sodium hypophosphite waste residue of cinder, the magnesium slag of 5%, the white clay of 5%, the titanium slag of 5% and 5% of 80% is put into
In batch mixer, batch mixing 0.4h, crosses 80 mesh sieves, mix homogeneously；
(2) step (1) mixed raw material is loaded crucible, be placed in high temperature furnace and melt through 4.6h 1380 DEG C of temperature, shape
Uniformly melt；
(3) melt of step (2) is poured into 250 DEG C of constant temperature, has in the stainless steel mould of definite shape and size,
In a mold after cooling 3min, furnace cooling after regulating temperature 430 DEG C and keeping 1.8h, obtain parent glass；
(4) parent glass after step (3) molding is placed in heat-treatment furnace, at a temperature of 740 DEG C, is incubated 4.4h carries out
Heat of crystallization processes, and obtains glass ceramics blank after cooling；
(5) the glass ceramics blank that step (4) obtains is carried out rough cutting, essence cutting, corase grind, fine grinding, refines and polish
After obtain glass ceramics finished product 4.
Embodiment 5:
(1) titanium slag of the cinder of 95%, the magnesium slag of 2% and 3% is put in batch mixer, batch mixing 0.4h, cross 90 mesh sieves, mixed
Close uniformly；
(2) step (1) mixed raw material is loaded crucible, be placed in high temperature furnace and melt through 5h 1380 DEG C of temperature, formed
Improving uniformity of melt；
(3) melt of step (2) is poured into 250 DEG C of constant temperature, has in the stainless steel mould of definite shape and size,
In a mold after cooling 3min, furnace cooling after regulating temperature 480 DEG C and keeping 2h, obtain parent glass；
(4) parent glass after step (3) molding is placed in heat-treatment furnace, at a temperature of 780 DEG C, is incubated 5h analyses
Brilliant heat treatment, obtains glass ceramics blank after cooling；
(5) the glass ceramics blank that step (4) obtains is carried out rough cutting, essence cutting, corase grind, fine grinding, refines and polish
After obtain glass ceramics finished product 5.
Effect example: the glass ceramics 1～5 prepared in above-described embodiment is carried out performance test, test index and side
Method is: rupture strength is tested according to GB/T9966.2-1988 method of testing, and Vickers hardness is according to the test of GB/T16534-2009
Method is tested, and test result is as shown in table 1 below:
Table 1 glass ceramics 1～7 the performance test results
From table 1 it follows that the pottery of the full solid waste high strength glass with cinder as major ingredient 1～5 that the present invention prepares
Vickers hardness number >=800MPa, rupture strength value >=250MPa, high breaking strength value reach 356MPa.Due in cinder
Rare earth element can fining glass liquid, eliminate bubble, promote glass ceramics compact conformation, in conjunction with the complex in other waste residues
The chemiluminescence of core agent, flux and brightener, the glass ceramics intensity that therefore prepared by the present invention is high, texture is good, it is possible to
Well applying in terms of manufacturing building and ornament materials, industry wear-and corrosion-resistant material and artware, reliable product quality, before market
Scape is wide.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (2)
1. the method preparing full solid waste high strength glass pottery with cinder for major ingredient, is characterized in that, its raw material and weight thereof
Ratio is: cinder 50 ~ 95%, magnesium slag 2 ~ 20%, white clay 0 ~ 15%, titanium slag 2 ~ 10% and sodium hypophosphite waste residue 3 ~ 10%；
The main component of described cinder is as follows, in mass ratio meter: SiO2 40~60%、Al2O3 14~22%、CaO 5~11%、CeO2 +
La2O33~6%；
The main component of described magnesium slag is as follows, in mass ratio meter: CaO 40 ~ 50%, SiO2 20~30%、A12O3 2~5%、MgO 6~
10%、Fe2O38~10%；
The main component of described white clay is as follows, in mass ratio meter: CaCO3 30~32%、CaSO4 2.5~3.5%、Mg(OH)2 25~
31%、SiO28~10%；
The main component of described titanium slag is as follows, in mass ratio meter: TiO2 30~40%、SiO2 20~30%、ZrO2 3~5%、BaO 1~
3%、ZnO 2~4%；
The main component of described sodium hypophosphite waste residue is as follows, in mass ratio meter: CaHPO3 44~46%、 Ca(OH)2 14~16%、
CaCO3 26~29%、NaH2PO3 3~4%；
Comprise the following steps:
(1) take each raw material for standby by above-mentioned weight ratio, each raw material is put in batch mixer, batch mixing 0.1 ~ 0.4h, crosses 50 ~ 90 mesh
Sieve, mix homogeneously；
(2) step (1) mixed raw material is loaded crucible, be subsequently placed in high temperature furnace, 1350 ~ 1380 DEG C of temperature through 3 ~ 5h
Fusing, forms improving uniformity of melt；
(3) by the melt cast of step (2) to the stainless steel mould of 250 DEG C of constant temperature, after cooling down 1 ~ 3min in a mold, regulate
Temperature is 400 ~ 500 DEG C and furnace cooling after keeping 1.5 ~ 2h, obtains parent glass；
(4) parent glass after step (3) molding is placed in heat-treatment furnace, at a temperature of 700 ~ 800 DEG C, is incubated 4 ~ 5h carries out
Heat of crystallization processes, and obtains glass ceramics blank after cooling；
(5) the glass ceramics blank that step (4) obtains is carried out rough cutting, essence cutting, corase grind, fine grinding, refine and polish after must
To glass ceramics finished product.
A kind of method preparing full solid waste high strength glass pottery for major ingredient with cinder, its feature
It is that its raw material and weight ratio thereof be: cinder 70%, magnesium slag 10%, white clay 10%, titanium slag 5% and sodium hypophosphite waste residue 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410469887.9A CN104230169B (en) | 2014-09-15 | A kind of method preparing full solid waste high strength glass pottery for major ingredient with cinder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410469887.9A CN104230169B (en) | 2014-09-15 | A kind of method preparing full solid waste high strength glass pottery for major ingredient with cinder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104230169A CN104230169A (en) | 2014-12-24 |
| CN104230169B true CN104230169B (en) | 2017-01-04 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1551667A1 (en) * | 1988-01-11 | 1990-03-23 | Завод "Автостекло" | Black glass |
| CN102276146A (en) * | 2011-05-19 | 2011-12-14 | 长沙理工大学 | Method for producing ceramic and glass pigment by using waste chromium and cobalt catalysts from fluorination process as raw materials |
| CN102807323A (en) * | 2012-09-12 | 2012-12-05 | 济南大学 | Method for recycling and reusing solid waste and glass prepared by using solid waste as raw material |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1551667A1 (en) * | 1988-01-11 | 1990-03-23 | Завод "Автостекло" | Black glass |
| CN102276146A (en) * | 2011-05-19 | 2011-12-14 | 长沙理工大学 | Method for producing ceramic and glass pigment by using waste chromium and cobalt catalysts from fluorination process as raw materials |
| CN102807323A (en) * | 2012-09-12 | 2012-12-05 | 济南大学 | Method for recycling and reusing solid waste and glass prepared by using solid waste as raw material |
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Granted publication date: 20170104 Termination date: 20190915 |