CN107628819B - A method of preparing the porous material of the phase containing melilite using magnesium slag, flyash, carbide slag - Google Patents
A method of preparing the porous material of the phase containing melilite using magnesium slag, flyash, carbide slag Download PDFInfo
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- CN107628819B CN107628819B CN201610564963.3A CN201610564963A CN107628819B CN 107628819 B CN107628819 B CN 107628819B CN 201610564963 A CN201610564963 A CN 201610564963A CN 107628819 B CN107628819 B CN 107628819B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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Abstract
The industrial solid castoffs discharge amount such as magnesium slag, flyash, carbide slag is big, occupies large amount of land resources, and dust easy to form, causes air and water pollution.The porous material of method of the invention using magnesium slag, flyash, carbide slag doping by high temperature sintering preparation phase containing melilite, the purpose of the treatment of wastes with processes of wastes against one another is not only reached, and porous material obtained, it can be used for sound insulation, heat preservation, the application field of industrial solid castoff recycling has been expanded in the fields such as filtering.
Description
Technical field
The present invention relates to a kind of methods of porous material using industrial solid castoff preparation phase containing melilite, belong to pottery
Ceramic material field.
Background technique
A kind of mineral in silicates mineral that melilite is made of calcium silicates/sodium metasilicate containing aluminium, magnesium, iron, change
Study a point general formula (Ca, Na)2(Al,Mg,Fe2+)[(Al,Si)SiO7].Cacoclasite Ca2Al(AlSi)O7And akermanite
(Ca2Mg(Si2O7) it is two kinds of most important mineral in melilite race, in ingredient, replaced between Mg-Al by perfect isomorphism, together
When with the replacement between Si-Al, therefore formed with the isomorphic replacement of cacoclasite and akermanite.These mineral be from
It is crystallized in alkaline magma rich in calcium.
Melilite is mainly used in the manufacturing fields such as ceramic glaze, ceramics, refractory material, thermal insulation material and cement.In addition
Akermanite Ca2Mg(Si2O7) be that one kind contains Si, the ceramics of Ca, Mg have bioactivity, have in bioengineered tissue compared with
Good application prospect.
Currently, large-scale industry is mainly derived from ore extraction with melilite, there are biggish ecology and environmental disruption hidden danger.
Fine chemistry industry mainly uses sol-gal process and the precipitation method to prepare with melilite, and raw materials used is chemically pure reagent, Wu Faman
Foot large-scale production and application.
And on the other hand, China discharges a large amount of flyash and various industrial slags every year, cover soil, pollution environment and
Increase investment, makes full use of these wastes to the level of resources utilization is improved, develop a circular economy, building a conservation-minded society has
Highly important meaning.But current China's industrial solid castoff, which recycles, mainly to be filled with temporary road and terrace, sintering system
The mode of standby clinker, the simple reprocessing processing such as sintering brickmaking utilizes, the type for the industrial solid castoff being utilized
It is all very limited with the scope of application of generation product.
The main chemical of flyash is SiO2、Al2O3、CaO、MgO、TiO2, sulfide etc..Magnesium slag is refining magnesium discharge
A kind of industrial residue, main chemical compositions CaO, SiO2、Al2O3Deng.Carbide slag be calcium carbide prepare obtain after acetylene with hydrogen
Calcium oxide solid slag as main component, while also containing SiO2、Al2O3And a small amount of CaCO3、Fe2O3, MgO, carbon slag etc. it is miscellaneous
Matter.
Understand according to inventor, the relevant report for manufacturing ceramics or refractory material using industrial solid castoff is fewer, In
The research that the wastes such as magnesium slag, carbide slag recycle in Industrial Solid Waste is also not very much.
Chinese patent application CN201210258832.4 is disclosed is with industrial residue magnesium slag, kaolin and commercial alumina
Raw material prepare calcium hexaluminate/anorthite complex phase light heat insulating refractory materials method by pyroreaction sintering process, should
Preparation method realizes the comprehensive utilization of magnesium slag to a certain extent, and its material have high temperature resistant, lightweight, heat-insulation and heat-preservation spy
Point is applicable to the liner high-temperature material of elevated temperature vessel and kiln.But this method has only digested a kind of industrial residue, kaolinite used
Soil and commercial alumina are still from ore and industrial production.
Chinese patent application CN201410581205.3 discloses a kind of magnesium slag and manganese slag castable refractory raw material, is a kind of
Unshape refractory, including 20~30 parts of aggregates, 70~80 parts of powders, 10~15 parts of additives, the aggregate is by corundum, magnesium
Aluminate composition；The powder is by α-Al2O3Powder, magnesium ground-slag, flyash, manganese ground-slag composition；The additive is water-soluble phenolic
Urea formaldehyde.It is formed after magnesium ground-slag is mixed with water soluble phenol resin in the invention and generates hydrated calcium silicate gel, can be improved
The curing rate of magnesium slag and manganese slag castable refractory.Although the preparation method has digested three kinds of Industrial Solid Wastes, but Industrial Solid used
Useless ratio is still less high.
Summary of the invention
It is few in view of the research for manufacturing ceramic material in current industrial solid castoff recycling, to magnesium slag, flyash, electricity
The comprehensive utilization of three kinds of solid waste of rock ballast is insufficient, and the present invention is in further investigation magnesium slag, flyash, carbide slag ingredient properties
On the basis of, the method for adulterating the porous material of preparation phase containing melilite by these three solid waste is proposed, is on the one hand solved
Certainly the problem of the treatment of wastes with processes of wastes against one another, on the one hand provide can be used for keeping the temperature, the porous material of the phase containing melilite of sound insulation or filtering etc.
Material.
Technical scheme is as follows:
A kind of preparation method of the porous material of the phase containing melilite: magnesium slag, flyash, carbide slag are mixed, the mixing
Object compression moulding, is sintered later.
Preferably magnesium slag: flyash: the mass ratio of carbide slag is 1:0.0625~0.8:0.0625~0.7, further preferably
For 1:0.25~0.8:0.07~0.5, more preferably 1:0.35~0.8:0.07~0.35, most preferably 1:0.4~0.6:
0.15~0.3.
Be preferably laminated to the condition of type are as follows: briquetting pressure be 60MPa~110MPa, further preferably 78MPa~
98MPa.Dwell time is 50~80s.
Well known to those skilled in the art, common various pressure forming methods are used equally for the present invention, including but not limited to,
Cold isostatic compaction, compression molding etc..It is preferable to use compression moldings.
It is preferred that sintering condition are as follows: heating rate is 5-15 DEG C/min, and sintering temperature is 1100~1200 DEG C, and soaking time is
3-5 hours.More preferable heating rate is 9-11 DEG C/min, soaking time 210-270min.
It is preferred that sintering processing is high temperature pressure-free sintering.
It is preferred that magnesium slag, flyash and carbide slag can be crushed before mixing or be crushed in mixing.It is preferred that making
The partial size of magnesium slag, flyash and carbide slag is at 1~100 μm in mixture, and further preferably 5~50 μm.
Well known to those skilled in the art, common breaking method can be used in the present invention, including but not limited to: squeeze powder
Broken, extruding-shearing crushing, splitting crushing, impact comminution etc., the grinding device that can be used includes but is not limited to: jaw crushing
Machine, column mill, Raymond mill, ball mill, Vertical Mill, rod milling, punching rotation crusher, hammer mill etc..
The present invention also provides the porous materials of the phase containing melilite prepared by above-mentioned preparation method.
It is preferred that the porous material of the phase containing melilite, total porosity is 19%~57%, bulk density is 1.38~
2.15g/cm3, water absorption rate is 8.9%~34.5%, and compression strength is 0.8MPa~98.4MPa.
The total porosity of the porous material of the further preferably described phase containing melilite is 25%~42%；It is preferred that its volume is close
Degree is 1.63~1.90g/cm3；It is preferred that its water absorption rate is 15.0%~25.5%；It is preferred that its compression strength be 10.0MPa~
63.0MPa。
Term " total porosity " used refers to the sum of closed porosity and apparent porosity in the present invention.
In the present invention term " bulk density " used be quality of the porous materials without free water and its total volume (including
The reality of material accounts for volume shared by volume and whole holes) ratio.
In the present invention term " water absorption rate " used be the water that all open pores are absorbed in porous materials quality with
The mass ratio value of its drying material.
Wherein the measuring method of total porosity, bulk density and water absorption rate uses Archimedes method.
Advantages of the present invention:
Three kinds of magnesium slag, flyash, carbide slag repressed sintering of solid waste, SiO therein2、Al2O3, CaO, MgO etc.
Constitutional changes form melilite phase, such as akermanite (Ca2Mg(Si2O7)) and/or cacoclasite (Ca2MgxAlx(SixAlx)
O7) phase, the material containing melilite phase is formd, a kind of melilite phase material for substituting ore source is provided.
In addition, carbonaceous remaining in flyash and carbide slag, calcium carbonate, calcium hydroxide generate CO during the sintering process2,
The stomata in firing material is formed, is not required to additionally add pore creating material, makes full use of the compositing characteristic of each Industrial Solid Waste, reduce and match
The complexity of material, and substantially increase ratio of the Industrial Solid Waste in ingredient.
The porous material of the obtained phase containing melilite, according to its total porosity, bulk density and compression strength, depending on using
Condition requirement, can be used for sound insulation, keep the temperature, filtering etc., widen the application field that Industrial Solid Waste recycles product.For example,
Filter it is of less demanding to the compression strength of material therefor, when the porous material of the phase prepared according to the methods of the invention containing melilite,
When total porosity and higher water absorption rate, filtering material can be used as；Sound insulation or heat preservation are more demanding to the compression strength of material therefor,
When the porous material of the phase prepared according to the methods of the invention containing melilite, compression strength in 10MPa or more, can be used as sound insulation or
Thermal insulation material.
Detailed description of the invention
XRD comparison diagram before and after the magnesium slag of Fig. 1 embodiment 1, flyash, carbide slag mixture sintering
Microcosmic porous shape appearance figure after the magnesium slag of Fig. 2 embodiment 1, flyash, carbide slag mixture sintering
Microcosmic porous shape appearance figure after the magnesium slag of Fig. 3 embodiment 2, flyash, carbide slag mixture sintering
XRD diagram after the magnesium slag of Fig. 4 embodiment 3, flyash, carbide slag mixture sintering
XRD diagram after the magnesium slag of Fig. 5 embodiment 5, flyash, carbide slag mixture sintering
Specific embodiment
The porous material compressive property of the phase containing melilite is measured using SANS-CMT5350 profile material universal testing machine；Material
Total porosity, bulk density, water absorption rate using Archimedes method measure；The object of material mutually uses Japanese Shimadzu XRD-6000 type
X-ray diffractometer is analyzed；The porous structure of material uses electron microscope observation.
The mixing of magnesium slag, flyash, carbide slag shakes ball mill using Rigaku-9306D model, shakes magnesium after ball milling
Slag, flyash, carbide slag partial size be 4-50 μm.
Compression molding mould therefor diameter is 20mm.Briquetting pressure is 64MPa~100MPa；Dwell time is 50~60s
Left and right.To be convenient for Mechanics Performance Testing, sample dimensional height is controlled in 20 ± 1mm.
Embodiment 1
Specific steps:
(1) three kinds of magnesium slag, flyash, carbide slag solid waste take 200g according to mass ratio 1:0.5:0.17；
(2) three kinds of slag charges are mixed with concussion ball mill, incorporation time 60s；
(3) uniformly mixed powder is placed among mold and is pressed and molded, briquetting pressure 95.9MPa, the dwell time
For 60s；
(4) sample after forming is placed in progress high temperature pressure-free sintering in Muffle furnace, heating rate is 10 DEG C/min, sintering
Temperature is 1150 DEG C, soaking time 240min, and sintering is completed, and is statically placed in natural cooling in Muffle furnace；
(5) sample carries out subsequent analysis test.
Surveyed compression strength is 29.97MPa, and total porosity 33.72%, water absorption rate 20.10%, bulk density is
1.68g/cm3.XRD material phase analysis and its porous microscopic appearance are shown in attached Fig. 1 and 2.
Embodiment 2
Specific steps:
(1) three kinds of magnesium slag, flyash, carbide slag solid waste take 200g according to mass ratio 1:0.36:0.07；
(2) three kinds of slag charges are mixed with concussion ball mill, incorporation time 60s；
(3) uniformly mixed powder is placed among mold and is pressed and molded, briquetting pressure 95.9MPa, the dwell time
For 60s；
(4) sample after forming is placed in progress high temperature pressure-free sintering in Muffle furnace, heating rate is 10 DEG C/min, sintering
Temperature is 1150 DEG C, soaking time 240min, and sintering is completed, and is statically placed in natural cooling in Muffle furnace；
(5) sample carries out subsequent analysis test.
Surveyed compression strength is 98.36MPa, total porosity 19.6%, water absorption rate 8.92%, and bulk density is
2.09g/cm3.Its microstructure is as shown in Fig. 3.
Embodiment 3
Specific steps:
(1) three kinds of magnesium slag, flyash, carbide slag solid waste take 200g according to mass ratio 1:0.42:0.25；
(2) three kinds of slag charges are mixed with concussion ball mill, incorporation time 60s；
(3) uniformly mixed powder is placed among mold and is pressed and molded, briquetting pressure 95.5MPa, the dwell time
For 60s；
(4) sample after forming is placed in progress high temperature pressure-free sintering in Muffle furnace, heating rate is 10 DEG C/min, sintering
Temperature is 1150 DEG C, soaking time 240min, and sintering is completed, and is statically placed in natural cooling in Muffle furnace；
(5) sample carries out subsequent analysis test.
Surveyed compression strength is 20.70MPa, and total porosity 33.74%, water absorption rate 18.97%, bulk density is
1.79g/cm3.Its XRD material phase analysis is as shown in Fig. 4.
Embodiment 4
Specific steps:
(1) three kinds of magnesium slag, flyash, carbide slag solid waste take 200g according to mass ratio 1:0.25:0.42；
(2) three kinds of slag charges are mixed with concussion ball mill, incorporation time 60s；
(3) uniformly mixed powder is placed among mold and is pressed and molded, briquetting pressure 95.5MPa, the dwell time
For 60s；
(4) sample after forming is placed in progress high temperature pressure-free sintering in Muffle furnace, heating rate is 10 DEG C/min, sintering
Temperature is 1150 DEG C, soaking time 240min, and sintering is completed, and is statically placed in natural cooling in Muffle furnace；
(5) sample carries out subsequent analysis test.
Surveyed compression strength is 0.87MPa, and total porosity 56.96%, water absorption rate 34.32%, bulk density is
1.66g/cm3。
Embodiment 5
Specific steps:
(1) three kinds of magnesium slag, flyash, carbide slag solid waste take 200g according to mass ratio 1:0.8:0.2；
(2) three kinds of slag charges are mixed with concussion ball mill, incorporation time 60s；
(3) uniformly mixed powder is placed among mold and is pressed and molded, briquetting pressure 95.5MPa, the dwell time
For 60s；
(4) sample after forming is placed in progress high temperature pressure-free sintering in Muffle furnace, heating rate is 10 DEG C/min, sintering
Temperature is 1150 DEG C, soaking time 240min, and sintering is completed, and is statically placed in natural cooling in Muffle furnace；
(5) sample carries out subsequent analysis test.
Surveyed compression strength is 32.47MPa, and total porosity 28.98%, water absorption rate 16.10%, bulk density is
1.80g/cm3.Its XRD material phase analysis is as shown in Fig. 5.
Claims (10)
1. a kind of preparation method of the porous material of phase containing melilite, it is characterised in that: magnesium slag, flyash, carbide slag are mixed,
The mixture compression moulding, is sintered later；Magnesium slag: flyash: the mass ratio of carbide slag be 1:0.25~0.8:0.07~
0.5；Briquetting pressure is 60MPa~110MPa；Sintering heating rate is 5-15 DEG C/min, and sintering temperature is 1100~1200 DEG C,
Soaking time is 3-5 hours；The porous material compression strength is 0.8MPa~98.4MPa, is measured with Archimedes method, total gas
Porosity is 19%~57%, and bulk density is 1.38~2.15g/cm3, water absorption rate is 8.9%~34.5%.
2. preparation method as described in claim 1, which is characterized in that the total porosity of the porous material of the phase containing melilite
It is 25%~42%, bulk density is 1.63~1.90g/cm3, water absorption rate is 15.0%~25.5%, and compression strength is
10.0MPa~63.0MPa.
3. preparation method as claimed in claim 1 or 2, it is characterised in that: magnesium slag: flyash: the mass ratio of carbide slag is 1:
0.35~0.8:0.07~0.35.
4. preparation method as claimed in claim 3, which is characterized in that magnesium slag: flyash: the mass ratio of carbide slag is 1:0.4
~0.6:0.15~0.3.
5. such as the described in any item preparation methods of claim 1-2, it is characterised in that: briquetting pressure is 78MPa~98MPa.
6. such as the described in any item preparation methods of claim 1-2, which is characterized in that the molding dwell time is 50~80s.
7. such as the described in any item preparation methods of claim 1-2, it is characterised in that: sintering heating rate is 9-11 DEG C/min,
Soaking time is 210-270min.
8. such as the described in any item preparation methods of claim 1-2, it is characterised in that: magnesium slag, flyash, carbide slag in mixture
Partial size be 1-100 μm.
9. preparation method as claimed in claim 8, which is characterized in that magnesium slag in mixture, flyash, carbide slag partial size be
5-50μm。
10. a kind of porous material of phase containing melilite, it is characterised in that: use the described in any item preparation sides claim 1-9
Method preparation.
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| CN108558361A (en) * | 2018-05-25 | 2018-09-21 | 北方民族大学 | The porosity adjustable porous ceramics and preparation method prepared with flyash, carbide slag |
| CN108756107B (en) * | 2018-06-27 | 2020-01-31 | 燕翔 | sand-lined acoustic panel based on glass wool |
| CN113636835B (en) * | 2021-08-30 | 2022-11-18 | 武汉理工大学 | Anorthite heat storage ceramic prepared from magnesium slag and preparation method thereof |
| CN114920578B (en) * | 2022-07-20 | 2022-10-04 | 淄博金狮王科技陶瓷集团有限公司 | Preparation method of porous anorthite/gehlenite complex-phase ceramic with low firing shrinkage rate |
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| JP2003062598A (en) * | 2001-08-27 | 2003-03-04 | Nippon Kaisui Kako Kk | Method for treating sludgy waste |
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| CN103351166B (en) * | 2012-07-25 | 2014-04-16 | 田玉明 | Calcium hexaluminate/gehlenite diphase heat-insulation refractory material and preparation method thereof |
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