CN110117162A - It is a kind of using blast-furnace cinder and red mud as the preparation of the alkali-resisting glass fiber of primary raw material - Google Patents
It is a kind of using blast-furnace cinder and red mud as the preparation of the alkali-resisting glass fiber of primary raw material Download PDFInfo
- Publication number
- CN110117162A CN110117162A CN201910484674.6A CN201910484674A CN110117162A CN 110117162 A CN110117162 A CN 110117162A CN 201910484674 A CN201910484674 A CN 201910484674A CN 110117162 A CN110117162 A CN 110117162A
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- Prior art keywords
- blast
- red mud
- alkali
- glass fibre
- furnace cinder
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
-
- 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
- C03C13/00—Fibre or filament compositions
- C03C13/001—Alkali-resistant fibres
-
- 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
- C03C13/00—Fibre or filament compositions
- C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
Abstract
The invention discloses a kind of using solid waste blast-furnace cinder and red mud as alkali-resistant glass fibre of primary raw material and preparation method thereof, the invention belongs to field be inorganic non-metallic material and offal treatment crossing domain, blast-furnace cinder and red mud are a kind of industrial solid castoffs reluctant at this stage.The present invention passes through Fe in blast-furnace cinder and red mud by adding blast-furnace cinder and red mud in the raw material of industry2O3, Al2O3, K2O, Na2These components of O, improve the alkaline resistance properties of alumina silicate glass, while improving the high temperature viscosity and crystallization property of glass.Mass percent in glass fibre: blast-furnace cinder 10%~45%, Bayer process red mud 8%~40%, quartz sand 46%~65%, aluminium oxide 5%~20%, magnesia 0.1%~7%, iron oxide 3%~17%, sodium oxide molybdena 0.1%~7%.
Description
Technical field
The present invention relates to a kind of using blast-furnace cinder and red mud as the preparation method of the alkali-resistant glass fibre of primary raw material, largely
Utilize two kinds of solid waste of blast-furnace cinder and red mud, belong to the crossing domain of inorganic non-metallic material and offal treatment,
Since it is with excellent alkaline resistance properties, to be used for composite material, the building fields such as glass reinforced concrete glass.
Background technique
A kind of waste residue being discharged from blast furnace when blast-furnace cinder is manUfaCtUre of pig iron is a kind of eutectic mixture, China's industry
The more than one hundred million tons of the annual emissions of waste residue, slag are the discarded object of power boiler discharge that ferrous metals industry influences carrying capacity of environment, these are outdoor
The melting waste slag of storage stores up appropriation of land, and pollution soil poisoning, water body and atmosphere seriously affect ecological environment, cause economy
Loss and the wasting of resources.The pollution waste residue that red mud is discharged as aluminium industry is that one kind is difficult to rationalize processing at this stage
Industrial solid castoff, about 70,000,000 tons of the annual emissions of global red mud, a large amount of red mud can only be stacked or be arranged by stockyard
Enter in ocean and handle, this not only occupies large amount of land resources, can also pollute to water resource and marine resources, to environment
Cause serious pollution.It is found according to investigation, due to containing CaO, SiO in blast-furnace cinder and red mud2、Fe2O3、Al2O3、
Na2O、TiO2Deng, it can be used as the main component of production glass, and alkali-resistant glass fibre can be produced, it is red to blast-furnace cinder
Therefore mud, manufactures alkali-resistant glass fibre with blast-furnace cinder and red mud and effectively solves environmental pollution using an approach is increased again,
Entreprise cost is reduced again, also improves properties of product.
A branch of the alkali-resistant glass fibre as glass fibre has good alkaline erosion ability, can be used as water
The reinforcing material of cement-based composite material.Alkali-resistant glass fibre is in construction material, road construction, urban beautification, civil engineering, water conservancy
It is used widely in many fields such as facility, pipeline and energy protective equipment.Current alkali-resistant glass fibre both domestic and external is main
It is because containing TiO2Etc. components so that glass fibre when being acted on lye can surface generate layer protecting film, slow down into one
The corrosion of step, so as to improve the alkali resistance of glass fibre.
Using blast-furnace cinder and red mud as research object, match proper amount of lime stone, commercial alumina, silica flour, adjusts each
One group of alumina silicate glass is melted in the content of raw material, and research material content variation is to performances such as corresponding glass structure, acid and alkali-resistances
Affecting laws select the preferable sample of alkaline resistance properties and carry out fiberizing performance test, and it is preferable finally to select alkaline resistance properties, and energy
Preferably meet the basic components of wire drawing requirement.
Mainly there are Mount Taishan glass, megalith group etc. in the producer of production glass fibre at present, the raw material master used in production
If the valuableness imported material such as pyrophillite, thus in cost, the peculiar advantage of blast-furnace cinder and red mud with cheap price,
And contain CaO, SiO in blast-furnace cinder red mud2、Fe2O3、Al2O3、Na2O, if preparing alkali-resistant glass fibre with it for raw material,
It then just will be greatly reduced cost.
Summary of the invention
The problems such as present invention is for the high cost of current alkali-resistant glass fibre and blast-furnace cinder and red mud big accumulating amount, provides
It is a kind of to pre-process blast-furnace cinder and red mud as alkali-resistant glass fibre of raw material and preparation method thereof.It is this with high alumina slag and
Red mud is the alkali-resisting glass fiber of primary raw material using silica flour, calcium oxide, commercial alumina as main component, by adjusting in raw material
Red mud, blast-furnace cinder, lime stone, commercial alumina, quartzy powder component, to glass fibre alkaline resistance properties, crystallization rate and high temperature
Viscosity further improves, and obtains that cost is relatively low, and processability is good, alkali corrosion resistance performance and alkali-resistant glass fibre currently on the market
Glass fibre similar in (AR glass fibre), the alkali proof fiber can be used as fibre reinforced materials, be spiked into cement base composite wood
In material, enhance the intensity and toughness of matrix.
Technical solution of the present invention is as follows: it is a kind of using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material, by each
The adjustment of raw material addition content, and then glass fibre component is adjusted, further to improve fiber alkali resistance, crystallization rate
And high temperature viscosity.The mass percentage of each raw material of proportion optimizing is as follows: blast-furnace cinder 10%~45%, Bayer process red mud 8%
~40%, quartz sand 46%~65%, aluminium oxide 5%~20%, magnesia 0.1%~7%, iron oxide 3%~17%, oxidation
Sodium 0.1%~7%.By processes such as pretreatment, ingredient, homogenizing, melting, clarifying and homogenizing, wire drawing, coolings, molding temperature is prepared
Spend lower, excellent water-fast, caustic corrosion performance inexpensive alkali-resistant glass fibre.
Contain following components in percentage by weight in blast-furnace cinder: SiO2 31%~40%, Al2O3 12%~18%, CaO
35%~45%, MgO 7%~10%, Na2O 0.3%~0.5%, K2O 0.20%~0.25%, ferriferous oxide 0.4%~
0.6%, TiO2 0.35%~0.5%, SiO contained therein2、Al2O3, CaO, MgO, etc. components be all glass fibre composition
Part, the presence of these components allow blast-furnace cinder to become possibility as the raw material of glass fibre.
Bayer process red mud contains following components in percentage by weight: SiO2 12%~12.6%, Al2O3 21.9%~
22.3%, CaO 9.2%~9.4%, MgO 3.8%~4%, Na2O+K2O 2.3%~2.5%, ferriferous oxide 5.1%~
11.6%, TiO2 1.5%~1.7%, other 0.2%~0.9%, SiO contained therein2、Al2O3, CaO, MgO, etc. components all
It is the component part of glass fibre, the presence of these components allows Bayer process red mud to become possibility as the raw material of glass fibre.
The blast-furnace cinder be pass through pretreated blast-furnace cinder, preprocess method are as follows: blast-furnace cinder before factory
It by water quenching, dries, homogenizing is ground into the powder of certain partial size, meets under the requirement as glass fibre raw material at 400 DEG C
Handled at a temperature of above 2~3 hours it is spare.
The preprocess method of the pretreatment red mud is as follows: Bayer process red mud is dried under 100 DEG C~200 DEG C air atmospheres
It is dry to remove moisture then grinding sieving (granularity is less than 250 μm).
The present invention is using high alumina slag and red mud as the preparation method of the alkali-resistant glass fibre of primary raw material, including following step
It is rapid: (1) Bayer process red mud under 200 DEG C~300 DEG C air atmosphere is dried remove moisture then grinding sieving (granularity is less than
250 μm), mixed red mud is kept the temperature under 600 DEG C~800 DEG C air atmospheres 4~5 hours it is spare.Blast-furnace cinder is dispatching from the factory
Before have been subjected to water quenching, dry, homogenizing, be ground into the powder of certain partial size, meet under the requirement as glass fibre raw material
2~3 hours (2) are handled at a temperature of 400 DEG C or more by pretreated blast-furnace cinder, red mud and lime stone, industry in step (1)
Aluminium oxide, silica flour are put into refractory container after mixing by corresponding proportion, and 4~6h of heat preservation is melted at 1450 DEG C~1550 DEG C
It obtains homogenizing clear glass metal, then being higher than forming temperature, (it is 10 that forming temperature, which takes viscosity of glass metal,3Institute when dPa.s
Corresponding temperature) 15~40 DEG C or so when continuous glass fibre is made by casing, it is then cooling that obtain alkali-resistant glass fibre (former
Silk), average fibre diameter is less than 30 microns.
Structural analysis test is carried out to above-mentioned alkali-resistant glass fibre, material phase analysis is carried out using XRD.For aspect of performance, adopt
With differential thermal analysis and water-fast, alkaline test, thermal stability and chemical stability are analyzed；Using rotation high-temperature viscosimeter,
It is about 10 that thermal gradient furnace and petrographic microscope measure glass forming temperature T1g3(to refer generally to glass viscosity respectively3When dPa.s temperature and
Crystallization ceiling temperature mound liquidus temperature), poor 80 DEG C by two temperatures, guarantee the continuous drawing of glass fibre.
Beneficial effects of the present invention: (1) alkali-resisting glass fiber obtained through above-mentioned preparation method improves blast-furnace cinder dosage,
The pollution for reducing environment reduces alkali-resisting glass fiber production cost simultaneously.(2) the alkali-resistant glass fibre alkali resistance is excellent, compares after tested
It was found that suitable with AR glass alkaline resistance properties, while there is good processability, thermal stability, can be applicable to it is a variety of require it is resistance to
Corrode in composite material.(3) raw material in this patent other than blast-furnace cinder red mud are technical grade batch, are enabled the invention to
Preferably it is applied in actual industrial production.
Specific embodiment
The present invention is further explained below by specific embodiment, following embodiments are only to assist in ability
Field technique personnel better understand the present invention, are not defined to its content.
In the present invention, considered critical is not carried out for blast-furnace cinder, red mud component and type.Example uses the mountain in Zibo
Aluminium Bayer red mud yard largely meets weight percentage SiO by a large amount of analysis detections2+Al2O3+ CaO+MgO+ iron
Oxide > 82% carries out a series of pretreatment to it, prepares the excellent glass fibre of alkaline resistance properties.
In the present invention, considered critical is not carried out for blast-furnace cinder, red mud component and type.The Blast Furnace Ore that example uses
Slag is the auxiliary product of Shandong large iron and steel enterprise, percentage composition SiO2+Al2O3+ CaO+MgO > 85% carries out it a series of
Pretreatment, prepare the excellent glass fibre of alkaline resistance properties.
Bayer process red mud is dried under 100 DEG C~200 DEG C air atmospheres remove moisture then grinding sieving (granularity is small
In 250 μm).Blast-furnace cinder has been subjected to water quenching before factory, dries, and homogenizing is ground into the powder of certain partial size, meets conduct
The requirement of glass fibre raw material 400 DEG C or more at a temperature of processing 2~3 hours it is spare.
The oxide composition of the alkali-resistant glass fibre raw material of industry is shown in Table 1
1 starting oxides of table are at being grouped as (wt%).
SiO2As Network former main in alumina silicate glass, main make is played to building glass network framework structure
With the SiO in glass structure2Exist in the form of [SiO4] is tetrahedral, the basic structural unit of [SiO4] as network skeleton
It is interconnected to constitute glass network framework, as alkaline earth oxides such as Network modifier CaO and MgO, it can provide
Free oxygen improves the O/Si ratio of system, and the silicon negative oxygen ion group in structure is made to be depolymerized to simpler anion group, and can be with
Play charge compensation and structure filling, to influence the structure and performance of glass.
SiO in this patent2Content 46%~65%, preferably 59~62%, processability through overtesting glass and
Chemical stability etc. all meets the production and application of product, if SiO2Content is lower than 50%, and the oxide for constituting vitreum subtracts
It is few, can, alkaline resistance properties water-fast to glass have an adverse effect content greater than 65%, viscosity of glass metal can be made to increase, unfavorable thousand
Glass fibre production.
Al2O3For the network intermediate oxide of glass, under given conditions, can the structural unit of [Al04] enter net
Network structure increases the viscosity of glass metal, reduces crystallization ability, and the certain promotion of the thermal stability and chemical stability to glass is made
With being best glass stabilizer, Al2O3SiO is greater than to glass viscosity effect2,, content, which crosses conference, reduces glass melting speed
Degree extends clarification, homogenising time.Al in the present invention2O3Content is 5%~20%, processability and chemical stability of glass etc.
Well, all meet the production and application of product.
Ti02Network structure is improved, a certain amount of addition can in the presence of forming body as network intermediate oxide
To reduce the coefficient of expansion and forming temperature, chemical stability is improved, excessive addition can promote crystallization, reduce glass forming ability.
Ti0 in this patent2Content meets the production and application of product 0.01%~3%.
Fe in ferriferous oxide2O3Be glass network intermediate oxide, partially play connection glass network work
With, keep glass network finer and close, although too high levels will affect the heat penetration and tendency towards devitrification of glass, it is unfavorable to produce to fiber,
But a certain amount of addition improves glass structure extent of polymerization to a certain extent.In the present invention ferriferous oxide content 3%~
17%, while controlling devitrification of glass and glass forming ability, improve the chemical stability and thermal stability of glass.
Due to the solid waste of raw material red mud complicated component, MnO can be introduced into glass2、P205Equal impurity, content is 0
~1 %, content is lower, smaller to glass fibre qualitative effects by experiment test discovery.
By pretreated blast-furnace cinder, red mud and lime stone, commercial alumina, dolomite, silica flour, fluorite, magnesia
It is put into refractory container after mixing by corresponding proportion, obtains homogenizing in 1450 DEG C~1550 DEG C 4~6h of melted heat preservation clear
Then clear glass metal is being higher than forming temperature while being 103dPa.s (forming temperature takes viscosity of glass metal corresponding temperature) 15
Continuous glass fibre is drawn by casing or bushing at~40 DEG C or so, then cooling obtains alkali-resistant glass fibre (precursor),
Average fibre diameter is less than 30 microns.
Raw material composition of the present invention is shown in Table 2
2 sample raw material of table forms table (wt%).
Firstly, pretreated blast-furnace cinder red mud and other batches are pressed in the way of being formed as glass in table 2
Ratio mixing is uniform, and preparing glass charge is made, and 4~6 h of heat preservation are melted at 1450 DEG C~1550 DEG C and obtain being homogenized clear glass
Liquid pours into graphite jig the both bulk glasses sample obtained containing a small amount of bubble, and then heat preservation 2~4 is small at 600~700 DEG C
Shi Jinhang annealing, eliminates thermal stress.
In this patent, the fibre-forming performance of experiment test fiber is drawn by laboratory monofilament, by homogenizing, clear melting glass
Glass is supplied in casing, and fiber is pulled straight from the nozzle of its bottom surface, and is retouched Electronic Speculum by button and observed drawn monofilament.
Glass test block is subjected to density measurement, glass density uses Archimedes's drainage, does medium using deionized water
Measurement is measured 3 times and is averaged.
Glass test block is subjected to crushing grinding, obtains partial size less than 75 μm of glass powders and 180 ~ 250 μm of particles.To each examination
Sample carries out XRD, SEM, water-fast, alkali resistance, differential thermal, forming temperature and liquidus temperature test analysis.
Industrial applicibility: being through the above illustrated this patent, and this patent one kind can be proved with solid waste
Object blast-furnace cinder and red mud are that alkali-resistant glass fibre of primary raw material and preparation method thereof has feasibility, and passes through existing life
What production. art can be achieved on, alkali-resistant glass fibre of the invention is in GRC(Glass fiber Reinforced Concrete
Glass concrete) composite material, battery separator, exterior-wall heat insulation etc. require to have in resistant material it is preferable practical
Property.
Claims (10)
1. it is a kind of using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material, it is characterized in that solid waste weight percent is such as
Under: blast-furnace cinder 10%~45%, Bayer process red mud 8%~40%.
2. it is according to claim 1 using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material, it is characterized in that: described
Blast-furnace cinder is to pass through pretreated blast-furnace cinder, preprocess method are as follows: blast-furnace cinder has been subjected to water quenching before factory, dries
Dry, homogenizing is ground into the powder of certain partial size, meets the temperature under the requirement as glass fibre raw material at 400 DEG C or more
Lower processing 2~3 hours spare.
3. it is according to claim 1 using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material, it is characterized in that: described
Red mud is to pass through pretreated red mud, and preprocess method is that Bayer process red mud is removed water in 100 DEG C~200 DEG C drying
Divide then grinding sieving (granularity is less than 250 μm).
4. it is described in any item using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material according to claims 1-3, it is special
Sign is: alkali-resistant glass fibre weight percent is as follows: SiO2 46%~65%, Al2O3 5%~20%, CaO 7%~25%,
MgO 0.1%~7%, Na2O 0.1%~7%, ferriferous oxide 3%~17%, TiO2 0.01%~3%, other 0~1%.
5. it is according to claim 4 using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material, it is characterized in that: described
Ferriferous oxide is iron oxide and ferrous oxide two oxides.
6. it is according to claim 4 using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material, it is characterized in that: described
The mass values of alkali-resistant glass fibre composition are A1=SiO2/Al2O3It is 3.1%~5.3%；The SiO2Content 53%~
63%, the Al2O3Content 10%~20%.
7. it is according to claim 4 using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material, it is characterized in that: described
The mass values of alkali-resistant glass fibre composition are A2=SiO2/ (Fe2O3+ FeO) it is 7%~9.1%；The SiO2Content
55%~63%, the ferriferous oxide content 6%~9%.
8. it is according to claim 4 using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material, it is characterized in that: described
The mass values of alkali-resistant glass fibre composition are A3=Al2O3/ (Fe2O3+ FeO) it is 1.6%~2.2%；The Al2O3Contain
Amount 10%~20%, the ferriferous oxide content 6%~9%.
9. according to claim 4 using blast-furnace cinder and red mud as the alkali-resistant glass fibre of raw material, it is characterized in that: it is described its
He is the oxide components that solid waste inevitably introduces, and includes P205、MnO2Equal ingredients, total mass percent
It is 0~1%, wherein " 0 " is only represented close to 0.
10. a kind of preparation method of alkali-resistant glass fibre, comprising the following steps:
(1) Bayer process red mud and blast-furnace cinder pretreatment is spare；
(2) pretreated blast-furnace cinder, red mud and lime stone, commercial alumina, silica flour are put after mixing by corresponding proportion
Enter in refractory container, 1450 DEG C~1550 DEG C be melted heat preservation 4~6h obtain homogenizing clear glass metal, then be higher than at
(it is 10 that forming temperature takes viscosity of glass metal to type temperature3Corresponding temperature when dPa.s) 15~40 DEG C or so when pass through set control
At continuous glass fibre, then cooling obtains alkali-resistant glass fibre (precursor), and average fibre diameter is less than 30 microns.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785989A (en) * | 2020-06-29 | 2020-10-16 | 中国科学院上海硅酸盐研究所 | Sealing material for solid oxide fuel cell using blast furnace slag as main raw material, and preparation method and use method thereof |
| CN114057492A (en) * | 2021-11-26 | 2022-02-18 | 江苏科技大学 | Beta' -Sialon-AlN-TiC composite ceramic material and preparation method thereof |
| CN114873923A (en) * | 2022-03-28 | 2022-08-09 | 中铝山东有限公司 | Red mud-based heat insulation material and preparation method thereof |
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| CN109052974A (en) * | 2018-06-27 | 2018-12-21 | 四川省玻纤集团有限公司 | A kind of distribution of basalt fibre, mineral mixture and production technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111785989A (en) * | 2020-06-29 | 2020-10-16 | 中国科学院上海硅酸盐研究所 | Sealing material for solid oxide fuel cell using blast furnace slag as main raw material, and preparation method and use method thereof |
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| CN114057492A (en) * | 2021-11-26 | 2022-02-18 | 江苏科技大学 | Beta' -Sialon-AlN-TiC composite ceramic material and preparation method thereof |
| CN114057492B (en) * | 2021-11-26 | 2022-11-15 | 江苏科技大学 | Beta' -Sialon-AlN-TiC composite ceramic material and preparation method thereof |
| CN114873923A (en) * | 2022-03-28 | 2022-08-09 | 中铝山东有限公司 | Red mud-based heat insulation material and preparation method thereof |
| CN114873923B (en) * | 2022-03-28 | 2023-08-22 | 中铝山东有限公司 | Red mud-based heat insulation material and preparation method thereof |
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