CN103395998A - Foam glass prepared from waste high-aluminum alkali-free boron-free glass fiber and manufacturing method thereof - Google Patents
Foam glass prepared from waste high-aluminum alkali-free boron-free glass fiber and manufacturing method thereof Download PDFInfo
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- CN103395998A CN103395998A CN2013103242690A CN201310324269A CN103395998A CN 103395998 A CN103395998 A CN 103395998A CN 2013103242690 A CN2013103242690 A CN 2013103242690A CN 201310324269 A CN201310324269 A CN 201310324269A CN 103395998 A CN103395998 A CN 103395998A
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Abstract
The invention discloses foam glass prepared from waste high-aluminum alkali-free boron-free glass fiber. The foam glass comprises 90-96wt% of waste glass fiber, 0.5-5wt% of SiC, 0.5-5wt% of coke, 0.5-7.5wt% of Sb2O5, 0.5-7.5wt% of CeO2, 0.5-7.5wt% of Na2SO4 and 0.5-7.5wt% of Na2CO3, wherein the waste glass fiber contains not less than 12wt% of Al2O3; and the molar ratio of Na2O/Al2O3 in the composition of the foam glass is more than 1. The invention further discloses a manufacturing method of the foam glass. The foam glass disclosed by the invention has the advantages of low density, high compressive and flexural strength and excellent quality performance, and can not only effectively improve the comprehensive utilization of industrial wastes, but also reduce the manufacturing cost of the foam glass and the environmental harm caused by the foam glass. In addition, the preparation process disclosed by the invention has the advantages of simple process and low production cost, and is suitable for industrial production.
Description
Technical field
The present invention relates to the multicellular glass technical field, relate in particular to a kind of multicellular glass and the manufacture method thereof of alkali-free without the glass fiber waste silk preparation of boron and high aluminium content of utilizing.
Background technology
Along with the development of Chinese national economy, the demand expanding day of building trade also improves, and construction material is in the developing period of update.multicellular glass is compared with other type material with traditional material, at mechanics, calorifics, the aspects such as acoustics index all have excellent performance, both had heat insulating, waterproof and dampproof, fire prevention, acid and alkali-resistance, density is little, a series of high-performances such as physical strength height, have again intrinsic permanent of glass material itself, security, reliability, anti-chemical corrodibility and be not subjected to the advantages such as ant mouse infringement, can be widely used in middle temperature heat insulating, the heat insulating of building inside and outside wall, waterproof and dampproof engineering, decorative engineering, petrochemical complex, refrigeration, the field such as subway and underground works.Simultaneously, the raw material of producing multicellular glass is mainly scrap glass, glass fiber waste silk, slag and flyash etc., and these wastes generally all are dropped or, only through simple landfill disposal, have not only wasted a large amount of resources, and to environment, brought very large harm.The preparation of multicellular glass and be applied as digestion these solid waste opened up an effective way, make social resources be able to regeneration, and solved preferably the pollution problem of solid-state rubbish to environment.Therefore, this novel low-cost energy-saving and environment friendly product of multicellular glass, will play a significant role in the change of China's novel wall material.
Regular foam glass is to utilize glass cullet to be main raw material, by adding whipping agent, suds-stabilizing agent, fusing assistant etc., through evenly being mixed to get admixtion, then admixtion is put into the high temperature steel mould,, through techniques such as preheating, sintering, foaming, annealing, make it to form the glass material of the even porous in a kind of inside.This class regular foam glass has that unit weight is little, thermal conductivity is low, water-intake rate is low, acid and alkali-resistance, the good characteristic such as high temperature resistant, but its physical strength is lower, the multicellular glass folding strength of different size, at 0.1～1MPa, has limited its use range as material of construction greatly in the market.
Glass fiber waste silk is the solid waste that produces in the glass fibre production process, adopts for a long time the method for landfill to process always.In prior art with medium-alkali glass fibre (Na
2O=11.04%) waste silk is main raw material, adds whipping agent coke, Wingdale etc. to prepare multicellular glass.Yet, belonging to network outer body in glass due to basic oxide, content has destroyed the [SiO in glass at most
4] tetrahedral network structure, therefore prepared its resistance to compression of multicellular glass and folding strength is still lower.
The alkali-free boron-free glass fibers is present most widely used a kind of glass fibre, and its annual discarded hard of producing is up to 120,000 tons.Alkali-free is without Al in boron and high alumina glass fiber waste silk
2O
3Percentage composition more than 10%, much larger than the Al in simple glass and medium-alkali glass fibre
2O
3Content (＜5%), utilize the Al in glass fibre
2O
3, make Al
3+Form [AlO
4] tetrahedron, with [SiO
4] tetrahedron forms unified network structure, can improve chemical stability, thermostability, the physical strength of multicellular glass.But alkali-free is without boron and high-content Al
2O
3Can cause the fusing point of material very high, this preparation for multicellular glass is one of gordian technique difficult problem.Simultaneously, in the time of also can causing the glass fibre melting without boron, surface tension is excessive, is unfavorable for the stable of bubble, this be prepare multicellular glass a gordian technique difficult problem two.Due to its high-melting-point that has, if adopt production of low-temperature foaming agent in coke, Wingdale etc. to be difficult to prepare qualified multicellular glass.For this reason, adopt high-temperature foaming agent SiC in prior art, by with O
2Reaction produces CO
2Gas and form bubble (SiC+O
2=Si+CO
2↑), but the oxygen in the foaming process Air is difficult to enter in powder and reacts with SiC, added oxygenate Sb for this reason
2O
3, but due to Sb
2O
3Decomposition temperature up to 1400 ℃, therefore, considerably beyond the temperature of fusion of glass powder, can not play the oxygen supply effect, cause foamed glass foaming incomplete, walls is too thick, makes the density of material higher.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of high alumina alkali-free boron-free glass fibers waste silk that utilizes for main raw material preparation, have that density is low, pressure-proof and snap-resistent intensity is high, the high-intensity foam glass of excellent performance, to improve the quality of multicellular glass, enlarge the scope of application, and the effectively comprehensive utilization of raising to trade waste, reduce the stomach cold that environment is brought.Another object of the present invention is to provide the manufacture method of the above-mentioned high-intensity foam glass that a kind of production technique is simple, production cost is low, to be suitable for suitability for industrialized production.
Purpose of the present invention is achieved by the following technical programs:
A kind of multicellular glass that utilizes the preparation of high alumina alkali-free boron-free glass fibers waste silk provided by the invention, it consists of: glass fiber waste silk 90～96wt%, SiC0.5～5wt%, coke 0.5～5wt%, Sb
2O
50.5～7.5wt%, CeO
20.5～7.5wt%, Na
2SO
40.5～7.5wt%, Na
2CO
30.5～7.5wt%; Contain Al in described glass fiber waste silk
2O
3〉=12wt%; Mol ratio Na during described multicellular glass forms
2O/Al
2O
3＞1.
The high aluminium content that multicellular glass of the present invention utilizes glass fiber waste silk is when improving mechanical strength, by adding appropriate Na
2CO
3Introduce the Na element and adjust Na
2O/Al
2O
3Mol ratio, greater than 1, makes mixed glass batch temperature of fusion be minimized.Introduce on this basis SiC, coke, CeO
2, Sb
2O
5As composite foamed system, due to CeO
2, Sb
2O
5Decomposition temperature consistent with the temperature of fusion of glass batch, so can produce a large amount of oxygen, make SiC, coke fully react and produce enough gas, material is foamed abundant, walls is thin, thereby has reduced the density of material.Simultaneously, Sb
2O
5Product S b after decomposition
2O
3Can reduce the surface tension of glass, thereby play steady bubble effect.
Further, multicellular glass of the present invention its preferably consist of: glass fiber waste silk 90～96wt%, SiC1～4wt%, coke 0.5～1wt%, Sb
2O
50.5～2wt%, CeO
20.5～2wt%, Na
2SO
40.5～2wt%, Na
2CO
30.5～3wt%.
In such scheme, the chemical composition of the described glass fiber waste silk of multicellular glass of the present invention is: SiO
255～65wt%, Al
2O
312～25wt%, CaO15～25wt%, Fe
2O
3＜1wt%, MgO＜2wt%, K
2O＜2wt%, Na
2O＜2wt%, TiO
2＜1wt%.
Further, described in multicellular glass of the present invention, glass fiber waste silk contains Al
2O
3Be advisable with 16～20wt%.
Another object of the present invention is achieved by the following technical programs:
The above-mentioned manufacture method of utilizing the multicellular glass of high alumina alkali-free boron-free glass fibers waste silk preparation provided by the invention comprises the following steps:
A, with glass fiber waste silk cleaning, oven dry, ball milling, after sieving, obtain glass powder;
B, glass powder and each are formed and add ball milling 2h in ball mill to form the multicellular glass admixtion;
C, described multicellular glass admixtion is joined in the high temperature steel mould, puts into foaming furnace and carry out following foam process process:
Pre-heating stage, be warming up to 300～500 ℃ from room temperature with the heat-up rate of 1～5 ℃/min, insulation 30～120min;
Foaming stages, be warming up to 850～1050 ℃ with the heat-up rate of 5～15 ℃/min;
The steady bubble stage, at 850～1050 ℃ of temperature, insulation 10～60min;
Cooling stages, be cooled to 500～750 ℃ with the cooling rate of 10～20 ℃/min;
Annealing stage, at 500～750 ℃ of temperature, insulation 20～60min, then cool to room temperature with the furnace and obtain multicellular glass.
The present invention has following beneficial effect:
The present invention utilizes alkali-free without boron and high alumina glass fiber waste silk, has obtained the high-intensity foam glass that density is low, pressure-proof and snap-resistent intensity is high, capability and performance is excellent, and prepared multicellular glass density is less than 0.22g/cm
3, folding strength, greater than 3.2Mpa, effectively improved the comprehensive utilization to trade waste greater than 2.2Mpa, ultimate compression strength, reduced the manufacturing cost of multicellular glass and the harm that environment is caused.Preparation process of the present invention is simple, and production cost is low, is suitable for suitability for industrialized production.
The present invention is described in further detail below in conjunction with embodiment.
Embodiment
The embodiment of the present invention adopts alkali-free (to contain Al without boron and high alumina
2O
316wt%) glass fiber waste silk is main raw material.The raw material of each embodiment multicellular glass forms as shown in table 1.
The raw material of table 1 various embodiments of the present invention multicellular glass forms (wt%)
The manufacture method of embodiment of the present invention multicellular glass, its step is as follows:
A, will the glass fiber waste silk cleaning, oven dry, ball milling, obtain glass powder after crossing 250 mesh sieves;
B, glass powder and each are formed and add ball milling 2h in ball mill to form the multicellular glass admixtion;
C, the multicellular glass admixtion is joined in the high temperature steel mould, puts into foaming furnace and carry out following foam process process:
Pre-heating stage, be warming up to 300～500 ℃ from room temperature with the heat-up rate of 1～5 ℃/min, insulation 30～120min;
Foaming stages, be warming up to 850～1050 ℃ with the heat-up rate of 5～15 ℃/min;
The steady bubble stage, at 850～1050 ℃ of temperature, insulation 10～60min;
Cooling stages, be cooled to 500～750 ℃ with the cooling rate of 10～20 ℃/min;
Annealing stage, at 500～750 ℃ of temperature, insulation 20～60min, then cool to room temperature with the furnace and obtain multicellular glass.
In various embodiments of the present invention multicellular glass manufacture method, the processing parameter of foaming process is as shown in table 2.
Table 2 various embodiments of the present invention multicellular glass manufacture method foaming process processing parameter
The performance perameter of the made multicellular glass that obtains of various embodiments of the present invention is as shown in table 3.
The performance perameter of the made multicellular glass that obtains of table 3 various embodiments of the present invention
Claims (5)
1. a multicellular glass that utilizes the preparation of high alumina alkali-free boron-free glass fibers waste silk, is characterized in that it consists of: glass fiber waste silk 90～96wt%, SiC0.5～5wt%, coke 0.5～5wt%, Sb
2O
50.5～7.5wt%, CeO
20.5～7.5wt%, Na
2SO
40.5～7.5wt%, Na
2CO
30.5～7.5wt%; Contain Al in described glass fiber waste silk
2O
3〉=12wt%; Mol ratio Na during described multicellular glass forms
2O/Al
2O
3＞1.
2. the multicellular glass that utilizes the preparation of high alumina alkali-free boron-free glass fibers waste silk according to claim 1, is characterized in that it consists of: glass fiber waste silk 90～96wt%, SiC1～4wt%, coke 0.5～1wt%, Sb
2O
50.5～2wt%, CeO
20.5～2wt%, Na
2SO
40.5～2wt%, Na
2CO
30.5～3wt%.。
3. the multicellular glass that utilizes the preparation of high alumina alkali-free boron-free glass fibers waste silk according to claim 1, is characterized in that the chemical composition of described glass fiber waste silk is: SiO
255～65wt%, Al
2O
312～25wt%, CaO15～25wt%, Fe
2O
3＜1wt%, MgO＜2wt%, K
2O＜2wt%, Na
2O＜2wt%, TiO
2＜1wt%.
4. according to claim 1 and 2 or 3 described multicellular glass that utilize high alumina alkali-free boron-free glass fibers waste silk preparation, it is characterized in that: described glass fiber waste silk contains Al
2O
316～20wt%.
5. the described manufacture method of utilizing the multicellular glass of high alumina alkali-free boron-free glass fibers waste silk preparation of one of claim 1-4 is characterized in that comprising the following steps:
A, with glass fiber waste silk cleaning, oven dry, ball milling, after sieving, obtain glass powder;
B, glass powder and each are formed and add ball milling 2h in ball mill to form the multicellular glass admixtion;
C, described multicellular glass admixtion is joined in the high temperature steel mould, puts into foaming furnace and carry out following foam process process:
Pre-heating stage, be warming up to 300～500 ℃ from room temperature with the heat-up rate of 1～5 ℃/min, insulation 30～120min;
Foaming stages, be warming up to 850～1050 ℃ with the heat-up rate of 5～15 ℃/min;
The steady bubble stage, at 850～1050 ℃ of temperature, insulation 10～60min;
Cooling stages, be cooled to 500～750 ℃ with the cooling rate of 10～20 ℃/min;
Annealing stage, at 500～750 ℃ of temperature, insulation 20～60min, then cool to room temperature with the furnace and obtain multicellular glass.
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|---|---|---|---|
| CN201310324269.0A CN103395998B (en) | 2013-07-30 | 2013-07-30 | A kind of utilize high-aluminum alkali-free boron-free glass fibers waste silk to prepare multicellular glass and manufacture method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310324269.0A CN103395998B (en) | 2013-07-30 | 2013-07-30 | A kind of utilize high-aluminum alkali-free boron-free glass fibers waste silk to prepare multicellular glass and manufacture method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103395998A true CN103395998A (en) | 2013-11-20 |
| CN103395998B CN103395998B (en) | 2015-11-18 |
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ID=49559792
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745029A (en) * | 2021-02-05 | 2021-05-04 | 中化学华陆新材料有限公司 | Preparation method of energy-saving aerogel composite foam glass |
| CN113354290A (en) * | 2021-06-25 | 2021-09-07 | 泰山玻璃纤维邹城有限公司 | Preparation method of foamed glass based on waste recycling in glass fiber production process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955319A (en) * | 2010-08-26 | 2011-01-26 | 陕西科技大学 | Method for preparing foamed glass by using waste fiberglass products |
| CN102050583A (en) * | 2010-10-27 | 2011-05-11 | 泰山玻璃纤维有限公司 | Chemical corrosion resistant fiberglass |
-
2013
- 2013-07-30 CN CN201310324269.0A patent/CN103395998B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955319A (en) * | 2010-08-26 | 2011-01-26 | 陕西科技大学 | Method for preparing foamed glass by using waste fiberglass products |
| CN102050583A (en) * | 2010-10-27 | 2011-05-11 | 泰山玻璃纤维有限公司 | Chemical corrosion resistant fiberglass |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745029A (en) * | 2021-02-05 | 2021-05-04 | 中化学华陆新材料有限公司 | Preparation method of energy-saving aerogel composite foam glass |
| CN113354290A (en) * | 2021-06-25 | 2021-09-07 | 泰山玻璃纤维邹城有限公司 | Preparation method of foamed glass based on waste recycling in glass fiber production process |
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| CN103395998B (en) | 2015-11-18 |
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