CN100408514C - Refractory material containing barium oxide - Google Patents
Refractory material containing barium oxide Download PDFInfo
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- CN100408514C CN100408514C CNB031562612A CN03156261A CN100408514C CN 100408514 C CN100408514 C CN 100408514C CN B031562612 A CNB031562612 A CN B031562612A CN 03156261 A CN03156261 A CN 03156261A CN 100408514 C CN100408514 C CN 100408514C
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- barium
- mullite
- refractory materials
- cement
- micro powder
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Abstract
The present invention relates to a refractory material solidified by barium aluminate cement, which is prepared by using barium aluminate cement with normal coagulation activities as solidified agents and using aluminum oxide micro powder, silicon oxide micro powder and mullite micro powder as auxiliary binding agents. The barium oxide content of the refractory material is from 0.1 to 10%, the total quantity of the used aluminum oxide micro powder, the used silicon oxide micro powder and the used mullite micro powder is from 3 to 37%, wherein the aluminum oxide micro powder is aluminum oxide particles with the average grain size of 10 to 0.5 micrometres and comprises hydrous aluminum oxide; the silicon oxide micro powder is silicon oxide particles with the average grain size of 10 to 0.5 micrometres and comprises grammite; the mullite micro powder is mullite particles with the average grain size of 10 to 0.5 micrometres. The material has the chemical characteristics that the material contains barium oxide, and has the performance characteristics of normal coagulation, high setting rate, good low-temperature workability, high refractability and good thermal shock resistance.
Description
Technical field
The present invention relates to the refractory materials of a kind of Lv Suan Barium cement solidification.Such materials chemistry feature is to contain aerobic Barium, has the characteristics normal, that setting rate is fast, the low-temperature construction performance is good, resistivity against fire is high and heat-shock resistance is good of condensing on the performance.The material of being invented is suitable for rapid construction, low-temperature construction, is used for large-scale or special odd-shaped goods, and the occasion that high performance requirements is arranged.
Background technology
Over year, unshape refractory has had very big development surplus in the of 20.The consumption of the unsetting material of developed country has reached 50% of refractory materials total amount.Some shaping materials also adopt the method production of unshape refractory.When refractory materials is difficult to use pressure forming, can makes its curing by the small number of curing agents that the vibration shaping utilization is added in advance and have demoulding strength, and then make large-scale or special odd-shaped refractory materials through thermal treatment.
Solidifying agent or wedding agent are the keys of unshape refractory.Solidifying agent is to produce solidification, and directly produces or cause keying action, and then makes material have the material of intensity.Wedding agent is to produce the bonded material.Wedding agent can be made up of solidifying agent separately, also can by solidifying agent and the secondary combined agent is compound forms, and the agent that can be cured of the lateral reactivity of some secondary combined agent excites.At present, but the solidifying agent or the wedding agent that generally use have several big classes of aluminous cement, phosphoric acid, water glass, colloidal sol and ALUMINA HYDRATE.
The price of aluminous cement is lower, but (＜10 ℃) setting rate is very slow under the low temperature, and needing sometimes could the demoulding more than 24 hours.Conventional aluminous cement needs the maintenance more than 3 days could bring into play intensity fully.Another shortcoming of aluminous cement is the high-temperature behavior that has a strong impact on refractory materials.Be the golden season of kiln maintenance winter, but this moment, aluminous cement was difficult to satisfy the demands.For guaranteeing that acceptable condenses, setting rate, usually need to strengthen cement mixing content and take the temperature control measure.Construction i.e. trouble, has seriously influenced the performance of material again.
The phosphoric acid class is the wedding agent commonly used of refractory materials.But phosphoric acid has the advantage of rapid construction, also can give the good thermal shock resistance of material and in the wear resistance of the following temperature section of middle temperature, but seriously influences high-temperature behavior.For example: the refractoriness under load of high alumina brick can arrive 1550 ℃, but phosphoric acid salt only is 1350 ℃ in conjunction with the refractoriness under load of high alumina brick.
Water glass is cheap, but contains strong solvent material Na in a large number
2O.So water glass can only be used for low-grade refractory materials.
Silicon sol has higher purity, but price is higher.The subject matter of silicon sol is that the content of solid matter is limited, and can not harden voluntarily.Volume with 5% is only brought 1.25% silicon oxide into after adding the silicon sol of silica content 25%.Binding substances seldom is difficult to produce considerable intensity.
But the main drawback of ALUMINA HYDRATE is the water requirement that increase to be shaped, sclerosis is slow, bonding strength is low, be easy to explosion.This kind material difficulty is used as main wedding agent.
Because of all restrictions, low cement deposit material and cement deposit material the back unshape refractory occurs and never have major progress.
Summary of the invention
Barium cement is the technology that once was studied in the 50-60 age, and higher because of price, hydration rate is too fast, and it is restive to condense, and made concrete intensity is lower, thereby lives down.The purpose of this research is to invent the wedding agent of the new Han Yangization Barium of a class, solves the various shortcomings that in the past existed, and develops the good characteristic of barium cement, and then develops a new refractory materials family.
The performance of cement is that effective mineral are given.Invalid mineral will influence performance; Toxic mineral will have a strong impact on performance, even material can not be used.For the existing more complete research of aluminous cement, the control that Dan Dui Barium cement minerals is formed is report not.The exploitation of the solution Dui Yu Barium cement of this problem the unknown is significant.
The mineral relevant Yu Barium cement have corundum (Al
2O
3), Barium feldspar (BaO.Al
2O
3.SiO
2), six Lv Suan Barium (BaO.6Al
2O
3), aluminic acid one barium (BaO.Al
2O
3), aluminic acid three barium (3BaO.Al
2O
3) and Gui Suan Er Barium (2BaO.SiO
2).Alumina barium cement can realize that mineral assemblage is BA-B
2S-B
3A, BA-B
2S-BAS
2And BA-BAS
2-BA
6Fine aluminium Suan Barium cement be combined as BA-B
3A and BA-BA
6Barium feldspar and six Lv Suan Barium are considered to not have the material of hydratability.Therefore, BA, B
3A and B
2S just becomes the emphasis of research.
BA, B have been synthesized in this research
2S and be rich in B
3The material of A.Condensing of BA of result of study explanation can be controlled by retardant (as oxalic acid, tartrate, citric acid etc.).B
2The fast of S can not be controlled by the retardant of routine with fixed attention.B
3A has than strong and stimulating the respiratory tract of human body and is unfavorable for environmental protection, and its aquation is faster, the more difficult control of condensing.As add organic acid moment, B
2The pH value of the slurry of S is acid, and slurry has certain dispersiveness; After second, pH value just is shown as alkalescence surplus in the of short 10, and slurry condenses rapidly.This shows that delayed coagulation relies on retardant to be adsorbed on the cement particle surface and produces shielding effect and produce.Because of aquation too fast, B
2The hydration rate of S is suitable with the rate of adsorption of retardant, and retardant can not effectively shield B
2S contains more B
2S or B
3Condensing of A cement also just is difficult to the energy Be Controlled.So effective mineralogical composition of cement should be BA, but can add corundum, also can contain the not BA of aquation on a small quantity
6And BAS
2, only (preferably not) contains B on a small quantity
2S and B
3A.
The combination of another innovation Shi Barium cement of the present invention and micro mist.The precedent of Shi Yong Barium cement and refractory materials micro mist during at present, less than Tong in refractory materials.
Micro mist has littler particle diameter, bigger specific surface area, better caking power and stronger chemically reactive.Utilize above-mentioned characteristic that the performance of refractory materials is improved significantly.Micro mist can be filled in the space of the dense accumulation body that coarse particles, fine particle and fine powder form, improve the density of material, help reducing cement mixing content, promote solid state reaction and sintering, thereby can reduce void content, burn back line variation, significantly improve indexs such as volume density, intensity, resistance to fouling and refractoriness under load, comprehensively the performance of enhancing fire-resistant material.
Make the present invention be implemented also to be, generate binding substances dystectic and energy and the coexistence of refractory materials principal crystalline phase by controlling the reaction of cement and micro mist.The felspathic fusing point of Barium is up to 1760 ℃, but anorthitic fusing point only is 1550 ℃.The Barium feldspar can coexist with corundum, mullite and side's (squama) are quartzy.So to Cheng Yi Barium feldspar be the high-temperature behavior that the wedding agent of feature can improve refractory materials to Xing in clay, high alumina, mullite, mullite and corundum refractory.In like manner, form six Lv Suan Barium in corundum-magnesium-aluminium spinel system, or formation Gui Suan Er Barium has similar effect in periclasite-magnesium-aluminium spinel system.
This research has prepared the Lv Suan Barium refractory cements that rate of set can be controlled by retardant.Secondly, be with this cement and micro mist combination.Under the low temperature, rely on and to be adsorbed on that the micro mist surface generates the very poor material of degree of crystallinity and the Shuiization Lv Suan Barium crystal generation that may grow up is subsequently condensed after the Lv Suan Barium aquation, curing and demoulding strength.Yangization Barium and micro mist are Chenged Barium feldspar, Barium feldspar-six Lv Suan Barium at aluminium silicon based material Sheng respectively by solid state reaction after the thermal treatment, generate six Lv Suan Barium in corundum-magnesium-aluminium spinel system, generate Gui Suan Er Barium as wedding agent or sintering aids in periclasite-magnesium-aluminium spinel system, and then can develop a new refractory materials family.This family use BA be the refractory cements of effective mineralogical composition as solidifying agent, this cement does not contain or seldom contains B
2S and B
3A.The reaction of the material of bringing into by cement after the thermal treatment and micro mist, by the character of combined phase generate respectively Yi Barium feldspar, Barium feldspar-six Lv Suan Barium, six Lv Suan Barium or Gui Suan Er Barium be feature in conjunction with phase.
The present invention has studied a kind of barytic refractory materials that contains, it is characterized in that: this refractory materials by barium aluminate cement with normal coagulation behaviour as solidifying agent, agent is prepared from as secondary combined by aluminum oxide and silica powder and mullite miropowder, the barium oxide content of this refractory materials is 0.1-10%, the resultant of the alumina powder that uses, ultrafine silica powder and mullite miropowder is 3-37%, wherein said alumina powder is that median size is the alumina particle of 10-0.5 micron, but comprises the aluminum oxide of aquation; Ultrafine silica powder is that median size is the silicon oxide particle of 10-0.5 micron, comprises the silicon ash; Mullite miropowder is that median size is the mullite particle of 10-0.5 micron.Utilize the present invention can make the aluminium silicon system or the magnesium-aluminium spinel series refractory material of excellent performance, described aluminium silicon series refractory material comprises clay or mullite or mullite-corundum or corundum material, the feature of this class material is: under the low temperature, rely on the aquation of barium aluminate and the booster action of micro mist to solidify; After the thermal treatment, aforementioned refractory substance or its compound hydrate of barium aluminate that at high temperature relies on obtain good performance mutually with the combination that micro mist reaction generation contains celsian-felspar and/or six barium aluminates; Above-mentioned aluminum-spinel series refractory material refers to the aluminum-spinel to be the refractory materials of principal character mineralogical composition, this material can contain corundum or magnesia, the feature of this class material is: under the low temperature, rely on the aquation of barium aluminate and the booster action of micro mist to solidify, after the thermal treatment, magnesium-aluminium spinel, corundum and magnesia or its compound hydrate of barium aluminate that at high temperature relies on obtain good performance mutually with the combination that micro mist reaction generation contains six barium aluminates and/or silicic acid two barium.
Above-mentioned barium aluminate cement is to be that raw material is the cement of main effective constituent by the calcining synthetic with aluminic acid one barium BA at 900-1600 ℃ by barium carbonate or hydrated barta and aluminum oxide or aluminium hydroxide or higher-grade alumina, and BA content is greater than 30% in this cement.Impurity resultant such as celsian-felspar, six barium aluminates is less than 20% in this cement, the aluminic acid three barium B that aquation is exceedingly fast
3A and silicic acid two barium B
2The resultant of toxic minerals such as S is less than 5%.
Embodiment
Embodiment 1:
Use carbon acid Barium and commercial alumina to be raw material, by 197.35: 101.96 ratios preparation raw material, through conventional technology mix, levigate, mix, after the shaping, drying, made grog in 4 hours 1500 ℃ of calcinings, make the sour Barium cement of aluminium through fine grinding again.X-ray examination shows that cement only contains BA, and the content of other materials is less than limit of detection.
The proportioning of refractory mortar is:
＜0.088mm fused corundom 50%;
Aforementioned BA cement 20%;
Alumina powder 20%;
Silicon ash 10%;
Set-retarding admixture tartrate 3%.
Sample is behind 7 ℃ and water mix, but about 1 hour of curring time got final product the demoulding after 2.5 hours, test specimen maintenance 6 hours after 110 ℃ handled 6 hours, compressive strength is 144Mpa.After adding setting accelerator, the made refractory mortar of aluminous cement needs under the same conditions can the demoulding more than 12 hours.
Embodiment 2:
Method by implementation column 1 prepares cement.The proportioning of refractory concrete is:
5-1mm fused corundom 50%;
1-0.088mm fused corundom 20%;
The refractory materials powder of being prepared by implementation column 1 30%.
Sample advances heat treatments at different again by method shaping, maintenance and the drying of implementation column 1.The performance of preproduction is as follows:
Heat-treat condition folding strength Mpa compressive strength Mpa line changes %
110℃×24H 19.8 139
1100℃×3H 17.4 113 0.04
1500℃×3H 27.7 155 -0.02
After the 1500 ℃ * 3H thermal treatment, 1570 ℃ of refractorinesss under load.
After the 1500 ℃ * 3H thermal treatment, folding strength conservation rate 84% after 1100 ℃ of air blast coolings 3 times.
It is higher that ultralow aluminous cement corundum castable contrast sample not only burns back line velocity of variation, and the refractoriness under load of 1500 ℃ * 3H after handling only be 1470 ℃, and the conservation rate of folding strength only is 61% after 1100 ℃ of air blast coolings 3 times.Therefore, the high-temperature comprehensive property of Lv Suan Barium cement deposit material and heat-shock resistance all are better than calcium aluminate curing ultra-low cement deposit material greatly.
Refractory material of the present invention have condense normal, setting rate fast, the low-temperature construction performance is good, fire resistance is high and thermal shock resistance Good characteristics are used for rapid construction, low-temperature construction, preparation is large-scale or the goods of special shape, and the field that high performance requirements is arranged Close and then have clear superiority. According to aforementioned principles, when cement mixing content further reduces, or be used for corundum-magnesium aluminate spinel system, During magnesium aluminate spinel-periclase system, the bond technology that the present invention studies also can obtain to be much better than the effect of aluminous cement Really.
Claims (3)
1. one kind contains barytic refractory materials, it is characterized in that: this refractory materials by barium aluminate cement with normal coagulation behaviour as solidifying agent, agent is prepared from as secondary combined by aluminum oxide and silica powder and mullite miropowder, the barium oxide content of this refractory materials is 0.1-10%, the resultant of the alumina powder that uses, ultrafine silica powder and mullite miropowder is 3-37%, and wherein said alumina powder is that median size is the alumina particle of 0.5-10 micron; Ultrafine silica powder is that median size is the silicon oxide particle of 0.5-10 micron; Mullite miropowder is that median size is the mullite particle of 0.5-10 micron, described barium aluminate cement is to be that raw material is the cement of main effective constituent by the calcining synthetic with aluminic acid one barium BA at 900-1600 ℃ by barium carbonate or hydrated barta and aluminum oxide or aluminium hydroxide or higher-grade alumina, BA content is greater than 30% in this cement, this cement comprises the resultant of impurity of celsian-felspar, six barium aluminates less than 20%, the aluminic acid three barium B that aquation is exceedingly fast
3A, silicic acid two barium B
2The resultant of S is less than 5%.
2. according to claim 1ly contain barytic refractory materials, it is characterized in that: described refractory materials is an aluminium silicon series refractory material, and this refractory materials comprises clay or mullite or mullite-corundum or corundum material.
3. according to claim 1ly contain barytic refractory materials, it is characterized in that: described refractory materials is a magnalium silicon spinel series refractory material, refers to the magnesium-aluminium spinel to be the refractory materials of principal character mineralogical composition, and this material contains corundum or magnesia.
Priority Applications (1)
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|---|---|---|---|
| CNB031562612A CN100408514C (en) | 2003-09-02 | 2003-09-02 | Refractory material containing barium oxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031562612A CN100408514C (en) | 2003-09-02 | 2003-09-02 | Refractory material containing barium oxide |
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| Publication Number | Publication Date |
|---|---|
| CN1590346A CN1590346A (en) | 2005-03-09 |
| CN100408514C true CN100408514C (en) | 2008-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (1)
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|---|---|---|---|---|
| CN107162609A (en) * | 2017-05-14 | 2017-09-15 | 长兴县煤山工业炉料有限公司 | A kind of wet spray material |
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| CN100337987C (en) * | 2005-04-18 | 2007-09-19 | 宜兴市诺明高温耐火材料有限公司 | Mullite silicon carbide refractory material for production of dry coke and its production |
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| CN104649689B (en) * | 2013-11-22 | 2016-09-14 | 中国石化工程建设有限公司 | A kind of castable refractory being applicable under low temperature environment construction and preparation method |
| CN106977216B (en) * | 2017-04-05 | 2019-09-13 | 洛阳理工学院 | Anti-erosion liner and preparation method thereof for aluminium melting furnace |
| CN106927700B (en) * | 2017-04-05 | 2019-04-02 | 洛阳理工学院 | One kind barium silicate cement containing baryta fledspar and preparation method thereof |
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| CN116253573B (en) * | 2022-12-26 | 2024-01-26 | 宜兴瑞泰耐火材料工程有限公司 | Corundum-zirconium mullite castable for hazardous waste furnace |
| CN116063090A (en) * | 2023-02-09 | 2023-05-05 | 鞍山市和丰耐火材料有限公司 | Ladle working lining carbon-free corundum spinel precast block and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099013A (en) * | 1993-12-07 | 1995-02-22 | 四川省建材工业科学研究院 | A kind of barium cement |
| CN1104194A (en) * | 1994-05-03 | 1995-06-28 | 淄博市淄川工业陶瓷厂 | Technology for production of anti-oxidation silicon carbide fire-retardant material |
-
2003
- 2003-09-02 CN CNB031562612A patent/CN100408514C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099013A (en) * | 1993-12-07 | 1995-02-22 | 四川省建材工业科学研究院 | A kind of barium cement |
| CN1104194A (en) * | 1994-05-03 | 1995-06-28 | 淄博市淄川工业陶瓷厂 | Technology for production of anti-oxidation silicon carbide fire-retardant material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162609A (en) * | 2017-05-14 | 2017-09-15 | 长兴县煤山工业炉料有限公司 | A kind of wet spray material |
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|---|---|
| CN1590346A (en) | 2005-03-09 |
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Assignee: Yixing Refractory Material Co.,Ltd. Assignor: RUITAI TECHNOLOGY Co.,Ltd. Contract record no.: 2011320000516 Denomination of invention: Refractory material containing barium oxide Granted publication date: 20080806 License type: Exclusive License Open date: 20050309 Record date: 20110406 |
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Assignee: Yixing Refractory Material Co.,Ltd. Assignor: RUITAI TECHNOLOGY Co.,Ltd. Contract record no.: 2011320000841 Denomination of invention: Refractory material containing barium oxide Granted publication date: 20080806 License type: Exclusive License Open date: 20050309 Record date: 20110620 |
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