CN100348536C - Antihydration MgO-CaO clinker and its preparation method - Google Patents
Antihydration MgO-CaO clinker and its preparation method Download PDFInfo
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- CN100348536C CN100348536C CNB02138990XA CN02138990A CN100348536C CN 100348536 C CN100348536 C CN 100348536C CN B02138990X A CNB02138990X A CN B02138990XA CN 02138990 A CN02138990 A CN 02138990A CN 100348536 C CN100348536 C CN 100348536C
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- CN
- China
- Prior art keywords
- oxalic acid
- mgo
- acid solution
- cao
- solution
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- Treatment Of Steel In Its Molten State (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention belongs to the technical field of fire-resistant materials. After magnesium-calcium sand is soaked in oxalic acid solution, and is dried, and the fire-resistant materials are prepared by heat processing at the protection of CO2 atmosphere; the magnesium-calcium sand comprises CaO and MgO as the main components, and impurities such as SiO2, Al2O3, Fe2O3, K2O, Na2O, etc. Oxalic acid is dissolved in water to prepare the oxalic acid solution, and the oxalic acid solution can be replaced by ammonium oxalate, or the composite solution of oxalic acid and ammonium oxalate. The present invention has the characteristics of obvious hydration resistance, erosion resistance, high high-temperature strength, simple technology and no pollution for molten steel, and is suitable for repairing inner linings of rotating furnaces, electric furnaces ladles and tundishs, and fire-resistant materials.
Description
One, technical field
The invention belongs to technical field of refractory materials, relate in particular to a kind of magnesium lime refractory and preparation method thereof.
Two, background technology
Along with the Clean Steel smelting technology, stainless steel smelting continuous advancement in technology particularly, the MgO-CaO fire resistant materials is because its superior physicals and excellent metallurgical effect, and abundant raw material resources and more and more being subject to people's attention.But wherein used MgO-CaO grog hydration resistance remains " bottleneck " of this material development, has done a large amount of research work for many years both at home and abroad:
1, in the MgO-CaO grog, introduces Al
2O
3, V
2O
5, AlF
3, MgF
3, CaF
2, or its mixture, to improve the hydration resistance (US 3753747) of grog;
2, mainly with dolomite mineral or light dolomite hydrate, magnesite or light-calcined magnesite hydrate, CeO
2Or contain CeO
2Mixed rare earth compound, ferric oxide or iron scale be raw material, obtain compound according to a certain ratio, behind mixing, adding binding agent mixes, be pressed into waste base or ball then, in the kiln of 1600～1650 ℃ of temperature, calcine, to make hydration resistance calcium-magnesium clinker (ZL 96109507);
3, generate one deck insoluble phosphate type coating on the granular grog of MgO-CaO surface with phosphoric acid or phosphate reaction.These phosphatic representatives are various phosphatic rock, as hydroxyapatite [Ca
10(PO
4)
6(OH)
2], phosphorus chloride lime stone [Ca
10(PO
4)
6Cl
2], fluoro phosphatic rock [Ca
10(PO
4)
6F
2], calcium phosphate [Ca
3(PO
4)
2], secondary calcium phosphate hydrate (CaHPO
42H
2And Calcium Pyrophosphate (Ca O) etc.,
2P
3O
7), calcium metaphosphate [Ca (PO
3)
2] wait (spy opens flat 69-161370).
The relevant research work that improves or improve MgO-CaO grog hydration resistance can be summarized as: 1) introduce such as Fe
2O
3, TiO
2, Al
2O
3, SiO
2, rare earth oxide etc. adds thing, burns till fine and close and the stronger MgO-CaO grog of anti-hydratability through high temperature; 2) the MgO-CaO grog is adopted solution surface such as phosphoric acid or phosphoric acid salt handle the MgO-CaO grog that obtains anti-hydratability improvement.
But these two class methods, the former generates eutectic because of the thing of introducing that adds with the grog reaction, can reduce the hot strength and the solidity to corrosion of material, and the phosphorus in latter's coating can dissolve in molten steel, the pollution molten steel.
Three, summary of the invention
MgO-CaO grog that task of the present invention provides a kind of anti-aquation, anti-erosion, can improve hot strength, technology is simple, molten steel is not polluted and preparation method thereof.
For finishing above-mentioned task, the technical solution adopted in the present invention is calcium magnesia sand to be soaked after drying in oxalic acid solution, at CO
2Thermal treatment is made under the atmosphere protection.
Calcium magnesia sand is to be main chemical compositions with CaO, MgO, contains SiO
2, Al
2O
3, Fe
2O
3, K
2O, Na
2O, etc. impurity.Its content is respectively: CaO is 0～100%, MgO is 100～0%, SiO
2Be 0～2%, Al
2O
3Be 0～1%, Fe
2O
3Be 0～5%, K
2O is 0～0.5%, Na
2O is 0～0.5%, and granularity is 20.00～0.50mm.
Calcium magnesia sand was soaked in oxalic acid solution 5～60 seconds, after 100～150 ℃ of dryings, at CO
2Soaking time 0.5～2h is made in 400～900 ℃ of thermal treatments under the atmosphere protection.
Oxalic acid solution is that oxalic acid is water-soluble, and the oxalic acid solution that is mixed with 0.5～5.0mol/l is made surperficial treatment agent.Also can adopt the composite solution of ammonium oxalate solution or oxalic acid and ammonium oxalate to replace oxalic acid solution.Its preparation is same as oxalic acid solution.
Since the present invention with the MgO-CaO grog at oxalic acid solution or ammonium oxalate solution or oxalic acid, ammonium oxalate composite solution to carrying out surface impregnation, again at CO
2Under the atmosphere protection its surperficial remaining CaO is blocked the CaCO of formation
3As second phase in the film, the crackle forward position that produces when thermal treatment contacts with second, and crackle has been changed the stress concentration of crack tip by deviation and branch, thereby forms one deck densification and flawless caoxalate and lime carbonate composite membrane on MgO-CaO grog surface.With independent CO
2Processing, phosphatizing and untreated comparing, aquation rate of body weight gain and Pulverization ratio obviously reduce.And because film is thinner, film decomposes under the high temperature, to the hot strength and the not influence of slag resistance of MgO-CaO grog.
Therefore, the present invention has tangible anti-aquation, anti-erosion, can improve hot strength, technology characteristic of simple, and molten steel is not polluted.The MgO-CaO grog of the present invention's preparation is suitable for the repairing of the liner and the refractory materials of converter, electric furnace, ladle and tundish.
Four, embodiment
Embodiment 1 is coffee-like calcium magnesia sand with outward appearance, and its chemical ingredients is respectively SiO
20.67%, Al
2O
30.19%, Fe
2O
30.55%, CaO 56.03%, MgO 41.80%, K
2O 0.021%, Na
2O 0.13%, I.L 0.51%, granularity 4.00～3.00mm soaked for 20 seconds in oxalic acid solution, after 110 ℃ of dryings, at CO
2The following 800 ℃ * 1h of atmosphere protection thermal treatment is made.
Simultaneously with independent CO
2Processing, Al (H
2PO
4)
3Solution and CO
2Combined Processing, without the comparing of any processing, aquation rate of body weight gain and Pulverization ratio are listed as following table respectively.
| Performance | Embodiment | Comparative example | ||
| Oxalic acid+CO 2 | CO 2 | Al(H 2PO 4) 3+CO 2 | Be untreated | |
| Rate of body weight gain % Pulverization ratio % | 0.04 1.1 3 | 0.1 1.7 | 0.14 2.31 | 0.46 2.55 |
Embodiment 2 is SiO with chemical ingredients
2Be 1.50%, Al
2O
3Be 0.88%, Fe
2O
3Be 1.14%, CaO is 24.91%, MgO is 71.17%, K
2O is 0.013%, Na
2O is 0.08%, I.L is 0.31% calcium magnesia sand, and its granularity is 5.00～2.00mm, soaks for 30 seconds in oxalic acid solution, after 110 ℃ of dryings, at CO
2The following 700 ℃ * 1h of atmosphere protection thermal treatment.Its aquation rate of body weight gain is 0.03%, and Pulverization ratio is 1.10%, and is 0.3% without the aquation rate of body weight gain of any processing, and Pulverization ratio is 2.10%.
Claims (1)
1, the preparation method of a kind of anti-hydration MgO-CaO grog is characterized in that calcium magnesia sand was soaked in oxalic acid solution 5～60 seconds, after 100～150 ℃ of dryings, at CO
2Soaking time 0.5～2h is made in 400～900 ℃ of thermal treatments under the atmosphere protection;
---calcium magnesia sand is to be main chemical compositions with CaO, MgO, contains SiO
2, Al
2O
3, Fe
2O
3, K
2O, Na
2Impurity such as O, its chemical ingredients is: CaO is 0～100%, MgO is 100～0%, SiO
2Be 0～2%, Al
2O
3Be 0～1%, Fe
2O
3Be 0～5%, K
2O is 0～0.5%, Na
2O is 0～0.5%, and granularity is 20.00～0.50mm;
---oxalic acid solution is that oxalic acid is water-soluble, and the oxalic acid solution that is mixed with 0.5～5.0mol/l is made surperficial treatment agent, also can adopt the composite solution of ammonium oxalate solution or oxalic acid and ammonium oxalate to replace oxalic acid solution, and its preparation is same as oxalic acid solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02138990XA CN100348536C (en) | 2002-08-30 | 2002-08-30 | Antihydration MgO-CaO clinker and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02138990XA CN100348536C (en) | 2002-08-30 | 2002-08-30 | Antihydration MgO-CaO clinker and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1478754A CN1478754A (en) | 2004-03-03 |
| CN100348536C true CN100348536C (en) | 2007-11-14 |
Family
ID=34147329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB02138990XA Expired - Fee Related CN100348536C (en) | 2002-08-30 | 2002-08-30 | Antihydration MgO-CaO clinker and its preparation method |
Country Status (1)
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602602B (en) * | 2009-07-06 | 2011-12-28 | 西安建筑科技大学 | Hydration-resistant MgO-CaO series fireproofing material and preparation method thereof |
| CN105439577B (en) * | 2015-11-25 | 2017-08-25 | 武汉科技大学 | A kind of nucleocapsid clad structure calcium magnesite and preparation method thereof |
| CN107663079A (en) * | 2016-07-29 | 2018-02-06 | 本钢板材股份有限公司 | A kind of calcium oxide sand gas phase preventing hydration method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10245284A (en) * | 1997-03-05 | 1998-09-14 | Okayama Ceramics Gijutsu Shinko Zaidan | Magnesian and calcian refractory |
| JP2001253766A (en) * | 2000-03-09 | 2001-09-18 | Council Scient Ind Res | Method for manufacturing high density hydration- resistant lime sintered compact |
| CN1332132A (en) * | 2001-08-13 | 2002-01-23 | 武汉科技大学 | Hydration-resisting refractory MgO-CaO material series and its prepn |
-
2002
- 2002-08-30 CN CNB02138990XA patent/CN100348536C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10245284A (en) * | 1997-03-05 | 1998-09-14 | Okayama Ceramics Gijutsu Shinko Zaidan | Magnesian and calcian refractory |
| JP2001253766A (en) * | 2000-03-09 | 2001-09-18 | Council Scient Ind Res | Method for manufacturing high density hydration- resistant lime sintered compact |
| CN1332132A (en) * | 2001-08-13 | 2002-01-23 | 武汉科技大学 | Hydration-resisting refractory MgO-CaO material series and its prepn |
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| Publication number | Publication date |
|---|---|
| CN1478754A (en) | 2004-03-03 |
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