CN101591184B - Method for preparing anti-hydration MgO-CaO series refractory material by using used magnesia carbon bricks - Google Patents
Method for preparing anti-hydration MgO-CaO series refractory material by using used magnesia carbon bricks Download PDFInfo
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- CN101591184B CN101591184B CN2009100232012A CN200910023201A CN101591184B CN 101591184 B CN101591184 B CN 101591184B CN 2009100232012 A CN2009100232012 A CN 2009100232012A CN 200910023201 A CN200910023201 A CN 200910023201A CN 101591184 B CN101591184 B CN 101591184B
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- magnesia carbon
- carbon brick
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Abstract
The invention discloses a method for preparing an anti-hydration MgO-CaO series refractory material by using used magnesia carbon bricks, which comprises the following steps: classifying and breaking the used magnesia carbon bricks and putting the classified and broken magnesia carbon bricks on the bottom of a reaction vessel, putting a MgO-CaO series material above the broken used magnesia carbon brick particle mixture, and putting the reaction vessel into a controlled atmosphere furnace; vacuumizing the controlled atmosphere furnace, charging Ar as a protective gas, heating the finance and keeping the temperature when the temperature reaches certain temperature range; and introducing O2 into the furnace so that the MgO and C in the used magnesia carbon brick particles perform carbon thermal reduction reaction to generate Mg steam which is diffused to get close to the MgO-CaO series material and reacts with the introduced O2 so as to generate a MgO compact film on the surface of the MgO-CaO series material, wherein the MgO compact film isolates the contact between CaO and water so that the anti-hydration performance of the MgO-CaO series refractory material is remarkably improved. The method changes the used magnesia carbon bricks into valuable and has the advantages of low production cost without a large number of treatment processes, sufficient reaction and high utilizationrate.
Description
Technical field
The present invention relates to utilize again with refractory; Be specifically related to a kind of method for preparing hydration-resisting refractory MgO-CaO material series with the back magnesia carbon brick of utilizing; This method produces Mg steam with MgO in the magnesia carbon brick of back and C heating carbothermic reduction reaction to take place; The vapour deposition of Mg steam re-oxidation generates the MgO film, the CaO on parcel MgO-CaO series refractory material surface, and the MgO-CaO series refractory material that makes has good hydration resistance.
Background technology
Because China's ferrous metallurgy, cement; Developing rapidly of industry such as pottery produces a large amount of refractories of using every year, wherein has only a very little part to be used by secondary or the degradation use; Do not produce high added value; The overwhelming majority is buried as solid waste, and this is contaminate environment not only, and the more important thing is and wasted the resource that can utilize again.Wherein occupy certain proportion with the back magnesia carbon brick, and utilization ratio is not high again with the back magnesia carbon brick, general using all is that degradation uses.
At present; Mainly contain following aspect with back the magnesia carbon brick research and the application that utilize: Chinese patent 200510018029.3 discloses and a kind of waste magnesia carbon brick has been obtained regeneration feed after carbon removal treatment again; This material can be respectively applied in the molded article and indefinite form goods of refractory materials; But because graphite itself also is a kind of fine Nonrenewable resources, carbon removal treatment certainly will cause the waste of graphite resource; Chinese patent 200810140933.5 utilization is used with the back magnesia carbon brick and is raw material, after processing such as selection, slagging-off, fragmentation, deironing, homogenizing and aquation, processes regenerative magnesia-carbon brick, but this complex process, and have shortcoming such as quality instability; Chinese patent 200610012954.X utilizes with the back magnesia carbon brick and prepares magnesium A Long, has shortcomings such as complex process, unstable product quality equally.In a word, still do not have good use, cause a large amount of environmental pollutions and the wasting of resources with the back magnesia carbon brick.
In addition, the MgO-CaO series refractory material has the physics and the chemical property of many excellences: 1. refractoriness is high; 2. high-temperature thermodynamics stable in properties; 3. good thermal shock stability; 4. slag resistance is good; 5. cleaning molten steel prevents nozzle clogging; 6. the raw material reserves are abundant, and product is pollution-free.Can be applied to field of iron and steel smelting and cement rotary kiln clinkering zone.But the MgO-CaO series refractory material is not used widely, and its major cause is the wherein easy and water reaction of free CaO, causes the product cracking, makes troubles for the production of MgO-CaO series refractory material, transportation, preservation, use.In order to address this problem, Chinese scholars was done many trials and research work, and existing general survey is following:
(1), makes that CaO generates the compound of anti-aquation or CaO crystal grain is wrapped in the MgO-CaO series refractory material through adding various additives;
(2) MgO-CaO series refractory material surface is coated, it is not contacted with water.
(3) employing packs, and itself and water are completely cut off.
The people of aforesaid method (1) research is more, and main additive comprises: Fe
2O
3, Al
2O
3, SiO
2, ZrO
2, TiO
2With rare earth oxide etc.The major cause that improves hydration resistance is; Additive and MgO-CaO based material react and generate liquid phase or form the sosoloid acceleration of sintering, make CaO, MgO grain growth, become stable big crystal grain; Be wrapped on the surface of CaO after the liquid phase that produces is solidified, form anti-aquation material.But add Fe
2O
3, Al
2O
3, SiO
2Can reduce the high-temperature behavior of MgO-CaO based material, some additive gets into molten steel, and molten steel is polluted.Make free CaO change into compound in addition or all be wrapped and lost its excellent purification of molten steel function.ZrO
2, TiO
2Cost an arm and a leg with the rare earth oxide additive, and have problems such as difficulties in dispersion.Rare earth oxide has certain radioactivity in addition, the harm personnel safety.
Aforesaid method (2) can be divided into the organism coating again and inorganics coats.Organism comprises: hydrophobic oils such as tar, pitch, paraffin and resin etc.But organism exists coating uneven, and the low temperature organism decomposes, shortcomings such as anti-hydration inefficacy.Inorganics coating method mainly contains with phosphoric acid or phosphoric acid salt and coats, and oxalic acid or oxalate coat, CO
2Carbonating processing etc.Phosphoric acid and phosphoric acid salt coat and make MgO-CaO based material surface C aO generate calcium phosphate compound, improve its hydration resistance, but phosphorus can pollute to molten steel, and coating layer come off easily in construction process, and hydration resistance lost efficacy.CO
2Carbonating is handled and is made MgO-CaO based material surface C aO generate CaCO
3, improve its hydration resistance, but adopt CO separately
2Handle, react slower, poor effect.Chinese patent 01128336.X utilizes CO
2CaCO with water vapour mixed gas and the anti-aquation of MgO-CaO based material surface C aO reaction generation
3Film, sneaking into water vapour can accelerated reaction, but because water vapour makes the CaO aquation more easily, causes cracking easily, wayward, also exist in addition coat uneven, shortcoming such as inefficacy easily.Chinese patent 02138990.X soaks drying with calcium magnesia sand in oxalic acid solution after, at CO
2Thermal treatment is processed under the gas shield, owing to form one deck fine and close caoxalate and lime carbonate composite package on MgO-CaO grog surface, hydration resistance is greatly enhanced; But owing to soak at oxalic acid solution; The MgO-CaO grog is contacted with water, cause cracking easily, wayward; And this method is through twice processing, complex process.
Though it is more that method (3) is used at present, fundamentally do not solve the MgO-CaO based material and be prone to the aquation problem, pack once revealing or opening bag, will lose anti-hydratability.
In a word, the hydration resistance problem of MgO-CaO series refractory material does not well solve, and has limited it and has used widely.
Therefore, how will make full use of with the back magnesia carbon brick, and realize Sustainable development, to one skilled in the art, be the focus of very being concerned about.
Summary of the invention
To above-mentioned background existing defective of technology or deficiency, the objective of the invention is to, a kind of method for preparing hydration-resisting refractory MgO-CaO material series with the back magnesia carbon brick of utilizing is provided.
In order to realize above-mentioned technical assignment, the present invention adopts following technical solution:
A kind of method for preparing hydration-resisting refractory MgO-CaO material series with the back magnesia carbon brick of utilizing is characterized in that, comprises the steps:
Step 1: to classifying with the back magnesia carbon brick, with carbon content greater than 10% be crushed to 0.01mm～5mm with back magnesia carbon brick, directly be positioned over reaction container bottom; Perhaps with carbon content less than 10% after magnesia carbon brick is crushed to 0.01mm～5mm with the back, in crushed particles, add an amount of carbon, carbon content is remained between 10%～20%, mix and be placed on reaction container bottom.
The carbon that wherein adds is carbon black, graphite, coke, coal dust, thin coke granule not capable of using in barren rock electrode ink or the metallurgical process.
Step 2: with the MgO-CaO based material, comprise that CaO content is that 10%～90% MgO-CaO is grog and goods, place the magnesia carbon brick particle top after the fragmentation, and reaction vessel is positioned in the controlled atmosphere generator.
Step 3: to the controlled atmosphere stove evacuation, charge into Ar then, body of heater is heated to 1450 ℃～1650 ℃, arrive in this TR and be incubated, and feed O as shielding gas
2, control O
2Flow; Guarantee that the Mg steam reaction that carbothermic reduction reaction generates is complete, treat that the MgO dense film that vapour deposition generates wraps up MgO-CaO based material surface C aO fully, and thicknesses of layers stops insulation after reaching 1-10 μ m; Soaking time is 1～8 hour, obtains hydration-resisting refractory MgO-CaO material series.
The present invention has obviously improved MgO-CaO series refractory material hydration resistance, also possesses the advantage of the following aspects simultaneously:
(1) will turn waste into wealth with the back magnesia carbon brick, promptly solve, it is fully used with back magnesia carbon brick problem of environmental pollution;
(2) only can use with the back magnesia carbon brick, save a large amount of treatment process through fragmentation, and sufficient reacting, utilization ratio is high;
(3) the MgO film that generates owing to vapour deposition, so compare even compact, MgO-CaO based material hydration resistance improves greatly.MgO film and MgO-CaO based material surface bonding are firm, are not easy to come off;
(4) use the MgO parcel; Do not introduce impurity component; Can not reduce the high-temperature behavior of MgO-CaO based material; Can not pollute molten steel; The MgO high-temperature stable; Anti-hydration can pyrolytic and ineffective, and only wraps up MgO-CaO based material surface, can not influence the excellent specific property of inner free CaO cleaning molten steel;
(5) use with the back magnesia carbon brick, than using magnesia and carbon black as reaction raw materials, cost is lower.
Description of drawings
Fig. 1 is the surface topography picture that makes CaO content 20%MgO-CaO series refractory material.
Fig. 2 is the surface topography picture that makes CaO content 56%MgO-CaO series refractory material.
Below in conjunction with accompanying drawing content of the present invention is done further explain.
Embodiment
The present invention utilizes with the back magnesia carbon brick and prepares hydration-resisting refractory MgO-CaO material series, wraps up one deck hydration resistance MgO dense film relatively preferably on MgO-CaO based material surface.Its know-why is: utilize with MgO and C in the magnesia carbon brick of back, under the Ar protection, carbothermic reduction reaction takes place in heating:
MgO(s)+C(s)＝Mg(g)+CO(g)
Produce Mg steam, Mg steam arrives MgO-CaO based material surface through diffusion, with the O that feeds
2Reaction:
Mg(g)+0.5O
2(g)＝MgO(s)
Vapour deposition generates the MgO dense film, and the CaO on parcel MgO-CaO based material surface improves its hydration resistance.
Follow above-mentioned know-why, the present invention takes following steps:
Step 1: to classifying with the back magnesia carbon brick, with the quality percentage composition of carbon greater than 10% after fragmentation, directly be positioned over reaction container bottom with back magnesia carbon brick; Perhaps with carbonaceous amount percentage composition less than 10% with the back magnesia carbon brick after fragmentation, add a certain amount of carbon again; The quality percentage composition of carbon is advisable between 10%-20%, because the quality percentage composition of carbon hour, MgO is less with the Mg quantity of steam of C reaction generation; It is thinner to generate the MgO film; It is not high that hydration resistance improves effect, but add too much, can increase cost again.The carbon that wherein adds is carbon black, graphite, coke, coal dust, thin coke granule not capable of using in barren rock electrode ink or the metallurgical process.Use the back broken granularity of magnesia carbon brick to be 0.01mm～5mm in this process.
Step 2: with the MgO-CaO based material, comprise that CaO content is that 10%～90% MgO-CaO is grog and goods, place brokenly, and reaction vessel is positioned in the controlled atmosphere generator with magnesia carbon brick particle top, back.
Step 3: to the controlled atmosphere stove evacuation, charge into Ar then, body of heater is heated to 1450 ℃～1650 ℃ as shielding gas; The high more effect of temperature is good more; Because the high more carbothermic reduction reaction that helps more of temperature, the Mg steam degree of supersaturation of generation is big more, and the MgO deposition is fast more; But consider the cost problem, 1600 ℃ more suitable.Be incubated after arriving this temperature, and feed O
2, control O
2Flow; Guarantee that the Mg steam reaction that carbothermic reduction reaction generates is complete, treat that the MgO dense film that vapour deposition generates wraps up MgO-CaO based material surface C aO fully, and thicknesses of layers stops insulation after reaching 1-10 μ m; General insulation 1～8 hour can obtain hydration-resisting refractory MgO-CaO material series.
Below be the optimum embodiment that the contriver provides, the invention is not restricted to these embodiment, magnesia carbon brick is prepared the excellent MgO-CaO series refractory material of qualified hydration resistance through experiment showed, of applicant all can be utilized usefulness in the scope that the present invention provides after.
Embodiment 1:
The back magnesia carbon brick of using of carbon content 11% is broken into the particle of particle diameter 0.01mm～5mm; Put into reaction container bottom; CaO content is respectively 20%, 56% and 90%, and granularity to be that the MgO-CaO based material of 2～4mm places respectively broken with magnesia carbon brick particle top, back.Reaction vessel is put into controlled atmosphere generator, fill the Ar protection after vacuumizing, insulation when being heated to 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃ respectively, and begin to feed O
2, O
2Flow velocity is 250l/h, and is incubated 4 hours, obtains the MgO-CaO series refractory material of anti-aquation.
The experiment of anti-aquation: respectively get the beaker that 50g puts into 100ml to the MgO-CaO based material of the particle diameter 2～4mm that handled and undressed MgO-CaO based material, and cover upper surface ware in the above; Put into pressure cooker, under pressure 0.15MPa condition, be incubated 2 hours; Take out sample; Make it 115 ℃ of dryings 20 hours, remove the particle of dried＜1.00mm again with the empty sieve sieve in the side of 1.00mm, represent its hydration resistance with quality increment rate and Pulverization ratio.
Quality increment rate=[(W
2-W
1)/W
1] * 100%
Pulverization ratio=[(W
1-W
3)/W
1] * 100%
In the formula: W
1Granular mass for the preceding 2～4mm of aquation experiment; W
2Be the quality after the aquation; W
3For after the aquation experiment, sieve goes＜the dried quality of larger particles behind the particle of 1.00mm.Experimental result is seen table 1.
The anti-aquation data of MgO-CaO based material after table 1 treatment of different temperature
Embodiment 2:
The back magnesia carbon brick of using of carbon content 11% is broken into the particle of particle diameter 0.01～5mm, puts into reaction container bottom, CaO content is respectively 20%, 56% and 90%, granularity is that the MgO-CaO based material of 2～4mm places broken using above the magnesia carbon brick particle of back respectively.Reaction vessel is put into controlled atmosphere generator, fill the Ar protection after vacuumizing, when being heated to 1600 ℃, begin insulation, and feed O
2, O
2Flow velocity is 250l/h, and be incubated 2 hours respectively, 4 hours, 6 hours, 8 hours.Anti-aquation data are seen table 2.
Table 2: the anti-aquation data of MgO-CaO based material after different soaking times are handled
Embodiment 3:
The back magnesia carbon brick of using of carbon content 5%, 10% is broken into the particle of particle diameter 0.01mm～5mm respectively, in the magnesia carbon brick particle of fragmentation, adds a certain amount of graphite respectively then and mix, making the carbon content in this mixture is 15%, puts into reaction container bottom.
With carbon content be respectively 15% and 20% with the back magnesia carbon brick, be broken into the particle of particle diameter 0.01mm～5mm respectively, directly put into reaction container bottom.
CaO content is respectively 20%, 56% and 90%; And granularity is that the MgO-CaO based material of 2mm～4mm places broken magnesia carbon brick particle top respectively; Reaction vessel is put into controlled atmosphere generator, fill the Ar protection after vacuumizing, when being heated to 1600 ℃, begin to feed O
2, O
2Flow velocity is 250l/h, and is incubated 4 hours respectively, obtains the MgO-CaO series refractory material of anti-aquation, and its anti-aquation data are seen table 3.
The anti-aquation data of table 3:MgO-CaO based material
In the foregoing description, the CaO content that makes is that 20% MgO-CaO series refractory material and CaO content are that the surface topography picture of 56% MgO-CaO series refractory material is referring to Fig. 1 and Fig. 2.
Claims (2)
1. a utilization uses the back magnesia carbon brick to prepare the method for anti-hydration MgO-CaO series refractory material, it is characterized in that, comprises the steps:
Step 1: to classifying with the back magnesia carbon brick, with carbon content greater than 10% be crushed to 0.01mm～5mm with back magnesia carbon brick, directly be positioned over reaction container bottom; Perhaps with carbon content less than 10% after magnesia carbon brick is crushed to 0.01mm～5mm with the back, in crushed particles, add an amount of carbon, carbon content is remained between 10%～20%, mix and be placed on reaction container bottom;
Step 2: with CaO content is that MgO-CaO of 10%～90% is grog and goods, places the magnesia carbon brick particle top after the fragmentation, and reaction vessel is positioned in the controlled atmosphere generator;
Step 3: to the controlled atmosphere stove evacuation, charge into Ar then, body of heater is heated to 1450 ℃～1650 ℃, arrive in this TR and be incubated, and feed O as shielding gas
2, control O
2Flow; Guarantee that the Mg steam reaction that carbothermic reduction reaction generates is complete, treat that the MgO dense film that vapour deposition generates wraps up MgO-CaO based material surface C aO fully, and thicknesses of layers stops insulation after reaching 1-10 μ m; Soaking time is 1～8 hour, obtains anti-hydration MgO-CaO series refractory material.
, the method for claim 1, it is characterized in that the carbon of described adding is carbon black, graphite, coke, coal dust, thin coke granule not capable of using in barren rock electrode ink or the metallurgical process.
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| CN103553690B (en) * | 2013-11-13 | 2014-11-26 | 武汉钢铁(集团)公司 | Heat treatment method after magnesia carbon brick recovery |
| CN105908255B (en) * | 2016-03-24 | 2018-03-16 | 西安建筑科技大学 | A kind of method that magnesia crystal whisker is prepared using waste magnesia carbon bricks |
| CN108866634B (en) * | 2018-07-27 | 2019-11-05 | 辽宁科技大学 | A method of magnesia crystal whisker is prepared using waste magnesia carbon brick substrate material as raw material |
| PL3772500T3 (en) * | 2019-08-05 | 2022-12-27 | Refractory Intellectual Property Gmbh & Co. Kg | Method for treating magnesia carbon products |
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