CN1308261C - Self flow type pumping wet spray high aluminum refractory material for steel ladle permanent lining - Google Patents
Self flow type pumping wet spray high aluminum refractory material for steel ladle permanent lining Download PDFInfo
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- CN1308261C CN1308261C CNB2004100256368A CN200410025636A CN1308261C CN 1308261 C CN1308261 C CN 1308261C CN B2004100256368 A CNB2004100256368 A CN B2004100256368A CN 200410025636 A CN200410025636 A CN 200410025636A CN 1308261 C CN1308261 C CN 1308261C
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Abstract
The present invention relates to a self flow type pumping wet method spray high alumina fireproofing material for ladle permanent linings. The fireproofing material is prepared from the components by the following weight percentage: 68 to 83% of high alumina bauxite, 10 to 18% of high alumina micro powder, 1 to 7 wt% of cyanite powder, 1 to 4% of silicon oxide superfine powder, 4 to 6% of calcium aluminate cement and 0.3 to 0.6% of additional high efficiency water reducing agent, wherein the mesoposition diameter D50 of the high alumina micro powder is less than 4 micrometers, and the mesoposition diameter D50 of the silicon oxide superfine powder is less than 1 micrometer. Through the optimization of the distribution characteristics and the combination of the fireproofing micro powder and the superfine powder of the base material fine powder materials, the fireproofing material of the present invention is prepared into a self flow type pumping spray fireproofing material with low water content, and the fireproofing performance of an integrated low cement material with high strength of the fireproofing material of the present invention is ensured. The fireproofing material of the present invention has favorable flow performance. The two kinds of micro powder have high fireproofing performance and low cost, the two kinds of micro powder are used as the micro powder components of the high alumina fireproofing materials for ladle permanent linings, and the two kinds of micro powder both have rationality of integrated technical and economic significance.
Description
Technical field
The present invention relates to ladle lining
Background technology
Refractory materials wet spray technology is one of great technical progress that occurs in recent years in the fire resisting material field in the world.The wet spray technology both can be applicable to the lining of building of various metallurgical furnace linings, and the repairing that also can be applicable to old furnace lining is safeguarded.This method will be mixed and stirred the blended refractory materials by certain water yield and will be pumped into nozzle, use pressurized air at the nozzle rear portion, make it to condense fast and be injected on the construction surface after being added to setting accelerator in the compound, form refractorily lined lining body or repair layer.This technology need not any mould just can form the refractory masses that needs thickness; Sprayed coating density is near the castable layer; Construction drops into that manpower is few, the engineering time short (be about integrated poured duration half), also can form the integrated permanent layer of uniform thickness to the long-time ladle construction of using back box hat distortion.This technology is promoted rapidly in developed countries such as America and Europe, Japan after occurring, and the middle steel in China Taiwan also begins to adopt the wet spray technology to carry out building lining and repairing maintenance of ladle.
The permanent ladle layer refractory materials need have guarantees fire performance safe in utilization, also need have higher middle low temperature intensity to obtain higher work-ing life.Low cement bonded high alumina refractory casting material can obtain good result of use by casting, builds lining but be applied to wet shotcrete technology technology, and its workability can not satisfy the ladle permanent lining wet spray and build the needs of lining to refractory materials.Each all laid particular emphasis on from method and narrated wet spraying about patent and document in the past, and related argumentation and existing refractory castable technology to refractory materials do not have remarkable difference." being used to generate the pourable refractory assemblies and the wet shotcrete technology method thereof of fine and close pouring fireproof material " that Japanese Patent JP-269399/96 describes, this refractory materials is a non-cement bonded refractory materials, intensity and 1000 ℃ low with interior medium temperature intensity after the oven dry of this type of refractory materials, discomfort is preferably the ladle permanent lining monolithic refractory.For this reason, according to pumping wet spray processing requirement, build lining at the ladle permanent lining wet spray and develop with high alumina refractory.
Summary of the invention
The object of the present invention is to provide a kind of pump delivery wet spray permanent ladle layer high alumina refractory, but require material have low pumping construction time of the moisture of mixing and stirring long, rely on deadweight and the potential energy difference airtight side by side realification that can flow voluntarily.This material can be blast injection firm attachment and keep shape to the construction surface after being pumped to spout and setting accelerator mixes, realize that ladle permanent lining does not have the mould construction.Ladle permanent lining behind the spraying application needs sclerosis within a short period of time, in use properties with on the life-span, reaches the effect of former vibrating casting moulding permanent ladle layer high alumina castable.
Generally speaking, but slip pumping and after injection is adhered to, can keep needing the unshape refractory of shape all to can be used for wet spray.Technology in the past is to the narration of wet spray technology with refractory materials, with present existing refractory castable technology type seemingly, not from wet spray arts demand and construction physique amount in conjunction with last setting wet spray refractory technology, but the pumping spraying application time was short after big, the slip of the pumping resistance of material mixed and stirred in the practice, easily cause line clogging that spraying application is interrupted, and the tamper of refractory materials recovers construction in the eliminating transport pipe, is very difficult in practice.Desire to guarantee the wet spray construction smoothly and obtain can be used for the high quality sprayable refractory furnace lining or the repair layer of smelting equipment, but adopt mix and stir the low pumping construction time of moisture long, the self-flow pattern pumping refractory materials of airtight realification is optimal selection to rely on deadweight and potential energy difference can flow side by side.
Weigh with rheol fluid type, the often more general simple rheological model of the flowing property of unshape refractory slip seems more complicated, both embodied the elastomerics of obeying hooke theorem to a certain extent, show the viscous body behavior of complying with Newton's law again, most vibration construction mould material all also shows thixotropic property, slurry takes place to flow after promptly being applied to stress on the slurry and reaching certain value, and the apparent viscosity of slurry reduces with the shearing rate increase in flowing, and is referred to as plastic flow.Change the size-grade distribution state of kind, fine powder and micro mist of kind, the micro mist of wedding agent in the refractory materials batching, perhaps change the kind and the add-on of dispersion agent, all will change the flow characteristics of unshape refractory slurry.Fig. 1 has represented the types of flow of the fluid materials that some are basic.
From wet spray technology and equipment basic demand angle to wet spray refractory materials rheological property, belong to glue-mould-the easy thixotroping refractory materials slip of elasticity slurry and belonging to glues-the no thixotroping refractory materials slip of plasticity slurry has the gravity flow performance, the easy pumping of such slurry, not plugging road and construction physique amount height can be elected to be wet spray self-flow pattern pumping refractory materials slurry rheology attribute type.
Because the rheological characteristics of wet spray refractory materials is mainly by the rheological the subject of knowledge and the object of knowledge decision of its fine powder matrix, the flowing of the mobile drive particulate material of matrix, the matrix slip reduces the rheological resistance in the particulate material rheology at the parcel on particulate material surface.Therefore, the rheological property of wet spray material depends on the setting and the optimization of matrix fine powder system rheological performance.The present invention changes conventional art and only carries out control of grade grating and ratio optimization, do not consider the traditional mode of size-grade distribution matching relationship between micro mist and super-fine powder from general particle and fine powder meaning, think and effectively disperseing under the prerequisite, the rheological characteristics that accumulation relation that spheric micro mist and super-fine powder particle are mutual and slip will determine slip.Thus, in the design that wet spray matrix of materials fine powder constitutes, the bimodal distribution high alumina micro mist (meso-position radius Dso≤4u that has selected for use ball milling to produce, two distribution of peaks Da=1.593, Db=10.1u) and commercially available iron alloy produce control of dust product silicon oxide super-fine powder (meso-position radius Dso≤1u, distribution main peak D=0.297) micro mist unitized construction, the sphericity of two kinds of micro mist particulate form is all higher, the relativeness of its distribution peak value particle diameter and meso-position radius cooperates the reasonable accumulation that has formed micro mist in spray material matrix, adjacent distributions peak value particle diameter ratio is 6.34 (Db/Da) and 5.36 (Da/D) between micro mist and super-fine powder, all greater than 4, to the particle packing calking obtain the matrix structure of compact high-strength and ball-shaped micro powder between particle and self " rolling " each other, " lubricating ", it is very favourable to reduce the slip rheological resistance.And for the wet spray refractory materials of hi-tech, the fire performance of two kinds of micro mists is higher, and price is lower, and its size-grade distribution is seen Fig. 2 a, 2b.
On the basis of above-mentioned micro mist combination basic ideas, can be optimized test to the fine particle of wet spray material and the slurry rheology of matrix fine powder constitution system, each sample refractory material gross weight of test is 110 grams, with particle diameter in the conventional wet spray material is that the following weight of material proportioning of 1mm can be set at 55% proportioning value and becomes simple multiple relation, can test proportion design such as table 1 about the slurry rheology of fine particle in the wet spray material and matrix fine powder constitution system:
Table 1
Test operation is: add 12 ml waters in the beaker that fills sample 111 grams (refractory material 110 grams, high efficiency water reducing agent 1 gram), after stirring slip concentrated and be poured on the sheet glass, slip is from flowing to this stable slip mud pie attitude of shape bases after 3 minutes, mensuration is by the mean value that the minimum and maximum diameter of mud cake on average draws, be defined as slip from degree of mobilization.Each sample changes the test determination result of slip from the degree of mobilization influence because of micro mist amount and ratio in the table 1, and is as shown in table 2:
Table 2
| Test piece number (Test pc No.) | The high alumina micro mist | The silicon oxide super-fine powder | Two micro mists ratio | From degree of |
| 0# | 20 | 0 | ∞ | 107 |
| 1# | 18.5 | 2 | 9.25∶1 | 121 |
| 2# | 17.5 | 2 | 8.75∶1 | 131 |
| 3# | 15 | 2 | 7.5∶1 | 146 |
| 4# | 12.5 | 2 | 6.25∶1 | 136 |
| 5# | 10 | 2 | 5∶1 | 128 |
| 6# | 10 | 4 | 2.5∶1 | 115 |
| 7# | 10 | 6 | 5∶3 | 102 |
Test-results mapping expression with table 2, referring to Fig. 3 a, Fig. 3 b, all there are favored area in high alumina micro mist proportional quantity and the two micro mist amount ratios that can find bimodal distribution intuitively, high alumina micro mist proportional quantity is that 10～18 scopes, two micro mist amount ratios are 5～8.75, slip from yield point value all more than 125mm, the corresponding gravity flow pump-conveying property of allocating the wet spray material behind the coarse particles into is good.Depart from this favored area, be unfavorable for spraying the gravity flow performance of slip, in the practice of construction operation, will increase pumping resistance and cause slip to stop up.In addition, by the General Principle of unsetting anti-material as can be known, make material obtain high workability can the matrix fine powder constitute, also be that material realizes that the matrix fine powder of premium propertiess such as low moisture and compact high-strength constitutes.Therefore, the determining of above-mentioned micro mist and combination thereof, to premium propertiess such as stable self-flow pattern pump-conveying property of wet spray ladle permanent lining refractory materials and compact high-strengths, very important.
According to above-mentioned analysis of experiments result, the wet spray refractory technology is to make material obtain to be suitable for the premium properties of wet spray technology, to the fine powder matrix design of material particle size distribution characteristic be the micro mist combination of certain matching relationship.Adopted a kind of size-grade distribution to be the meso-position radius D of bimodal distribution
50Less than 4 microns high alumina micro mists and a kind of meso-position radius D
50Silicon oxide super-fine powder less than 1 micron.The particle diameter of two distribution of peaks of this high alumina micro mist size-grade distribution when the distribution main peak particle diameter ratio of this two distribution of peaks and silicon oxide super-fine powder size-grade distribution all greater than 4.The add-on of high alumina micro mist in the wet spray refractory materials is 10～18%, and the gravity flow pump-conveying property that is lower than 10% o'clock spray material does not reach processing requirement, easily because of the self drainage fast blocking pipe that descends; Surpass at 18% o'clock, the construction moisture of spray material will obviously rise, and will be unfavorable to the intensity and the high volume stability of spray material.The add-on of silicon oxide super-fine powder is 1～4%, and the gravity flow pump-conveying property that is lower than 1% o'clock spray material does not reach processing requirement; Surpass at 4% o'clock, the construction moisture of spray material will obviously rise, and will be unfavorable to the fire performance and the high volume stability of spray material.
Technical solution of the present invention is:
A kind of ladle permanent lining self-flow pattern pumping wet spray high alumina refractory, its composition weight percent is:
Alumine 68～83%,
High alumina micro mist 10～18%,
Silicon oxide super-fine powder 1～4%,
Aluminous cement 4～6%,
High efficiency water reducing agent adds 0.3～0.6%;
Wherein, the size-grade distribution of high alumina micro mist is bimodal distribution, meso-position radius D
50Less than 4 microns, the meso-position radius D of silicon oxide super-fine powder
50Less than 1 micron; The particle diameter of two distribution of peaks of high alumina micro mist size-grade distribution when the main peak particle diameter ratio of these two distribution of peaks and silicon oxide super-fine powder size-grade distribution all greater than 4.
Further, spraying high alumina refractory of the present invention also comprises aquamaine stone flour 1～7wt%, under the higher temperatures certain expansion is arranged all in using with maintenance, and can adjust its add-on to the requirement that the permanent liner high volume changes according to different ladles.
Preferred 14～the 16wt% of high alumina powder content, the silicon oxide super-fine powder is preferably 1.5～2.5wt%.
High efficiency water reducing agent is sodium polyacrylate, sulfonated melamine compound resin (trade(brand)name SM), B-naphthene sulfonic acid formal (trade(brand)name FDN) and coumarone one indene resin sodium sulfonate (trade(brand)name CRS).
Beneficial effect of the present invention
The present invention had both guaranteed the fire performance of the low cement integral material of its high strength, made it to have good rheological property again.Key is by fire-resistant class micro mist, super-fine powder distribution characteristics and its Combination Optimized in the matrix fine materials, and making becomes low moisture self-flow pattern pumping sprayable refractory.The fire performance of other technologies such as high alumina refractory, low cement combination technology, micro mist and super-fine powder help combination technology and the short technology of coagulating, and all directly adopt existing low cement in conjunction with high alumina castable and wet spray refractory technology.
The micro mist structure that adopts the higher and ceramic super-fine powder that is bimodal distribution of particulate form sphericity and spheric amorphous silicon oxide super-fine powder to make up, the accumulation calking relation of micro mist in the spray material matrix is optimized, in the finely disseminated fine powder between particulate rheological resistance little, ball-shaped micro powder " lubricates " between the coarse grain particles of aggregates, makes spray material gravity flow pump-conveying property good.The ceramic super-fine powder of bimodal distribution is compared with powder materials such as commonly used alumina powder, clays, and producing control of dust with commercially available iron alloy, to get silicon oxide super-fine powder conformability better.In addition, the fire performance of two kinds of micro mists is higher, and price is lower, is combined on the comprehensive meaning of Technological Economy as the micro mist of permanent liner high alumina refractories all to have reasonableness.
Description of drawings
Fig. 1 is several typical rheology type synoptic diagram;
Fig. 2 a is the high alumina micro mist size-grade distribution synoptic diagram that main peak is bimodal peak cloth;
Fig. 2 b is the size-grade distribution synoptic diagram of silicon oxide super-fine powder;
Fig. 3 a is that two micro mist amount ratios are to the influence synoptic diagram of slip from degree of mobilization;
Fig. 3 b is that high alumina micro mist proportional quantity is to the influence synoptic diagram of slip from degree of mobilization;
Fig. 4 is the wet spray refractory materials from degree of mobilization value extinction curve synoptic diagram in time.
Embodiment
Embodiment sees Table 3.
Table 3
| Furnish component (wt%) | Embodiment | Comparative example | ||||
| 1 | 2 | 3 | 4 | 1 | ||
| Alumine | 8～5mm | 12 | 12 | 12 | 12 | 12 |
| 5～3mm | 13 | 13 | 13 | 13 | 12 | |
| 3～1mm | 20 | 20 | 20 | 20 | 20 | |
| 1～0.1 | 18 | 18 | 18 | 18 | 18 | |
| -0.088mm | 6 | 16 | 12 | 12 | 8 | |
| Kyanite | -0.1mm | 7 | 1 | 3 | 6 | 7 |
| Alumina powder | D
50≤2.5 | 15 | ||||
| The high alumina micro mist | D 50≤4μ | 18 | 14.5 | 15 | 11 | |
| The silicon oxide super-fine powder | D 50≤1μ | 1 | 1.5 | 2 | 3 | 2 |
| Aluminous cement | Secar71 | 5 | 4 | 5 | 5 | 5 |
| Sodium hexametaphosphate 99 | Add | 0.15 | ||||
| The naphthene sulfonic acid formal subtracts | Add | 0.5 | 0.5 | 0.5 | 0.5 | |
| Moisture % is mixed and stirred in construction | Add | 6 | 6 | 6 | 6 | 6.5 |
| From degree of mobilization value, mm | | 160 | 170 | 177 | 174 | 175 |
| 20min | 157 | 167 | 175 | 162 | 130 | |
| The gravity flow pump-conveying property | 20min | Better | Good | Good | Better | Difference |
| Volume density, g/ | 110℃×24h | 2.80 | 2.81 | 2.81 | 2.83 | 2.90 |
| Folding strength, | 110℃×24h | 9.5 | 8.5 | 11.0 | 12.1 | 10.2 |
| 1500℃×3h | 12.3 | 12.0 | 13.0 | 14.2 | 15.6 | |
| Burn back line velocity of variation, % | 1500℃×3h | +0.7 | -0.1 | +0.3 | +0.6 | -0.1 |
Table 3 illustrated embodiment all has the pumping construction performance that obviously is better than prior art thinking its preparing materials, and has the required good physicals suitable with other materials of the anti-material of ladle permanent lining, and these materials were all implemented in pilot scale and commerical test.Be good with embodiment 2,3 especially wherein, its 20min does not have obvious decline from degree of mobilization value and pump-conveying property, can guarantee that wet spray builds lining construction direct motion.
Material and the material that adopts conventional alumina powder to technical solution of the present invention carry out performance measurement and wet spray pilot scale simulation comparison test.Referring to Fig. 4, it shows the extinction curve from the degree of mobilization value of two kinds of materials.From test-results, the material that adopts conventional alumina powder and silicon oxide super-fine powder to cooperate by the prior art thinking has bloated property flow state to a certain degree, although also can obtain lower moisture and the high flowing property of mixing and stirring at the slip initial stage of making, but descend fast along with the prolongation of time from the degree of mobilization value, 20 minutes from yield point value by 175mm, drop to 130mm, the pipe-line transportation that realizes longer distance by pumping is very difficult, and this slurry is relatively poor to the particulate load, particle easily produces sedimentation in the gravity flow process, line clogging has taken place in pumping, can not satisfy the workability requirement of wet spray to self-flow pattern pumping spray material.And the wet spray material embodiment of employing micro mist assembled scheme of the present invention did not have obvious decline from yield point value in 2,3,20 minutes, and slurry does not have tangible particles settling phenomenon.Fig. 4 shows the extinction curve from the degree of mobilization value of two kinds of materials.
Ladle permanent lining wet spray refractory materials of the present invention has been carried out the on-the-spot industrialness use-testing of secondary, the integral spray that 150 tons electric furnace ladle and 300 tons of converter ladles are carried out permanent liner is built the lining test respectively, secondary has all successfully been realized spraying and has been built lining, the whole ladle permanent lining even compact that spraying obtains, lining physique amount is better than former loose tool vibrating casting construction.When use to 423 stove and 485 stoves, to whole ladle permanent lining strip inspection, lining body situation meets the requirements fully, because its wet spray is built the inhomogeneous factor of body inside that causes constructing such as particles settling can not take place in the lining process, be better than the former loose tool vibrating casting permanent liner of constructing with the globality of back furnace lining.
Ladle permanent lining self-flow pattern pumping wet spray high alumina refractory of the present invention is in manufacturing processed, and the alumine raw material is refractory castable technology or the related wet spray material of document technology routinely, allocates into the form of certain size particles and fine powder combination.Cement and admixture technology are also all with reference to the low-cement refractory pouring material technical thought.
What the present invention designed and developed is combined as the ladle permanent lining wet spray refractory materials of feature with bimodal distribution high alumina micro mist and silicon oxide super-fine powder, pump-conveying property is good, construction operation is smooth and easy, be easy to large-scale ladle permanent lining or other large scale industry stove furnace linings enforcement wet spray are built lining, it is good that the ladle permanent lining quality that lining obtains is built in spraying, and the type approval test proof can obtain and pour into a mould lining identical or better work-ing life.This material can directly be built in the lining at all kinds of ladle permanent lining wet sprays and be applicable, also can build and adopt in the lining at equipment container permanent liner wet sprays such as hot metal ladle, tundish, working temperatures such as process furnace, soaking pit are no more than thermal technology's stove of 1500 ℃, and the wet spray that can be directly used in working lining is built lining.Because wet spray is built the advance and the anti-material of the low high sprayed aluminum of cement of high strength of lining technology and used the general suitability that has, the present invention builds in the lining at the stove of the similar performance requirement of all kinds of steel mills and all can promote the use of.
Claims (4)
1. ladle permanent lining self-flow pattern pumping wet spray high alumina refractory, its composition weight percent is:
Alumine 68～83%,
High alumina micro mist 10～18%,
Silicon oxide super-fine powder 1～4%,
Aluminous cement 4～6%,
High efficiency water reducing agent adds 0.3～0.6%;
Wherein, the size-grade distribution of high alumina micro mist is bimodal distribution, meso-position radius D
50Less than 4 microns, the meso-position radius D of silicon oxide super-fine powder
50Less than 1 micron; In the high alumina micro mist particle size distribution figure two distribution of peaks in the ratio of corresponding particle diameter and this two distribution of peaks and the silicon oxide super-fine powder particle size distribution figure main peak the ratio of corresponding particle diameter all greater than 4.
2. ladle permanent lining self-flow pattern pumping wet spray high alumina refractory as claimed in claim 1 is characterized in that, also comprises aquamaine stone flour 1～7wt%.
3. ladle permanent lining self-flow pattern pumping wet spray high alumina refractory as claimed in claim 1 is characterized in that the high alumina powder content is 14～16wt%, and silicon oxide super-fine powder content is 1.5～2.5wt%.
4. ladle permanent lining self-flow pattern pumping wet spray high alumina refractory as claimed in claim 1, it is characterized in that described high efficiency water reducing agent is any one in sodium polyacrylate, sulfonated melamine compound resin, beta-naphthalenesulfonic-acid formal or the coumarone-indene resin sodium sulfonate.
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| CN100427563C (en) * | 2006-06-27 | 2008-10-22 | 武汉理工大学 | Preparation method of high temperature heat storage material |
| CN100482612C (en) * | 2006-08-30 | 2009-04-29 | 宝山钢铁股份有限公司 | Fire resistive material for coke oven door |
| CN102161212B (en) * | 2011-01-18 | 2013-06-05 | 北京利尔高温材料股份有限公司 | Method for manufacturing low-cost slag blocking dam |
| CN104193232B (en) * | 2014-07-24 | 2016-05-25 | 杨培强 | A kind of high-thermal conductivity mixed solidifying soil and preparation method thereof |
| CN108117401B (en) * | 2017-12-26 | 2020-09-29 | 河南欣昌耐材股份有限公司 | Quick-drying self-flow castable for permanent layer of ladle |
| CN108083825B (en) * | 2017-12-26 | 2020-09-29 | 河南欣昌耐材股份有限公司 | Quick-drying self-flowing castable for permanent layer of regenerated ladle |
| CN109053167B (en) * | 2018-09-05 | 2019-06-25 | 北京东峰兴达耐火材料有限公司 | Vacuum boiler burner hearth gravity flow pouring material |
| CN113307642A (en) * | 2021-06-24 | 2021-08-27 | 山东同得利集团有限公司 | Wet spraying refractory material |
| CN114105616B (en) * | 2021-11-30 | 2023-11-14 | 中钢集团洛阳耐火材料研究院有限公司 | Rocket launching platform low-loss protective material |
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| 不定形耐火材料的制备技术与应用技术走向 李再耕，洛阳工业高等专科学校学报，第12卷第2006.1.2期 2002 * |
| 不定形耐火材料的制备技术与应用技术走向 李再耕，洛阳工业高等专科学校学报，第12卷第2006.1.2期 2002;微粉对矾土基超低水泥浇注料性能的影响 刘新红，耐火材料，第1卷第38期 2004 * |
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