CN103360088B - A kind of copper smelting-furnace rare oxygen combustor nozzle brick and making method - Google Patents

Abstract

The present invention relates to a kind of copper smelting-furnace rare oxygen combustor nozzle brick and making method, it is characterized in that the percent mass of described burner block consists of: electric smelting height chromium corundum 20-60%, high-purity plate diamond spar or fused white corundum 20-60%, Cr ₂o ₃micro mist 5-20%, SiO ₂micro mist 1-10%, corundum powder 1-10%, Al ₂o ₃micro mist 1-10%, zirconium mullite 1-10%, aluminium Silica hydrogel 3-6%, additional high efficiency water reducing agent 0.1-0.16%.Making method comprises mould material preparation, cast, maintenance, drying and burns till.The invention provides burner block work-ing life more than six months, even up to more than 9 months, meet the service requirements of rare oxygen burner.

Description

A kind of copper smelting-furnace rare oxygen combustor nozzle brick and making method

Technical field

The present invention relates to composition and the making method of the rare oxygen burner burner block of a kind of copper smelting-furnace.Belong to fire resisting material field

Background technology

Oxygen is as gas requisite in Copper making technique, be widely used in various melting, blowing and refinery practice, the effect of oxygen is intensified smelting and converting process, reduce fuel consumption in combustion processes, reduce the discharge of flue dust and pollutent, but traditional full-oxygen combustion exists temperature non, the oxygen under high temperature-combustion flame exerts an adverse impact to heating process and fire resisting material of furnace body, seriously can reduce lining life.In recent years, for reducing the peak temperature of oxygen-combustion flame, burner company of the U.S. develops rare oxygen combustion technology, be characterized in that high speed oxygen and fuel jet are before mixed firing, to a large amount of burner hearth flue gases be entrainmented, and greatly reduce combustion flame temperature, make burning more even, and this rare oxygen combustion technology is successfully applied to anode furnace refining, the unusual effect of saving of fuel 45-55%, smoke discharge amount reduction by 70% can be realized.Although rare oxygen burner has obvious effects of energy saving and emission reduction, but compared with common air-fuel, its flame temperature is high, and the copper ashes entrainmented up, the agent of erosion of copper liquid to burner burner block are large, therefore the work-ing life of burner block is significantly reduced, the work-ing life of the burner block of general high-quality corundum mullite rock is only about one month, burner block badly damaged and change frequently and become the maximum bottleneck promoting rare oxygen combustion technology.

For many years, the corundum-mullite material that copper smelting-furnace burner block used adopts low cement to combine always, although this burner block has good heat to shake stability and high-temperature behavior, but the aggressiveness of its resistance to copper ashes is poor, though in traditional copper smelting-furnace available about 6 months, being used as rare its life-span of oxygen burner, to only have one month even lower.

China Patent Publication No. CN97112850.2 provides one " new and compound burning-free nozzle brick for coke oven and manufacture method ", its AL ₂o ₃, ZrO ₂, SiO ₂content be respectively 50-75%, 60-90%, 55-75%, although this burner block also has good heat to shake stability, be obviously not all right from the erosion of the visible anti-copper ashes of composition.China Patent Publication No. CN200710158734.2 provides a kind of thermal shock resistant burner brick and preparation method thereof, its feed composition is: aluminium powder 24% ~ 30%, alumine aggregate and alumina fine powder 14% ~ 31%, chromium oxide powder 45% ~ 56%, additional Sodium Fluoride powder 1% ~ 2% and be the binding agent of 10G: 0.6 ~ 1.4ML with material rate.Though this material has good thermal shock resistance, intensity only has 25-35Mpa, and volume density is only at 1.8-2.38g/cm ³, obvious its is kept out incessantly the erosion of the rare like this slag of copper ashes, and separately it adopts burner block shaping of mechanical pressing to this shape of rare oxygen burner block and complexity thereof to be also impracticable.

The present invention attempts by the composition analysis of copper ashes and copper metallurgy melt and SiO2 the erosion of refractory materials, penetration study, and in conjunction with phasor, wish by adopting high chromium corundum and being main raw material with high-purity corundum, the mould material providing a kind of high-purity chromium corundum non-cement to combine pours into a mould the rare oxygen burner block of preparation, anti-copper ashes corrodes, anti-sweep of gases and excellent heat shake stability to make it have concurrently, improves the work-ing life of rare oxygen burner block.

Summary of the invention

The anti-erosion existed with rare oxygen burner block for current copper smelting-furnace and the irreconcilable subject matter of resistance to thermal shock, the object of the present invention is to provide a kind of there is the infiltration of high temperature resistant, high strength, anti-copper ashes, high-quality burner block that strong, the anti-rapid heat cycle of the agent of erosion is taken into account well and making method, to meet in Copper making the service requirements requiring burner.

To achieve the above object of the invention, the technical scheme that the present invention takes is:

1, with electric smelting height chromium corundum for main raw material:

Research shows, the major cause that rare oxygen burner block damages is the infiltration of slag.In the process of copper metallurgy, various fluidity of molten is all very good, in the melt such as slag and matte, sulfide melt because fusing point is low, viscosity is little, at SO ₂though good to refractory materials wettability in atmosphere, infiltration is the darkest, because temperature is low, and may be little to the structure deteriorate of refractory materials.And FeO-SiO ₂be slag be then the major cause causing firebrick structure to peel off.Owing to containing a large amount of sulfide in sulfide ore and matte, in order to deironing, SiO must be added ₂slag making, therefore when melting and blowing, FeO-SiO ₂be that slag is very large.Burner block in use, FeO-SiO ₂melt can infiltrate in brick along its capillary channel such as pore and crackle is logical, and the metamorphic layer formed with original brick structure and different in kind that interacts with it, the structure spalling of burner block is formed when temperature variation.Structure spalling deteriorates gradually unlike dissolving, erosion, but the unexpected flake-off of several millimeters, tens millimeters, obviously, the infiltration of melt is darker, and metamorphic layer is rear thick, and structure spalling harm is also more serious.The degree of depth (X) that melt permeates in refractory materials can be expressed from the next:

$X=\sqrt{\frac{\mathrm{r\σ}\cos \mathrm{\θ}}{\mathrm{\η}}\mathrm{\τ}}$

In formula, σ is the surface energy of melt, and θ is melt contact angle on refractory materials.If wettability is bad, contact angle θ >90 °, cos θ are negative value, and melt just can not infiltrate refractory materials.η is the viscosity of melt, and r is the radius of refractory materials emptying aperture gap, and τ is the time.

As can be seen from the above equation: reduce refractory materials pore radius, increase contact angle, increase the viscosity of melt, reduce the surface energy of melt, the degree of depth that melt infiltrates refractory materials can be reduced.

Cr ₂o ₃the very high eutectic mixture of Solid solution, high melting compound or temperature of fusion can be formed, such as: Cr with a lot of oxide compound ₂o ₃with SiO ₂the temperature of fusion of eutectic mixture can be formed up to 1720 DEG C, Cr ₂o ₃the FeO-Cr that fusing point is 2100 DEG C can be formed with FeO ₂o ₃, Cr ₂o ₃with Cu ₂o can form the compound of fusing point more than 1600 DEG C.In addition, Cr ₂o ₃can also improve the viscosity of slag widely, therefore, slag infiltrates containing Cr ₂o ₃the degree of depth of high refractory materials is general more not containing Cr ₂o ₃refractory materials much shallow.Accordingly, the present invention with high-purity electric smelting chromium corundum for aggregate, its Cr ₂o ₃mass percentage up to 50-80%, and introduces higher Cr in fine powder ₂o ₃micro mist, effectively improves the anti-FeO-SiO of material ₂slag and Cu ₂the penetrating power of O, effectively can alleviate the structure spalling of burner block.

2, the application of high-purity corundum:

Cr ₂o ₃although have good anti-FeO-SiO ₂the osmotic energy effect of slag, but its heat-shock resistance is poor, and if all adopt high chromium corundum, not only cost is high, and the thermal shock resistance of material can significantly reduce.Show after deliberation: corundum is to FeO-SiO ₂infiltration, the agent of erosion of slag are slightly worse than Cr ₂o ₃, but its compact structure, heat-shock resistance are low is far away better than Cr ₂o ₃, and AL ₂o ₃and Cr ₂o ₃unlimited Solid solution can be formed.The present invention adopts high-purity corundum and electric smelting height chromium corundum as composite particles, the tiny crack that the difference of the coefficient of thermal expansion between the two can be utilized to be formed, and the heat improving material is further shaken stability.The present invention's high-purity corundum used can be fused white corundum or plate diamond spar, also can be two kinds of corundum compound uses.

3, with AL ₂o ₃-SiO ₂gel (aluminium Silica hydrogel) combines and replaces traditional cement combination:

For improving anti-erosion and the permeability resistance of burner block further, the present invention selects with AL ₂o ₃-SiO ₂gel combines and replaces traditional cement and combine, thus completely eliminates the CaO content in matrix, reduces the temperature occurring liquid phase, improves the erosion of the high-temperature behavior of material and anti-copper ashes, perviousness.

4, the use of composite superfine powder:

Improve anti-erosion and the permeability resistance of material, except need selecting suitable material composition, namely another important approach is the pore miniaturization of material, and the present invention adopts Cr ₂o ₃, AL ₂o ₃, SiO2, ZrO ₂, zirconium mullite, at least three or more the super-fine powder compound such as corundum, to reach outside diminishing, high-strength, fine and close requirement, improve further the erosion of anti-copper ashes and the perviousness of anti-copper ashes of material, and further increase material because of copper ashes and permeate the structure spalling caused.The particle size range using super-fine powder is 1-10 μ.

5, the copper smelting-furnace provided by the invention weight percentage of the concrete raw material of rare oxygen burner block is:

Electric smelting height chromium corundum coarse particles particle diameter described in burner block provided by the invention is 8-0mm, and electric smelting plate diamond spar or high chromium corundum particle diameter are 10-0mm.Concrete manufacture craft is:

1) mould material preparation: proportioning weighing is carried out in the above-mentioned combination provided, and wherein fine powder is first put in V-Mixer and mixed 15-25 minute, to ensure the even of matrix of materials.Then the fine powder of coarse particles and mixing, bonding agent, admixture are mixed in sand cutting machine, total mixing time is 10-15 minute again;

2) pour into a mould: after adding water in the compound be mixed wet mixing 3-5 minute, pour into a mould burner block;

3) maintenance: burner block maintenance 20-24 hour demoulding in mould of cast, and maintenance 48-60 hour in atmosphere again;

4) dry: the burner block after maintenance need through 110-120 DEG C of prebake conditions drying, and the time is 5-10 hour;

5) burn till: dried burner block burns till through 1550-1600 DEG C of 4-6hr.

Embodiment

Substantive distinguishing features of the present invention and significant progress is illustrated further below by specific embodiment.

Table 1 lists proportioning and the comparative example of the embodiment of the present invention 1 and 2

The Copper making prepared with above-mentioned technique rare oxygen combustor nozzle brick uses through reality, and its life-span reaches more than 6 months, have up to more than 9 months, meet the service requirements of rare oxygen burner.

Claims (5)

1. the rare oxygen combustor nozzle brick of smelting steel stove, is characterized in that the percent mass of described burner block consists of:

2., by burner block according to claim 1, it is characterized in that:

(1) the electric smelting height chromium corundum particle diameter described in is 8-0mm;

(2) the high-purity plate diamond spar described in or fused white corundum particle diameter are 10-0mm;

(3) Cr described in ₂o ₃micro mist, SiO ₂micro mist, corundum powder, Al ₂o ₃micro mist, zirconium not stone grain size of micropowder scope are 1-10 μm.

3., by burner block according to claim 1, it is characterized in that: Cr2O in described electric smelting height chromium corundum ₃mass percentage be 50-80%.

4. make the method for burner block as claimed in claim 1 or 2, it is characterized in that step is:

1) mould material preparation: proportioning weighing is carried out in combination claim 1 provided, and wherein fine powder is first put in V-Mixer and mixed, to ensure the even of matrix of materials; Then electric smelting height chromium corundum, high-purity plate diamond spar or fused white corundum coarse particles are mixed with the fine powder mixed, aluminium Silica hydrogel, additional water reducer in sand cutting machine again;

2) pour into a mould: after the wet mixing that adds water in the compound be mixed, pour into burner block;

3) maintenance: by step 2) the first maintenance demoulding in mould of the burner block poured into a mould, and maintenance in atmosphere again;

4) dry: the burner block after maintenance need through 110-120 DEG C of prebake conditions drying;

5) burn till: dried burner block need burn till through 1550-1600 DEG C.

5. method as claimed in claim 4, is characterized in that:

A) step 1) large or fine granule mixing time be 10-15 minute;

B) step 2) described in the wet mixing time be 3-5 minute;

C) step 3) demoulding after maintenance 20-24 hour in first mould, then maintenance 48-60 hour in atmosphere;

D) step 4) described in prebake conditions time of drying be 5-10 hour;

E) step 5) described in firing time be 4-6 hour.