阅读说明：本技术 一种多铁口高炉用环保无水炮泥及其制备方法 (Environment-friendly anhydrous stemming for multi-taphole blast furnace and preparation method thereof ) 是由 贾石磊 于海东 李学超 于 2020-07-29 设计创作，主要内容包括：本发明属于高炉用耐火材料技术领域,公开了一种多铁口高炉用环保无水炮泥及其制备方法。所述炮泥由骨料、粉料和复合结合剂组成,按质量百分含量计,骨料为38％～45％；粉料为40％～47％；复合结合剂为10％～16％；所述复合结合剂由Carbores T60、Carbores T10、环保蒽油、Carbores P和润湿剂混合而成,所述复合结合剂的苯并a芘含量小于150mg/kg,水分含量≤1.0％。本发明原料中包含多种再生耐火材料和含碳原料,不仅有利于降低生产成本,同时制得的炮泥产品使用时操作方便,干燥速度适中、蠕动性和填充性好,好打泥,易开口,铁口深度稳定,抗冲刷、抗渣性能稳定,而其实际应用时的吨铁炮泥消耗量小于0.5kg,苯并芘含量小于25mg/kg,更有利于改善高炉生产区域环境,保证作业人员身体健康。(The invention belongs to the technical field of refractory materials for blast furnaces, and discloses environment-friendly anhydrous stemming for a multi-taphole blast furnace and a preparation method thereof. The stemming consists of aggregate, powder and a composite binder, wherein the aggregate accounts for 38-45% by mass percent; 40 to 47 percent of powder; 10 to 16 percent of composite binder; the composite binder is prepared by mixing Carbores T60, Carbores T10, environment-friendly anthracene oil, Carbores P and a wetting agent, wherein the content of benzo a pyrene in the composite binder is less than 150mg/kg, and the content of water is less than or equal to 1.0%. The raw materials of the invention comprise a plurality of regenerated refractory materials and carbon-containing raw materials, which is not only beneficial to reducing the production cost, but also convenient to operate when the prepared stemming product is used, has moderate drying speed, good peristalsis and filling property, good stemming, easy opening, stable taphole depth, stable anti-scouring and slag-resisting properties, and the consumption of per ton stemming in practical application is less than 0.5kg, the benzopyrene content is less than 25mg/kg, thereby being more beneficial to improving the production area environment of a blast furnace and ensuring the health of operating personnel.)

1. The environment-friendly anhydrous stemming for the multi-taphole blast furnace is characterized by being prepared from the following raw materials in percentage by mass:

38% -45% of aggregate;

40 to 47 percent of powder;

10-16% of composite binder;

the composite binder is prepared by mixing Carbores T60, Carbores T10, environment-friendly anthracene oil, Carbores P and a wetting agent, wherein the content of benzo a pyrene in the composite binder is less than 150mg/kg, the content of water is less than or equal to 1.0%, the kinematic viscosity at 60 ℃ is 100-250 centipoises, and the carbon residue value is greater than 30.00 wt% when the composite binder is detected at 800 ℃ for 7 min.

2. The environment-friendly anhydrous stemming for a multi-taphole blast furnace according to claim 1, characterized in that: the aggregate is formed by mixing regenerated slide plate materials, pyrophyllite, carbon roasting crushed materials and ceramic kiln shed plate particles, the aggregate granularity is composed of two particle grades which are larger than 0.074mm and smaller than or equal to 1mm and larger than 1mm and smaller than or equal to 3mm, and the mass percentage is 30-40% to 70-60%.

3. The environment-friendly anhydrous stemming for a multi-taphole blast furnace according to claim 2, characterized in that: the regenerated slide plate material is a rear slide plate material for large steel ladles and is prepared by sorting, shelling, coarse breaking, magnetic separation, fine breaking and grading slide plates from rear off-line steel ladles of 300 tons or more, wherein Al in the regenerated slide plate material₂O₃The content is more than or equal to 80.00wt percent, the content of C and SiC is more than or equal to 10.00wt percent, and Fe₂O₃The content is less than or equal to 1.00 wt%, and the particle size of the regenerated slide plate material is composed of two particle compositions of which the particle size is larger than 0.074mm and smaller than or equal to 1mm and larger than 1mm and smaller than or equal to 3mm, and the mass percentage is 30-40% to 70-60%.

4. The environment-friendly anhydrous stemming for a multi-taphole blast furnace according to claim 2, characterized in that: SiO in the pyrophyllite₂More than or equal to 80.00 wt% of Al₂O₃The content is 10.00-15.00 wt%, and the particle size is more than 0.074mm and less than or equal to 1mm and more than 1mm and less than or equal to 1mmTwo kinds of particles with the particle size of 3mm are graded and composed, and the mass percentage is 30-40% to 70-60%.

5. The environment-friendly anhydrous stemming for a multi-taphole blast furnace according to claim 2, characterized in that: the carbon roasting crushed aggregates are selected from residual waste products which are unqualified after the roasting of carbon products through quality inspection or cutting chips generated during the processing of roasting semi-finished products, the particle size of the carbon roasting crushed aggregates is less than or equal to 2mm, and the fixed carbon content is more than or equal to 90.00 wt%; the ceramic kiln shed plate particles are selected from shed plate materials of silicon oxide combined with silicon carbide, silicon carbide combined with silicon carbide or silicon nitride combined with silicon carbide, which are removed after being used in a ceramic industrial kiln, wherein SiC + Si₃N₄The content is more than or equal to 85.00wt percent, and the particle size is less than or equal to 2 mm.

6. The environment-friendly anhydrous stemming for a multi-taphole blast furnace according to claim 1, characterized in that: the particle size of the powder is less than 0.074mm, and the powder is prepared by mixing clay, ferrosilicon nitride, silicon nitride-bonded silicon carbide brick powder, green silicon carbide micro powder, white corundum powder and an additive.

7. The environment-friendly anhydrous stemming for a multi-taphole blast furnace according to claim 6, characterized in that: the clay is selected from Guangxi ball clay with particle size less than or equal to 0.044mm and Al₂O₃Content is more than or equal to 32.00 wt%, Fe₂O₃The content is less than or equal to 1.00 wt%; the grain size of the silicon nitride iron is less than or equal to 0.074mm, wherein Si₃N₄The content is more than or equal to 75.00 wt%, and the Fe content is 10.00-15.00 wt%; the silicon nitride and silicon carbide combined brick powder is prepared by selecting, crushing, magnetically separating and processing residual linings removed after being used in the steel industry, the particle size of the residual linings is less than or equal to 0.044mm, and SiC and Si are added₃N₄The content is more than or equal to 80.00 wt%; the green silicon carbide micro powder is selected from dust extraction powder recovered in the processing process of a green silicon carbide finished product, the particle size d50 of the dust extraction powder is 5 mu m, and the SiC content is more than or equal to 95.00 wt%; the granularity of the white corundum powder is less than or equal to 0.044mm, wherein Al₂O₃The content is more than or equal to 99.00wt percent, and Na₂The content of O is less than or equal to 1.00 wt%; the additive has a particle size of 0.088mm or less and contains Al as main chemical component₂O₃、SiO₂C, Al, Si, S and B₂O₃。

8. The environment-friendly anhydrous stemming for a multi-taphole blast furnace according to claim 1, characterized in that: the composite bonding agent is a liquid bonding agent and comprises the following raw materials in percentage by mass:

9. the environment-friendly anhydrous stemming for a multi-taphole blast furnace according to claim 8, characterized in that: the environment-friendly anthracene oil is a distillate of a certain temperature point in 280-360 ℃ after benzopyrene is removed from crystallized anthracene oil in Henan or Shanxi through an activated carbon filter screen; the wetting agent is Glydol N1003 produced by German Stema chemical industry.

10. The method for preparing the environment-friendly anhydrous stemming for the multi-taphole blast furnace according to any one of claims 1 to 9, comprising the following steps:

(1) weighing the raw materials according to a formula, firstly putting Carbores T60, Carbores T10, environment-friendly anthracene oil, Carbores P and a wetting agent into a reaction kettle at 120 ℃, and mixing and stirring for 8 hours to prepare a composite binder for later use; uniformly mixing clay, ferrosilicon nitride, silicon nitride-bonded silicon carbide brick powder, green silicon carbide micro powder, white corundum powder and additive raw materials to prepare powder for later use;

(2) adding the rest raw materials into an electric oil heating planetary mixing mill, mixing for 3min, adding the prepared powder, stirring, mixing and stirring for 5min, adding a composite binder with the temperature kept at 60 +/-5 ℃, mixing and stirring for 40min to prepare mixed pug, and sampling and detecting Marxia value when the temperature of the mixed pug reaches 65 +/-5 ℃;

(3) and discharging after the Marshall value is measured to be qualified, then extruding and molding by using a mud extruder, and cutting and packaging to obtain the stemming product.

Technical Field

The invention belongs to the technical field of refractory materials for blast furnaces, and particularly relates to environment-friendly anhydrous stemming for a multi-taphole blast furnace and a preparation method thereof.

Background

Blast furnace iron making is the most mainstream smelting mode in the world at present, and from the whole steel production flow, the cost of the iron making process accounts for about 50%, and the energy consumption accounts for about 70%. With the continuous improvement of the smelting technical equipment level and the comprehensive energy consumption of the blast furnaceThe large-scale blast furnace with the advantages of stability, high yield, low consumption, long service life, energy conservation and environmental protection is a necessary trend for iron-making development. At present, the China continental area is put into production or is built at 4000m³More than 23 blast furnaces are used, the iron yield per day of each blast furnace is increased continuously along with the increasing volume of the blast furnace, the number of the iron outlets is increased gradually, and the number of the large blast furnaces with two or more than two iron outlets for continuous and alternate iron tapping is increased. The stemming is used as a key refractory material for blocking a tap hole in the running process of the blast furnace, and the quality and the performance of the stemming directly influence the safe running of the blast furnace; meanwhile, the continuous popularization of high-smelting-strength technologies such as high wind temperature, oxygen-enriched coal injection, high wind pressure, low-silicon smelting and the like puts higher requirements on the use of the stemming, so that the method not only requires long-time tapping and stable taphole depth, is beneficial to protecting the furnace wall near the taphole, but also requires that the taphole channel stemming iron-seeping slag and the leakage-stopping probability are extremely low

However, the existing anhydrous stemming for the multi-taphole blast furnace is mainly formed by mixing and grinding alumina and brown fused alumina serving as aggregates and a plastic matrix material or a bonding agent, and often has the problems of unreasonable formula matching, poor fire resistance, low strength, poor slag corrosion resistance, large mud consumption, difficult taphole maintenance and the like; in addition, the binding agent generally adopts traditional coal tar, anthracene oil or coal pitch, and because the content of the benzo a pyrene in the coal products is different from 5000mg/kg to 12000mg/kg, the pollution is large in the production and use processes of stemming, a large amount of toxic yellow smoke is often emitted, the content of the benzo a pyrene in smoke dust is higher to 1000mg/kg, the environment is seriously polluted, the working condition is worse, the development requirement of energy conservation and environmental protection under new situation is difficult to meet, and the benzo a pyrene is one of the accepted carcinogens in the world and can seriously threaten the health of workers.

Based on the above, the development of the anhydrous stemming for the multi-taphole blast furnace, which has the advantages of excellent performance, safety, environmental protection and less mud consumption, has very important practical significance.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide the environment-friendly anhydrous stemming for the multi-taphole blast furnace and the preparation method thereof, wherein the stemming has the advantages of stable taphole depth, easy mud beating, good tapping, anti-scouring, low benzopyrene content and less mud consumption in use.

The invention provides an environment-friendly anhydrous stemming for a multi-taphole blast furnace, which is prepared from the following raw materials in percentage by mass:

38% -45% of aggregate;

40 to 47 percent of powder;

10-16% of composite binder;

the aggregate is formed by mixing regenerated smooth plates, pyrophyllite, carbon roasting crushed materials and ceramic kiln shed plate particles, the particle size of the aggregate is composed of two particle grades which are larger than 0.074mm and smaller than or equal to 1mm and larger than 1mm and smaller than or equal to 3mm, and the mass percentage of the aggregate is 30-40% to 70-60%.

Preferably, the regenerated slide plate material is a rear slide plate material for large-sized steel ladles, and is prepared by sorting, shelling, coarse breaking, magnetic separation, fine breaking and grading slide plates from rear off-line steel ladles of 300 tons or more, wherein Al in the regenerated slide plate material₂O₃The content is more than or equal to 80.00wt percent, the content of C and SiC is more than or equal to 10.00wt percent, and Fe₂O₃The content is less than or equal to 1.00 wt%, and the particle size of the regenerated slide plate material is composed of two particle compositions of which the particle size is larger than 0.074mm and smaller than or equal to 1mm and larger than 1mm and smaller than or equal to 3mm, and the mass percentage is 30-40% to 70-60%.

Preferably, SiO in the pyrophyllite₂More than or equal to 80.00 wt% of Al₂O₃The content is 10.00-15.00 wt%, the granularity is composed of two particle grades which are more than 0.074mm and less than or equal to 1mm and more than 1mm and less than or equal to 3mm, and the mass percentage is 30-40% to 70-60%.

Preferably, the carbon roasting crushed aggregates are selected from residual waste products which are unqualified after the roasting of carbon products through quality inspection or cutting chips generated during the processing of roasting semi-finished products, the granularity of the carbon roasting crushed aggregates is less than or equal to 2mm, and the fixed carbon content is more than or equal to 90.0 wt%.

It is preferable thatThe ceramic kiln shed plate particles are selected from shed plate materials of silicon oxide combined with silicon carbide, silicon carbide combined with silicon carbide or silicon nitride combined with silicon carbide, which are removed after being used in a ceramic industrial kiln, wherein SiC + Si₃N₄The content is more than or equal to 85.00wt percent, and the particle size is less than or equal to 2 mm.

Specifically, the particle size of the powder is less than 0.074mm, and the powder is prepared by mixing clay, ferrosilicon nitride, silicon nitride-bonded silicon carbide brick powder, green silicon carbide micro powder, white corundum powder and an additive.

Preferably, the clay is selected from Guangxi ball clay with the particle size of less than or equal to 0.044mm and Al₂O₃Content is more than or equal to 32.00 wt%, Fe₂O₃The content is less than or equal to 1.00wt percent.

Preferably, the grain size of the silicon iron nitride is less than or equal to 0.074mm, wherein Si₃N₄The content is more than or equal to 75.00 wt%, and the Fe content is 10.00-15.00 wt%.

Preferably, the silicon nitride and silicon carbide combined brick powder is prepared by selecting, crushing, magnetically separating and processing residual linings removed after being used in the steel industry, the particle size of the residual linings is less than or equal to 0.044mm, and SiC and Si are mixed₃N₄The content is more than or equal to 80.00wt percent.

Preferably, the green silicon carbide micro powder is selected from dust extraction powder recovered in the processing process of a green silicon carbide finished product, the particle size d50 is 5 mu m, and the SiC content is more than or equal to 95.0 wt%.

Preferably, the granularity of the white corundum powder is less than or equal to 0.044mm, wherein Al₂O₃The content is more than or equal to 99.00wt percent, and Na₂The content of O is less than or equal to 1.00wt percent.

Preferably, the particle size of the additive is less than or equal to 0.088mm, and the main chemical component is Al₂O₃、SiO₂C, Al, Si, S and B₂O₃。

Specifically, the composite binder is a liquid binder and is prepared by mixing Carbores T60, Carbores T10, environment-friendly anthracene oil, Carbores P and a wetting agent, wherein the content of benzo (a) pyrene in the composite binder is less than 150mg/kg, the content of water is less than or equal to 1.0%, the kinematic viscosity at 60 ℃ is 100-250 centipoises, and the carbon residue value is greater than 30.0 wt% when the composite binder is detected at 800 ℃ for 7 min.

Specifically, the composite binding agent comprises the following raw materials in percentage by mass:

specifically, the environment-friendly anthracene oil is a distillate of a certain temperature point in 280-360 ℃ after benzopyrene in the crystallized anthracene oil of Henan or Shanxi is removed by an activated carbon filter screen.

Specifically, the wetting agent is Glydol N1003 produced by German Stelman chemical industry.

The invention also provides a preparation method of the environment-friendly anhydrous stemming for the multi-taphole blast furnace, which comprises the following steps:

(1) weighing the raw materials according to a formula, firstly putting Carbores T60, Carbores T10, environment-friendly anthracene oil, Carbores P and a wetting agent into a reaction kettle at 120 ℃, and mixing and stirring for 8 hours to prepare a composite binder for later use; uniformly mixing clay, ferrosilicon nitride, silicon nitride-bonded silicon carbide brick powder, green silicon carbide micro powder, white corundum powder and additive raw materials to prepare powder for later use;

(2) adding the rest raw materials into an electric oil heating planetary mixing mill, mixing for 3min, adding the prepared powder, stirring, mixing and stirring for 5min, adding a composite binder with the temperature kept at 60 +/-5 ℃, mixing and stirring for 40min to prepare mixed pug, and sampling and detecting Marxia value when the temperature of the mixed pug reaches 65 +/-5 ℃;

(3) and discharging after the Marshall value is measured to be qualified, then extruding and molding by using a mud extruder, and cutting and packaging to obtain the stemming product.

Compared with the prior art, the invention has the advantages that:

1. the raw materials comprise various regenerated refractory materials and carbon-containing raw materials, so that the energy conservation and environmental protection are facilitated, the resource is efficiently utilized, the production cost is reduced, and the fire resistance, the erosion resistance and the sintering strength of the stemming are greatly improved; the performance of the bonding agent is improved through compounding of multiple raw materials, the quality and the performance of the stemming product are ensured, and the stemming product is safer and more environment-friendly in production and use.

2. The composite binder provided by the invention is prepared by mixing Carbores T60, Carbores T10, environment-friendly anthracene oil, Carbores P and a wetting agent, wherein the content of benzo a pyrene is less than 150mg/kg, and the content of water is less than or equal to 1.0%. Compared with the traditional stemming binding agent, the composite binding agent provided by the invention has less usage amount, the pollution of the prepared stemming product is lower when the prepared stemming product is used, the wetting agent added in the composite binding agent is more favorable for reducing the friction among particles, and the plasticity and the stability of the stemming are increased, and the detection result shows that the content of benzo a pyrene in the prepared stemming product is less than 25mg/kg and is far lower than 100mg/kg specified in the industry standard 'anhydrous stemming for blast furnace' YB/T4196-2018, so that volatile gas and pungent smell are not generated in the production and processing process, no dense smoke and yellow smoke are splashed when the stemming is tapped, the environment of a production area of the blast furnace is favorably improved, and the body health of operators is ensured.

3. Experiments prove that when the environment-friendly anhydrous stemming provided by the invention is used on a plurality of large blast furnaces with a plurality of tapholes, the environment-friendly anhydrous stemming is convenient to operate, has moderate drying speed, good peristalsis and filling property, good stemming, easy opening, stable taphole depth and long tapping time, and can better maintain the furnace wall in the taphole area; meanwhile, the anti-scouring and anti-slag performances are stable, the probability of iron leakage and iron breakage is low, the consumption of per ton of iron gun mud is low (per ton of iron is less than 0.5kg), the cost performance of the product is high, and the market prospect is good.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the following examples, the regenerated slide plate material is a rear slide plate material for large-sized steel ladles, and is prepared by sorting, shelling, coarse crushing, magnetic separation, fine crushing and grading slide plates from rear off-line steel ladles of 300 tons or more, wherein Al in the regenerated slide plate material is₂O₃The content is more than or equal to 80.00wt percent, the content of C and SiC is more than or equal to 10.00wt percent, and Fe₂O₃Less than or equal to 1.00wt percent; SiO in the pyrophyllite₂More than or equal to 80.00 wt% of Al₂O₃The content is 10.00-15.00 wt%; the carbon roasting crushed aggregates are selected from residual waste products which are unqualified after the roasting of carbon products through quality inspection or cutting chips generated during the processing of roasting semi-finished products, the particle size of the carbon roasting crushed aggregates is less than or equal to 2mm, and the fixed carbon content is more than or equal to 90.00 wt%; the ceramic kiln shed plate particles are selected from shed plate materials of silicon oxide combined with silicon carbide, silicon carbide combined with silicon carbide or silicon nitride combined with silicon carbide, which are removed after being used in a ceramic industrial kiln, wherein SiC + Si₃N₄The content is more than or equal to 85.00 wt%, and the particle size is less than or equal to 2 mm; the granularity of the powder is less than 0.074 mm; the clay is selected from Guangxi ball clay with particle size less than or equal to 0.044mm and Al₂O₃Content is more than or equal to 32.00 wt%, Fe₂O₃The content is less than or equal to 1.00 wt%; the grain size of the silicon nitride iron is less than or equal to 0.074mm, wherein Si₃The content of N4 is more than or equal to 75.00 wt%, and the content of Fe is 10.00-15.00 wt%; the silicon nitride and silicon carbide combined brick powder is prepared by selecting, crushing, magnetically separating and processing residual linings removed after being used in the steel industry, the particle size of the residual linings is less than or equal to 0.044mm, and SiC and Si are added₃N₄The content is more than or equal to 80.00 wt%; the green silicon carbide micro powder is selected from dust extraction powder recovered in the processing process of a green silicon carbide finished product, the particle size d50 of the dust extraction powder is 5 mu m, and the SiC content is more than or equal to 95.00 wt%; the granularity of the white corundum powder is less than or equal to 0.044mm, wherein Al₂O₃The content is more than or equal to 99.00wt percent, and Na₂The content of O is less than or equal to 1.00 wt%, the granularity of the additive is less than or equal to 0.088mm, the composite binder is a liquid binder, the content of benzo (a) pyrene in the composite binder is less than 150mg/kg, the content of water is less than or equal to 1.0%, the kinematic viscosity of the composite binder at 60 ℃ is 100-250 centipoises, the carbon residue value detected at 800 ℃ for × 7min is more than 30.0 wt%, the lubricant is Glydol N1003 produced by Germany and Sema chemical industry, and the typical value of the chemical components of the additive is Al₂O₃22.33 wt% SiO₂4.06 wt%, C30.87 wt%, Al 12.81 wt%, Si 12.62 wt%, S10.54 wt%, B₂O₃The content was 6.77%.