CN113149665A - Environment-friendly bonding agent and stemming for blast furnace - Google Patents
Environment-friendly bonding agent and stemming for blast furnace Download PDFInfo
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
Abstract
The invention provides an environment-friendly binding agent for a blast furnace and stemming, wherein the environment-friendly binding agent for the blast furnace consists of low-temperature distillate oil of coal tar under the normal pressure condition and high-temperature distillation range asphalt, the distillation range temperature of the low-temperature distillate oil is below 400 ℃, and the high-temperature distillation range asphalt is residue of the coal tar after distillation at the temperature of above 500 ℃. The invention provides an environment-friendly bonding agent for a blast furnace and stemming, wherein the content of 3, 4-benzopyrene in the environment-friendly bonding agent is less than 50ppm, so that the problems of toxicity and pollution caused by using coal tar as a bonding agent or short quality guarantee period and poor practicability caused by using resin as a bonding agent are effectively solved, the service performance of the stemming is not influenced, and the stemming capable of being popularized and applied in a large range is obtained.
Description
Technical Field
The invention relates to the technical field of refractory materials for iron-making systems, in particular to an environment-friendly bonding agent and stemming for a blast furnace.
Background
The stemming is a refractory material for a blast furnace iron-making system, and after tapping of a blast furnace is finished, the stemming is required to block an iron notch, and then smelting is continued. With the continuous strengthening of blast furnace smelting and the increasing large-scale blast furnace, the requirement on stemming for a blast furnace taphole is higher and higher. If the stemming quality is poor, a series of problems can be caused, such as a wet taphole, a broken taphole, a shallow taphole and the like, so that the normal production is influenced, and even personal safety accidents are caused. Therefore, the stemming is required to have the following properties: (1) the plasticity and the cohesiveness are good, and the steel can be easily extruded into an iron notch and filled with gaps and cracks; (2) the porosity is proper, so that moisture is conveniently discharged; (3) the volume stability is good, and the shrinkage does not occur in the sintering process; (4) has proper high-temperature strength, good opening performance, easy opening, good slag resistance, good scour resistance and good molten iron corrosion resistance.
The stemming comprises two parts, namely refractory aggregate and a binding agent, wherein the refractory aggregate refers to corundum, mullite, flint clay and other refractory raw materials and coke, mica and other modified materials, and the binding agent is water or tar, phenolic resin and other organic materials. The water-containing stemming using water as a binder is called water-containing stemming, and the anhydrous stemming using organic materials such as tar and resin as binders is called anhydrous stemming. Due to the fact that the water adding amount of the water-containing stemming is high, a large amount of water in the stemming volatilizes out when meeting high-temperature molten iron in the tapping process, and molten iron splashing, namely the phenomenon of iron mouth wetting, is easily caused; and because the output of the blast furnace is improved, the flow of the iron slag is increased, and the defects of easy flushing into a bell mouth and the like are overcome. Therefore, anhydrous stemming is currently the most commonly used.
However, the anhydrous stemming using tar as a binding agent generates smoke in the heating process, releases a large amount of organic smoke, contains more benzopyrene, and 3, 4-benzopyrene is a very strong carcinogenic substance, and researches show that: the death rate of lung cancer is increased by 5 percent when the content of benzopyrene in the air is increased by 1 percent, and extremely unpleasant odor is generated to worsen the working environment and seriously affect the physical health of stokehole workers. Even though some documents report that a mixture of tar and anthracene oil is used as a binder, the problem of high content of benzopyrene is not well solved because the proportion of tar is still not small.
The anhydrous stemming adopting the resin as the bonding agent can improve the operating environment and solve the pollution problem, but the cost is greatly improved, and the stemming is fast to cure and short in quality guarantee period, so that the practicability is poor. For example, chinese patent application CN101580397A discloses a blast furnace stemming with low benzopyrene content, wherein carbon-containing resin and carbon-containing resin solvent are used as binding agent, and the benzopyrene content in the stemming does not exceed 1000 ppm.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an environment-friendly bonding agent for a blast furnace and stemming.
The invention adopts the following technical scheme:
the invention provides an environment-friendly binding agent for a blast furnace, which consists of low-temperature distillate oil of coal tar under normal pressure and high-temperature distillation range asphalt, wherein the distillation range temperature of the low-temperature distillate oil is below 400 ℃, and the high-temperature distillation range asphalt is residue of coal tar after distillation at the temperature of above 500 ℃.
Aiming at the pollution problem caused by adopting tar as a binding agent, the prior improvement method adopts resin as one method, and reduces the using amount of the tar to compound the tar with components such as asphalt or anthracene oil and the like. As mentioned above, the resin has short shelf life and high cost, and is not suitable for popularization. The tar is compounded with other components to treat the symptoms and not the root causes, benzopyrene in the tar still exists, the pollution problem is not well solved, and the performance of the stemming is even affected. In the prior art, tar is dehydrated and desalted, air stirring is performed under ozone, and then benzopyrene is removed through a filter screen containing activated carbon, but the step of removing benzopyrene is complicated, and the production cost is increased. According to the research of the invention, the coal tar distillate oil below 400 ℃ and the high-temperature distillation range asphalt distilled at the temperature above 500 ℃ are compounded to be used as the binding agent, wherein the content of 3, 4-benzopyrene is less than 50ppm, so that the problems of toxicity and pollution caused by using the coal tar as the binding agent are effectively solved, the service performance of the stemming is not influenced, and an unexpected technical effect is achieved.
The low-temperature distillate oil comprises light oil, phenol oil, naphthalene oil, wash oil, anthracene oil and the like. The light oil is distillate cut from coal tar under atmospheric distillation and has a distillation range of 170 ℃ and the yield of 0.4-0.8 percent of that of anhydrous coal tar. The phenol oil is distillate at the temperature of 170-210 ℃ cut by coal tar atmospheric distillation, and the yield is 1.4-2.3% of that of anhydrous coal tar. The naphthalene oil is distillate cut from coal tar atmospheric distillation and having a distillation range of 210-230 ℃, and the yield is 11-13% of that of anhydrous coal tar. The washing oil is distillate cut from coal tar under normal pressure distillation and with the distillation range of 230-300 ℃, and the yield is 4.5-6.5%. The anthracene oil is distillate cut from coal tar under normal pressure distillation and having a distillation range of 300-330 ℃, and the yield is 14-20% of that of anhydrous coal tar.
Further, the mass ratio of the low-temperature distillate oil to the high-temperature distillation range asphalt is 0.5-1.5: 1. Under the proportion, the obtained bonding agent is environment-friendly and pollution-free, and indexes such as viscosity and the like meet the requirement of preparing the stemming with excellent strength, porosity and other properties.
The invention also provides stemming for the blast furnace, which comprises the environment-friendly bonding agent for the blast furnace. The stemming adopting the environment-friendly binding agent disclosed by the invention has the advantages that no black smoke is emitted in the using process, the pollution and the damage to the human health are reduced to the minimum, the cost is lower, and the stemming can be popularized and applied in a large range.
In a preferred embodiment of the invention, the blast furnace stemming comprises the following components in parts by weight: 20-40 parts of refractory raw materials, 15-30 parts of silicon carbide, 5-10 parts of clay, 15-25 parts of coke, 10-20 parts of Guangxi mud, 5-15 parts of pyrophyllite and 16-20 parts of environment-friendly binding agents.
Preferably, the refractory raw material comprises one or more of flint clay, bauxite and corundum, wherein the mass ratio of the granular material with the granularity of more than 0.088mm is 10-20%, and the balance is powdery material.
The silicon carbide consists of 10-18% of granular materials with the granularity larger than 0.088mm and the balance of powdery materials.
The coke particle size is greater than 0.088 mm.
The particle size of the pyrophyllite is less than 0.088 mm.
Further, when the blast furnace volume is less than 1000m3The stemming for the blast furnace comprises the following components in parts by weight: 20-40 parts of flint clay, 15-20 parts of 90 silicon carbide, 5-10 parts of clay, 15-25 parts of coke, 10-20 parts of Guangxi mud, 8-15 parts of pyrophyllite and 16-20 parts of environment-friendly bonding agent.
When the volume of the blast furnace is 1000-2500 m3The stemming for the blast furnace comprises the following components in parts by weight: 20-35 parts of bauxite, 15-20 parts of 90 silicon carbide, 5-10 parts of clay, 15-25 parts of coke, 10-20 parts of Guangxi mud, 10-15 parts of pyrophyllite and 16-20 parts of the environment-friendly binding agent.
When the volume of the blast furnace is more than 2500m3The stemming for the blast furnace comprises the following components in parts by weight: 25-40 parts of corundum, 20-30 parts of 97 silicon carbide, 5-10 parts of clay, 15-20 parts of coke, 10-15 parts of Guangxi mud, 5-15 parts of pyrophyllite and 16-20 parts of environment-friendly bonding agent.
The invention also provides a preparation method of the stemming for the blast furnace, which comprises the following steps:
weighing granular refractory raw materials, silicon carbide and coke according to a proportion, and uniformly mixing to obtain a material A; weighing powdery refractory raw materials, clay, silicon carbide, Guangxi mud and pyrophyllite according to a proportion, and uniformly mixing to obtain a material B;
putting the material A into a preheated stirrer, adding 10-16% by mass of an environment-friendly bonding agent, and stirring for 3-5 min; and adding the material B and 3-5% of an environment-friendly binding agent, stirring for 40-50 min, grinding until the Marxia value meets the requirement, extruding by using a vacuum mud extruder, and sealing and packaging for later use. Wherein the addition amount of the environment-friendly bonding agent is based on the sum of the material A and the material B.
The invention provides an environment-friendly bonding agent for a blast furnace and stemming, wherein the content of 3, 4-benzopyrene in the environment-friendly bonding agent is less than 50ppm, so that the problems of toxicity and pollution caused by using coal tar as a bonding agent or short quality guarantee period and poor practicability caused by using resin as a bonding agent are effectively solved, the service performance of the stemming is not influenced, and the stemming capable of being popularized and applied in a large range is obtained.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. 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.
Unless otherwise specified, the starting materials used in the examples of the present invention are all commercially available.
Example 1
The embodiment provides stemming for a blast furnace, which comprises the following components in parts by weight: 27 parts of flint clay, 18 parts of 90SiC, 6 parts of clay, 21 parts of coke (the granularity is more than 0.088mm), 16 parts of Guangxi mud, 12 parts of pyrophyllite (the granularity is less than 0.088mm) and 20 parts of environment-friendly bonding agent.
The environment-friendly bonding agent is composed of coal tar, low-temperature distillate oil at the temperature of below 400 ℃ and high-temperature distillation range asphalt distilled at the temperature of above 500 ℃ at normal pressure according to the mass ratio of 1:1, and the content of 3, 4-benzopyrene in the environment-friendly bonding agent is less than 50 ppm.
The proportion of the granules with the particle size larger than 0.088mm in the flint clay is 16 percent, and the balance is powdery material.
The proportion of granules with the grain size of more than 0.088mm in 90SiC is 10 percent, and the balance is powdery material.
The embodiment also provides a preparation method of the stemming for the blast furnace, which comprises the following specific steps:
weighing granular flint clay, silicon carbide and coke according to a proportion, and uniformly mixing to obtain a material A;
weighing powdery flint clay, silicon carbide, Guangxi mud and pyrophyllite according to a proportion, and uniformly mixing to obtain a material B;
putting the material A into a preheated stirrer, adding an environment-friendly bonding agent accounting for 10-16 wt% of the total weight of the material A and the material B, and stirring for 3-5 min; and then, sequentially adding the material B and a binding agent accounting for 3-5 wt% of the total of the material A and the material B, stirring for 40-50 min, sampling and detecting the Marxia value in the mud grinding process, if the Marxia value is higher, prolonging the mud grinding time, detecting again until the Marxia value meets the requirement, finally extruding by using a vacuum mud extruder, and sealing and packaging for later use.
The stemming provided by the embodiment is more suitable for being used for the stemming with the volume less than 1000m3The blast furnace of (1).
Example 2
The embodiment provides stemming for a blast furnace, which comprises the following components in parts by weight: 28 parts of 85 alum soil material, 17 parts of 90SiC, 7 parts of clay, 18 parts of coke (granularity is more than 0.088mm), 15 parts of Guangxi mud, 15 parts of pyrophyllite (granularity is less than 0.088mm) and 18 parts of environment-friendly bonding agent.
The environment-friendly bonding agent is composed of coal tar, low-temperature distillate oil at the temperature of below 400 ℃ and high-temperature distillation range asphalt distilled at the temperature of above 500 ℃ at normal pressure according to the mass ratio of 1:1, and the content of 3, 4-benzopyrene in the environment-friendly bonding agent is less than 50 ppm.
The proportion of granules with the particle size of more than 0.088mm in 85 alumina material is 14 percent, and the balance is powdery material.
The 90SiC contains 11 percent of granules with the granularity of more than 0.088mm, and the balance is powdery material.
The embodiment also provides a preparation method of the stemming for the blast furnace, which comprises the following specific steps:
weighing granular bauxite material, silicon carbide and coke according to a proportion, and uniformly mixing to obtain material A;
weighing powdery bauxite material, clay, silicon carbide, Guangxi mud and pyrophyllite according to a proportion, and uniformly mixing to obtain material B;
putting the material A into a preheated stirrer, adding an environment-friendly bonding agent accounting for 10-16 wt% of the total weight of the material A and the material B, and stirring for 3-5 min; and then, sequentially adding the material B and a binding agent accounting for 3-5 wt% of the total of the material A and the material B, stirring for 40-50 min, sampling and detecting the Marxia value in the mud grinding process, if the Marxia value is higher, prolonging the mud grinding time, detecting again until the Marxia value meets the requirement, finally extruding by using a vacuum mud extruder, and sealing and packaging for later use.
The stemming provided by the embodiment is more suitable for being used in the volume of 1000-2500 m3The blast furnace of (1).
Example 3
The embodiment provides stemming for a blast furnace, which comprises the following components in parts by weight: 25 parts of brown corundum, 24 parts of 97SiC, 7 parts of clay, 15 parts of coke (granularity is more than 0.088mm), 10 parts of Guangxi mud, 9 parts of pyrophyllite (granularity is less than 0.088mm) and 16 parts of environment-friendly bonding agent.
The environment-friendly bonding agent is composed of coal tar, low-temperature distillate oil at the temperature of below 400 ℃ and high-temperature distillation range asphalt distilled at the temperature of above 500 ℃ at the normal pressure according to the mass ratio of 0.8:1, and the content of 3, 4-benzopyrene in the environment-friendly bonding agent is less than 50 ppm.
The proportion of the granular material with the granularity of more than 0.088mm in the brown fused alumina is 12 percent, and the rest is the powdery material.
97SiC, the proportion of granules with the particle size of more than 0.088mm is 11 percent, and the balance is powdery material.
The embodiment also provides a preparation method of the stemming for the blast furnace, which comprises the following specific steps:
weighing granular brown corundum, silicon carbide and coke according to a proportion, and uniformly mixing the materials to obtain a material A;
weighing powdery brown corundum, clay, silicon carbide, Guangxi mud and pyrophyllite according to a proportion, and uniformly mixing to obtain a material B;
putting the material A into a preheated stirrer, adding an environment-friendly bonding agent accounting for 10-16 wt% of the total weight of the material A and the material B, and stirring for 3-5 min; and then, sequentially adding the material B and a binding agent accounting for 3-5 wt% of the total of the material A and the material B, stirring for 40-50 min, sampling and detecting the Marxia value in the mud grinding process, if the Marxia value is higher, prolonging the mud grinding time, detecting again until the Marxia value meets the requirement, finally extruding by using a vacuum mud extruder, and sealing and packaging for later use.
The stemming provided by the embodiment is more suitable for being used for the stemming with the volume larger than 2500m3The blast furnace of (1).
Comparative example 1
This comparative example provides a stemming, which differs from example 1 in that tar is used instead of the environmentally friendly binder.
Comparative example 2
This comparative example provides a stemming, which differs from example 2 in that tar is used instead of the environmentally friendly binder.
Comparative example 3
This comparative example provides a stemming, which differs from example 3 in that tar is used instead of the environmentally friendly binder.
Performance testing
The stemming provided by each of the above examples and comparative examples was measured according to national standards for shelf life, bulk density, compressive strength, linear change rate, and porosity, and the results were as follows:
table 1 comparison of properties of anhydrous stemming with different binders
The results show that: the anhydrous stemming is equivalent to a comparative example (the existing anhydrous stemming) in use performance, can completely replace the existing anhydrous stemming, and compared with the existing anhydrous stemming, the anhydrous stemming uses the environment-friendly binding agent, reduces the content of benzopyrene, overcomes the defects of pollution and harm to body health, and optimizes the applicability and popularization value.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The environment-friendly binding agent for the blast furnace is characterized by consisting of low-temperature distillate oil of coal tar under normal pressure and high-temperature distillation range asphalt, wherein the distillation range temperature of the low-temperature distillate oil is below 400 ℃, and the high-temperature distillation range asphalt is residue of coal tar after distillation at a temperature above 500 ℃.
2. The environment-friendly bonding agent for the blast furnace as recited in claim 1, wherein the mass ratio of the low-temperature distillate oil to the high-temperature distillation range asphalt is 0.5-1.5: 1.
3. A stemming for a blast furnace, comprising the environmentally friendly bonding agent for a blast furnace as set forth in claim 1 or 2.
4. The stemming for a blast furnace according to claim 3, wherein the stemming for a blast furnace comprises the following components in parts by weight: 20-40 parts of refractory raw materials, 15-30 parts of silicon carbide, 5-10 parts of clay, 15-25 parts of coke, 10-20 parts of Guangxi mud, 5-15 parts of pyrophyllite and 16-20 parts of environment-friendly binding agents.
5. The stemming according to claim 4, wherein the refractory raw material comprises one or more of flint clay, bauxite and corundum, and the mass proportion of the granular material with the granularity of more than 0.088mm is 10-20%.
6. The stemming for a blast furnace according to claim 4 or 5, wherein the silicon carbide consists of 10 to 18% by mass of a granular material having a particle size of more than 0.088mm and the balance of a powdery material;
and/or, the coke particle size is greater than 0.088 mm;
and/or the particle size of the pyrophyllite is less than 0.088 mm.
7. The stemming according to any one of claims 4 to 6, wherein the blast furnace volume is less than 1000m3The stemming for the blast furnace comprises the following components in parts by weight: 20-40 parts of flint clay, 15-20 parts of 90 silicon carbide, 5-10 parts of clay, 15-25 parts of coke, 10-20 parts of Guangxi mud, 8-15 parts of pyrophyllite and 16-20 parts of environment-friendly bonding agent.
8. The stemming according to any one of claims 4 to 6, wherein the blast furnace volume is 1000 to 2500m3The stemming for the blast furnace comprises the following components in parts by weight: 20-35 parts of bauxite, 15-20 parts of 90 silicon carbide, 5-10 parts of clay, 15-25 parts of coke, 10-20 parts of Guangxi mud, 10-15 parts of pyrophyllite and 16-20 parts of the environment-friendly bonding agent.
9. The stemming according to any one of claims 4 to 6, wherein the blast furnace volume is more than 2500m3For said blast furnaceThe stemming comprises the following components in parts by weight: 25-40 parts of corundum, 20-30 parts of 97 silicon carbide, 5-10 parts of clay, 15-20 parts of coke, 10-15 parts of Guangxi mud, 5-15 parts of pyrophyllite and 16-20 parts of environment-friendly bonding agent.
10. The method for preparing stemming for a blast furnace according to any one of claims 4 to 9, comprising:
weighing granular refractory raw materials, silicon carbide and coke according to a proportion, and uniformly mixing to obtain a material A; weighing powdery refractory raw materials, clay, silicon carbide, Guangxi mud and pyrophyllite according to a proportion, and uniformly mixing to obtain a material B;
putting the material A into a preheated stirrer, adding an environment-friendly bonding agent accounting for 10-16% of the total mass of the material A and the material B, and stirring for 3-5 min; and adding the material B and an environment-friendly bonding agent accounting for 3-5% of the total mass of the material A and the material B, stirring for 40-50 min, grinding until the Marshall value meets the requirement, extruding by using a vacuum mud extruder, and sealing and packaging for later use.
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| CN116854490A (en) * | 2022-11-14 | 2023-10-10 | 太原科技大学 | Environment-friendly carbonaceous binding agent for blast furnace, preparation method and stemming for blast furnace |
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