CN111606583B - Equipment and method for producing cement by using liquid steel slag as raw material - Google Patents
Equipment and method for producing cement by using liquid steel slag as raw material Download PDFInfo
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- CN111606583B CN111606583B CN202010483497.2A CN202010483497A CN111606583B CN 111606583 B CN111606583 B CN 111606583B CN 202010483497 A CN202010483497 A CN 202010483497A CN 111606583 B CN111606583 B CN 111606583B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/02—Phosphate cements
- C04B12/027—Phosphate cements mixtures thereof with other inorganic cementitious materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B11/00—Making pig-iron other than in blast furnaces
- C21B11/08—Making pig-iron other than in blast furnaces in hearth-type furnaces
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses equipment and a method for producing cement by taking liquid steel slag as a raw material, and the equipment comprises a furnace body, a horizontal flow liquid hole, an ascending flow liquid channel and an overflow hole, wherein the furnace body is cylindrical, the bottom of the furnace body is provided with an iron discharging hole, a first refractory material frame is arranged in the furnace body, a carbon material is arranged in the first refractory material frame, a furnace wall side-inserted combustion spray gun and a liftable top combustion spray gun are arranged on the side wall of the furnace body positioned on the upper side of the first refractory material frame, the liftable top combustion spray gun is connected with the top of the furnace body in a liftable manner through a sleeve, and the top of the furnace body is provided with a slag liquid inlet and an inclined conical furnace cover. Under the condition of not influencing steel smelting, high-temperature liquid slag is used for adding silicon-aluminum correction raw materials, the silicon-aluminum correction raw materials flow through a carbon reduction bed and an active lime saturation area in the furnace to decompose RO phase, FeOx is reduced, molten iron is recycled, liquid cement clinker is generated, and heat released by the liquid cement clinker during cooling and solidification can be recovered.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of metallurgical slag, in particular to equipment and a method for producing cement by taking liquid steel slag as a raw material.
Background
Blast furnace gas, slag and steel slag are the first three-position byproducts in steel smelting, the blast furnace gas is completely recycled, the slag is also utilized 99% in a cement mixed material and a concrete admixture, but the utilization rate of the steel slag is very low, the comprehensive utilization rate is only 30-40%, wherein the blast furnace gas, the slag and the steel slag are about 10% when used in cement and concrete, and most of the blast furnace gas, the slag and the steel slag are stockpiled and discarded.
The main chemical components of the slag, the steel slag and the portland cement clinker are basically similar, but the content of oxides is greatly different, and the chemical content of the steel slag is closer to that of the portland cement clinker compared with the slag; the slag, the steel slag and the portland cement clinker have similar mineral compositions; phase (C)The steel slag and the portland cement clinker all contain B ore (. beta. -C) as compared with the slag2S), A ore (C)3S), calcium aluminoferrite, calcium ferrite (C)2F) Free calcium oxide (f-CaO), and the like, which make the steel slag have hydration activity; the steel slag also contains RO phase, and the steel slag with lower alkalinity contains olivine (CaO. RO. SiO2) And multiflora rose pyroxene (3CaO. RO.2SiO)2). However, compared with silicate cement clinker, the steel slag has low A ore content and is solid-melted with iron, sulfur and the like; the B ore is subjected to phase change in the cooling process part to form gamma C with low activity2S, and is solidly fused with P2O5；P2O5More than 0.3% may result in C3S is decomposed, so that the coagulation time of the steel slag is greatly prolonged, and the activity of the steel slag is reduced; meanwhile, the steel slag has high content of free calcium oxide (f-CaO) and periclase, and the volume stability of the free calcium oxide (f-CaO) and the periclase is influenced.
The steel slag is not used as slag in a large amount and effectively, and the main reasons are as follows: 1. the steel slag components have large fluctuation and the mineral composition is unstable due to the change of steel-making varieties, raw materials and operation processes; 2. the steel slag has low glass phase content, low hydration activity, slow hydration speed and slow slurry strength increase; 3. the steel slag ROf-CaO and MgO are hydrated slowly, and when hydrated, the volume expansion causes the hardened cement paste to generate local expansion stress, which causes serious poor cement stability; 4. the grindability is poor. Therefore, the steel slag is piled up for years.
For a long time, the steel slag treatment process and method are the subject and hot spot of industrial research. The mechanical activation, thermal activation and chemical activation of cooled solid steel slag are currently adopted; the mechanical activation is to repeatedly grind the steel slag for a long time to improve the fineness of the slag powder, and the lower the activity, the finer the grinding is, the activity can be activated; the thermal activation is to carry out steam curing during the curing of the cement paste or to increase the steam pressure and temperature in a pressure container so as to increase the hydration speed; the chemical activation is to add strong alkali or alkaline salt into the milled steel slag to activate the activity of the steel slag and accelerate the hydration hardening.
The steel slag is difficult to grind, the requirement on activation fineness is high, and a large amount of energy is consumed; the alkali activator has great difference in excitation effect on different steel slag, has limited effect on improving the cement performance and leaves hidden danger on the later stability of concrete; the thermal activation is only suitable for curing cement products and is not suitable for pouring large-volume concrete; the three types of activation greatly increase the cost, sometimes even cause no repayment, and limit the improvement of the utilization rate of the steel slag.
The separation process of the RO phase in the steel slag considers that the steel slag has low content of active minerals and high content of inert minerals (mainly the RO phase, Fe2O3 and Fe), the existence of up to 25 to 40 percent of the inert minerals greatly influences the hydration activity of the steel slag, and the key point for effectively separating the inert minerals and the active minerals in the steel slag into steel slag resources.
The separation process of the RO phase comprises the steps of grinding the steel slag until the RO phase is dissociated from steel slag crystals, and then carrying out screening, gravity separation, magnetic separation, electric separation, water separation, leaching and flotation; in order to reduce the grinding dissociation cost, a microwave radiation heating process is adopted; the steel slag powder is roasted to enhance the magnetism of the inert mineral with middle magnetism, so as to be beneficial to the magnetic separation process.
No matter which sorting process is adopted, the steel slag is subjected to dry grinding, pneumatic sorting, dry magnetic separation, wet grinding, wet magnetic separation and dehydration; long flow, high energy consumption and unclear selection.
In recent years, research on the reconstruction of steel slag has been carried out. Steel slag reconstruction is reconstructed online (namely online) and offline (calcining);
the on-line reconstruction is that various regulating components are added in the process of discharging the steel slag, and the regulating components and the molten steel slag are subjected to chemical reaction by using the waste heat of the steel slag to form metallic iron and reconstructed slag with high gelling activity.
Calcining and reconstructing, namely grinding the clay and the limestone together with the steel slag according to different proportions, and reconstructing the steel slag at high temperature.
Yuanmeixia et al, in "research on clinker using slag as raw material for firing" because the chemical components of the slag used are CaO and SiO, as compared with those of portland cement clinker2Low content of, but Fe2O3The content is much higher, therefore, the proper amount of limestone and clay is added to adjust the components, thereby preparing the low-silicon high-siliconFerrosilicate cement clinker. The calcined clinker is crushed and ground and then is made into cement with a certain amount of ground gypsum, and physical experiment detection of various formula cements shows that when the lime saturation coefficient and the aluminum rate are similar, the high strength of the silicon rate value is high; when the silicon rate and the aluminum rate are close, the lime has high saturation coefficient value and high strength. Researches show that the steel slag calcination of the portland cement clinker is feasible, and the batching scheme is suitable for adopting high KH value and improving the silicon rate and the aluminum rate as much as possible.
The invention patent of patent publication No. CN1004546B, entitled "method for producing high-iron cement by using high-activity converter steel slag", discloses a method for producing high-iron cement by adding activated calcium oxide and high-quality bauxite while adding slagging raw materials under normal smelting process conditions of a converter to obtain modified converter steel slag, adding a proper amount of dihydrate gypsum after hot splashing and crushing, and then grinding. The method adjusts the content and the ratio of main oxides of the steel slag in the furnace to be close to the range required by common silicate cement clinker, and produces the No. 325 cement; the invention is successfully tested in a 120-ton converter, and is identified by all the techniques of the Ministry of metallurgy in 1988.
The steel slag reconstruction is to use the steel slag as a raw material for producing cement, and produce clinker through secondary calcination or back melting; the processes and the methods need crushing, grinding and mixing, the utilization rate of the steel slag is low, and energy is consumed. On-line reconstruction, in order to utilize the enthalpy of high-temperature liquid steel slag, the regulating material needs to be quickly added when the liquid steel slag is discharged beside a converter, a steelmaking slag-discharging site is occupied, and slag-discharging time is prolonged, so that steelmaking production is influenced; whether the adjusting components are added into a slag tank before the liquid steel slag is discharged or are added along with the liquid steel slag, the high-temperature solid-liquid phases are difficult to be uniformly mixed and completely carry out chemical reaction, so that the 28-day hydration activity index of the reconstructed steel slag powder is only improved by 4-8 percent, and the improvement range is not large; the steel slag is modified in the converter, which influences the smelting of steel.
The technical problem to be solved by the invention is as follows: 1. how to utilize the high-temperature slag liquid to finish RO phase decomposition in liquid phase under the premise of not influencing converter smelting to ensure that C2S is converted to C3S, a process method; 2. simple and reliable, low investment for practical productionThe apparatus of (1).
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides equipment and a method for producing cement by using liquid steel slag as a raw material.
In order to achieve the purpose, the invention adopts the following technical scheme:
an apparatus for producing cement by using liquid steel slag as a raw material comprises a furnace body, a horizontal flow liquid hole, an ascending flow liquid channel and an overflow hole, wherein the furnace body is cylindrical, the bottom of the furnace body is provided with an iron discharging hole, a first refractory material frame is arranged in the furnace body, a carbon material is arranged in the first refractory material frame, a furnace wall side-inserted combustion spray gun and a liftable top combustion spray gun are arranged on the side wall of the furnace body positioned on the upper side of the first refractory material frame, the liftable top combustion spray gun is connected with the top of the furnace body in a liftable manner through a sleeve, the top of the furnace body is provided with a slag liquid inlet and an inclined conical furnace cover, a slag liquid inlet is arranged at the slag liquid inlet and is provided with a gas seal device, one side of the top of the furnace body, which is far away from the iron discharging hole, is communicated with the horizontal flow liquid hole, a heating molybdenum electrode is arranged in the horizontal flow liquid hole, a correction material feeding hole is arranged on the horizontal flow liquid hole, the horizontal flow cave is communicated with the ascending flow liquid channel, a second refractory material frame is arranged in the ascending flow liquid channel, active lime is arranged in the second refractory material frame, and the ascending flow liquid channel is communicated with the overflow cave.
Further, the furnace body is made of refractory materials, and the horizontal flow liquid hole is a rectangular pipeline and is made of steel plates and refractory materials.
Furthermore, the inclined conical furnace cover is inclined, and the liftable top combustion spray gun is arranged at the center of the inclined conical furnace cover through a sleeve.
Furthermore, a plurality of mounting holes for mounting the furnace wall side-inserted combustion spray gun are formed in the furnace body.
A method for producing cement by using liquid steel slag as a raw material comprises the following steps:
the method comprises the following steps: hoisting and loading the high-temperature slag liquid discharged by steel making into equipment by using a heat-insulating slag pot; the liquid or molten slag is firstly heated by the top and two side burning spray guns, then flows through the carbon reduction bed, FeOx is reduced into Fe to be discharged, and the RO phase is decomposed;
step two: the decomposed slag liquid flows into a molybdenum electrode heating area, is heated by a molybdenum electrode again, and the heated slag liquid is added with a proper amount of mineral powder, bauxite and iron-selecting tailing sand and then flows into an active lime saturation area;
step three: slag liquid flowing through the active lime saturation zone, C2S is converted to C3S，Fe2O3、Al2O3Reaction to form C3A and C4AF; carrying out pneumatic atomization and rapid cooling solidification on the reacted slag liquid;
step four: adding a proper amount of dihydrate gypsum, monopotassium phosphate and borax to prepare the No. 425 cement.
Furthermore, the top and two side combustion spray guns are used for heating molten steel slag to be in a flowing state, so that the liquid steel slag has a certain superheat degree and is consumed by heat required by carbothermic reduction, and flue gas formed by combustion is stirred to facilitate dephosphorization and deferrization; the combustion medium can be gas, fuel oil or coal, carbon.
Furthermore, the carbon reduction bed is formed by filling coke into a high-grade refractory material frame, and the lump size of the coke is 80-150 mm; the slag liquid flows through a carbon reduction bed, FeOx is reduced, an RO phase (CaO-FeO-MnO-MgO continuous solid solution) is disintegrated, iron and manganese are reduced and sink to the bottom of the equipment and are periodically discharged, magnesium oxide forms periclase, fCaO is SiO2 Al2O absorption to C2S、CA。
Furthermore, the molybdenum electrode area is used for supplementing heat consumed by carbon thermal reduction to the slag liquid and facilitating C for the slag liquid to flow through a saturated lime area2S to C3S, carrying out endothermic reaction; because the slag liquid is subjected to iron and manganese removal, the molybdenum electrode is reduced from being corroded by active oxides, and the molybdenum electrode is adopted for heating.
Furthermore, the addition of a proper amount of mineral powder, bauxite and iron tailing sand supplements and adjusts the silicon rate and the aluminum rate correction raw materials on the basis of sampling and testing the chemical components of the slag liquid, and the adjustment principle is that the silicon rate and the aluminum rate are adjusted as much as possibleThe liquid steel slag is utilized, so the silicon rate and the aluminum rate are low; fe2O3、Al2O3The addition of the correction raw materials is to adjust the silicon rate and the aluminum rate and increase the fluidity of the slag liquid; therefore, mineral powder, bauxite, iron tailings sand are preferred but not limited thereto, and fly ash, blast furnace dust, red mud, etc. may be mentioned.
Furthermore, the active lime saturation area is formed by filling active lime into a high-grade refractory material frame; calcium oxide has the same melting point as carbon, the temperature in the slag liquid is not enough to melt, and C molten in the slag liquid2S、CA、Fe2O3、Al2O3Flows into an active lime saturation area to react with CaO in a liquid phase and a solid phase to generate C3S、C3A、C4AF cement main minerals; the chemical reaction of the slag liquid in the lime saturation area is similar to the slagging in a steel-making converter, but the iron oxide is much less than the phosphorus oxide, which is more beneficial to C3And (5) generating S.
Compared with the prior art, the invention has the beneficial effects that:
1. under the condition of not influencing steel smelting, high-temperature liquid slag is used for adding silicon-aluminum correction raw materials, the silicon-aluminum correction raw materials flow through a carbon reduction bed and an active lime saturation area in the furnace to decompose RO phase, FeOx is reduced, molten iron is recycled, liquid cement clinker is generated, and heat released by the liquid cement clinker during cooling and solidification can be recovered.
2. The clinker is ground and added with dihydrate gypsum, potassium dihydrogen phosphate and borax, so that magnesium oxide influencing stability in the steel slag forms a magnesium potassium phosphate cement component, and the bad stability phenomenon is eliminated.
3. The equipment is a vertical cylindrical furnace body, the furnace type is simple, the airtightness is good, the heat loss is less, and the occupied area is small; the submerged combustion has the advantages of stirring function, rapid heat and mass transfer, high reaction speed, low blast pressure and low power consumption.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a schematic view of the overall structure of an apparatus and a method for producing cement using liquid steel slag as a raw material according to the present invention;
FIG. 2 is a schematic view of the cement production process flow of the equipment and method for producing cement by using liquid steel slag as a raw material according to the present invention.
In the figure: the furnace comprises a discharge tap hole 1, a furnace body 2, a refractory material 3, a carbon material 4, a first refractory material frame 5, a furnace wall side-inserted combustion spray gun 6, a slag-liquid inlet air seal device 7, a slag-liquid inlet 8, an inclined conical furnace cover 9, a liftable top combustion spray gun 10, a flue gas outlet 11, a heating molybdenum electrode 12, a calibration material inlet 13, a horizontal flow liquid hole 14, an ascending flow liquid channel 15, active lime 16, a second refractory material frame 17 and an overflow hole 18.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Referring to fig. 1, an apparatus for producing cement by using liquid steel slag as raw material comprises a furnace body 2, a horizontal flow liquid hole 14, an up-flow liquid channel 15 and an overflow hole 18, wherein the furnace body 2 is cylindrical, an iron discharging port 1 is arranged at the bottom of the furnace body 2, a first refractory material frame 5 is arranged in the furnace body 2, a carbon material 4 is arranged in the first refractory material frame 5, a furnace wall side-inserted combustion spray gun 6 and a liftable top combustion spray gun 10 are arranged on the side wall of the furnace body 2 at the upper side of the first refractory material frame 5, the liftable top combustion spray gun 10 is connected with the top of the furnace body 2 in a liftable manner through a sleeve, a slag liquid inlet 8 and an inclined conical furnace cover 9 are arranged at the top of the furnace body 2, a slag liquid inlet air seal device 7 is arranged at the slag liquid inlet 8, a flue gas outlet 11 is arranged at one side of the top of the furnace body 2 away from the iron discharging port 1, the horizontal flow liquid hole 14 is communicated with a heating molybdenum electrode 12, the horizontal flow cave 14 is provided with a correcting material inlet 13, the horizontal flow cave 14 is communicated with an upflow channel 15, a second refractory material frame 17 is arranged in the upflow channel 15, active lime 16 is arranged in the second refractory material frame 17, and the upflow channel 15 is communicated with an overflow cave 18.
Further, the furnace body 2 is made of refractory 3, and the horizontal flow liquid level hole 14 is a rectangular pipe and is made of steel plate and refractory 3.
Further, the inclined cone-shaped furnace cover 9 is inclined, and the liftable top combustion lance 10 is arranged at the center of the inclined cone-shaped furnace cover 9 through a sleeve.
Further, the furnace body 2 is provided with a plurality of mounting holes for mounting the furnace wall side-inserted combustion lance 6.
Referring to fig. 2, a method for producing cement using liquid steel slag as a raw material, the method comprising the steps of:
the method comprises the following steps: hoisting and loading the high-temperature slag liquid discharged by steel making into equipment by using a heat-insulating slag pot; the liquid or molten slag is firstly heated by the top and two side burning spray guns, then flows through the carbon reduction bed, FeOx is reduced into Fe to be discharged, and the RO phase is decomposed;
step two: the decomposed slag liquid flows into a molybdenum electrode heating area, is heated by a molybdenum electrode again, and the heated slag liquid is added with a proper amount of mineral powder, bauxite and iron-selecting tailing sand and then flows into an active lime saturation area;
step three: slag liquid flowing through the active lime saturation zone, C2S is converted to C3S，Fe2O3、Al2O3Reaction to form C3A and C4AF; carrying out pneumatic atomization and rapid cooling solidification on the reacted slag liquid;
step four: adding a proper amount of dihydrate gypsum, monopotassium phosphate and borax to prepare the No. 425 cement.
Furthermore, the top and two side combustion spray guns are used for heating molten steel slag to be in a flowing state, so that the liquid steel slag has a certain superheat degree and is consumed by heat required by carbothermic reduction, and flue gas formed by combustion is stirred to facilitate dephosphorization and deferrization; the combustion medium can be gas, fuel oil or coal, carbon.
Furthermore, the carbon reduction bed is formed by filling coke into a high-grade refractory material frame, and the lump size of the coke is 80-150 mm; the slag liquid flows through a carbon reduction bed, FeOx is reduced, an RO phase (CaO-FeO-MnO-MgO continuous solid solution) is disintegrated, iron and manganese are reduced and sink to the bottom of the equipment and are periodically discharged, magnesium oxide forms periclase, fCaO is SiO2 Al2O absorption to C2S、CA。
Furthermore, the molybdenum electrode area is used for supplementing heat consumed by carbon thermal reduction to the slag liquid and facilitating C for the slag liquid to flow through a saturated lime area2S to C3S, carrying out endothermic reaction; because the slag liquid is subjected to iron and manganese removal, the molybdenum electrode is reduced from being corroded by active oxides, and the molybdenum electrode is adopted for heating.
Furthermore, the adding of a proper amount of mineral powder, bauxite and iron tailing sand is based on sampling and testing the chemical components of the slag liquid, the silicon rate and the aluminum rate are supplemented and adjusted to correct raw materials, and the adjustment principle is to utilize liquid steel slag as far as possible, so that the silicon rate and the aluminum rate are low; fe2O3、Al2O3The addition of the correction raw materials is to adjust the silicon rate and the aluminum rate and increase the fluidity of the slag liquid; therefore, mineral powder, bauxite, iron tailings sand are preferred but not limited thereto, and fly ash, blast furnace dust, red mud, etc. may be mentioned.
Furthermore, the active lime saturation area is formed by filling active lime into a high-grade refractory material frame; calcium oxide has the same melting point as carbon, the temperature in the slag liquid is not enough to melt, and C molten in the slag liquid2S、CA、Fe2O3、Al2O3Flows into an active lime saturation area to react with CaO in a liquid phase and a solid phase to generate C3S、C3A、C4AF cement main minerals; chemical reaction of slag liquid in lime saturation area, similar to slag formation in steel-making converterIron oxide is much less than phosphorus oxide, and is more favorable to C3And (5) generating S.
The working principle is as follows: when the furnace is started, before liquid steel slag is added, water is injected into the water-cooled wall, the combustion spray gun is ignited to preheat the reaction furnace, when the temperature in the furnace rises to 1200 ℃, the heat-preservation slag pot is hoisted, slag liquid conveyed by the converter is poured into the furnace inlet, after the liquid level of the slag liquid reaches a set height, combustion is adjusted, pulverized coal is sprayed, the temperature of the slag liquid is controlled to 1650 ℃, the slag liquid flows through the carbon thermal reduction bed, RO and Ca3(PO4) Decomposition, iron and manganese sedimentation and phosphorus gasification rising; the slag liquid flowing out of the carbon reduction bed enters a molybdenum electrode heating area of the inflow channel to supplement heat to 1650 ℃; adding a correction raw material, flowing into a riser, and entering an active lime saturation area to generate cement clinker; slag liquid is continuously added into the furnace inlet, cement clinker is continuously discharged from the furnace outlet, and continuous production is carried out; the liquid cement clinker is atomized into powder by air force, cooled by heat exchange, added with dihydrate gypsum, potassium dihydrogen phosphate and borax, and milled into cement.
Example 1
In the examples, steel slag from a certain steel mill is used, and the chemical composition is shown in the following table
| Composition (I) | SiO2 | Al2O3 | FeO | CaO | MgO | MnO | P2O5 | f-CaO | T.Fe |
| Content% | 10.20 | 1.21 | 12.32 | 41.58 | 11.49 | 3.09 | 1.50 | 8.07 | 20.16 |
The comparative cement used in the examples was a P II 42.5 cement from a cement plant, the chemical composition and physical properties of which are given in the following table
Standard sands in the examples: the cement mortar test adopts Chinese I SO standard sand (GB 178-97)
Water in the examples: tap water is used for forming steel slag paste and mortar, and distilled water is used for measuring free calcium oxide.
In the examples, the raw materials are corrected: the correcting raw materials comprise coal ash and iron powder;
industrial analysis of the coal is shown in the following Table
| ω(Mad) | ω(Vad) | ω(Aad) | ω(Fcad) | Qnet.ad |
| 0.06％ | 22.42％ | 28.56％ | 49.02 | 20930KJ/Kg |
In the examples, the slag liquid flows through the carbon reduction bed to take the slag sample for chemical analysis, and the analysis result is as follows:
| composition (I) | SiO2 | Al2O3 | Fe2O3 | CaO | MgO | Others |
| Content% | 14.80 | 2.439 | 0 | 66,80 | 14.6 | 1.36 |
According to the analysis result of the assay, adding 10% of the correction raw material iron powder into the reference cement component; 13 percent of coal ash. The chemical composition of the resulting cement is as follows:
| composition (I) | SiO2 | Al2O3 | Fe2O3 | CaO | MgO |
| Content% | 20.61 | 5.35 | 4.79 | 61.02 | 7.8 |
Mixing 4% of dihydrate gypsum with the generated cement clinker, adding 3% of monopotassium phosphate and 0.5% of borax into the mixture, grinding the mixture into powder with standard fineness, and preparing the cement.
The detection standard of the physical properties of the cement is in accordance with GB175-2007 general Portland cement; GB/T8074-2008 & lt & ltmethod for determining specific surface area of cement & gt Bo's method & lt; GB/T1346-2011 test method for water consumption, setting time and stability of standard consistency of cement; GB/He 17671 and 1999 method for testing the strength of cement mortar.
Basic properties of cement
| Specific surface area/m 2.Kg-1 | Grinding time/s | Water storage capacity ratio of standard consistency | The swelling ratio% | Stability of |
| 410 | 250 | 0.23 | 0.06 | Qualified |
Breaking and compression strength of cement mortar
Example 2
In the examples, steel slag from a certain steel mill is used, and the chemical composition is shown in the following table
| Composition (I) | SiO2 | Al2O3 | TiO2 | CaO | MgO | Na2O | P2O5 | K2O | T.Fe |
| Content% | 14.73 | 4.06 | 0.86 | 48.00 | 7.62 | 0.17 | 1.04 | 0.075 | 14.3 |
The comparative cement used in the examples was a P II 42.5 cement from a cement plant, the chemical composition and physical properties of which are given in the following table
Standard sands in the examples: the cement mortar test uses water in the example of Chinese I SO standard sand (GB 178-97): tap water is used for forming steel slag paste and mortar, and distilled water is used for measuring free calcium oxide.
In the examples, the raw materials are corrected: the correcting raw materials comprise coal ash and iron powder;
industrial analysis of the coal is shown in the following Table
| ω(Mad) | ω(Vad) | ω(Aad) | ω(Fcad) | Qnet.ad |
| 0.06％ | 22.42％ | 28.56％ | 49.02 | 20930KJ/Kg |
In the examples, the slag liquid flows through the carbon reduction bed to take the slag sample for chemical analysis, and the analysis result is as follows:
| composition (I) | SiO2 | Al2O3 | Fe2O3 | CaO | MgO | Others |
| Content% | 19.39 | 5.92 | 0.14 | 57.29 | 9.11 | 3.36 |
According to the analysis result of the assay, 8% of the calibration raw material iron powder is added according to the components of the reference cement; 3 percent of coal ash. The chemical composition of the resulting cement is as follows:
| composition (I) | SiO2 | Al2O3 | Fe2O3 | CaO | MgO |
| Content% | 22.14 | 6.84 | 4.01 | 67.02 | 9.13 |
Mixing 4% of dihydrate gypsum with the generated cement clinker, adding 3% of monopotassium phosphate and 0.5% of borax into the mixture, grinding the mixture into powder with standard fineness, and preparing the cement.
The detection standard of the physical properties of the cement is in accordance with GB175-2007 general Portland cement; GB/T8074-2008 & lt & ltmethod for determining specific surface area of cement & gt Bo's method & lt; GB/T1346-2011 test method for water consumption, setting time and stability of standard consistency of cement; GB/He 17671 and 1999 method for testing the strength of cement mortar.
Basic properties of cement
| Specific surface area/m 2.Kg-1 | Grinding time/s | Water storage capacity ratio of standard consistency | The swelling ratio% | Stability of |
| 410 | 185 | 0.23 | 0.03 | Qualified |
Breaking and compression strength of cement mortar
The above results show that: the liquid steel slag can be used for generating cement in liquid flow, and the method has the advantages of short flow, simple equipment, convenient operation, low energy consumption, recyclable slag liquid heat and reduced resource consumption.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. An apparatus for producing cement by using liquid steel slag as a raw material comprises a furnace body (2), a horizontal flow liquid hole (14), an ascending flow liquid channel (15) and an overflow hole (18), and is characterized in that the furnace body (2) is cylindrical, an iron notch (1) is arranged at the bottom of the furnace body (2), a first refractory material frame (5) is arranged in the furnace body (2), a carbon material (4) is arranged in the first refractory material frame (5), a furnace wall side-inserted combustion spray gun (6) and a liftable top combustion spray gun (10) are arranged on the side wall of the furnace body (2) on the upper side of the first refractory material frame (5), the liftable top combustion spray gun (10) is connected with the top of the furnace body (2) in a liftable manner through a sleeve, a slag liquid inlet (8) and an inclined conical furnace cover (9) are arranged at the top of the furnace body (2), a liftable slag liquid inlet (8) is provided with a liftable gas seal device (7), the improved iron tap is characterized in that a flue gas outlet (11) is formed in one side of the top of the furnace body (2), one side, away from the iron discharging port (1), of the furnace body (2) is communicated with a horizontal flow liquid tunnel (14), a heating molybdenum electrode (12) is arranged in the horizontal flow liquid tunnel (14), a correction material adding port (13) is formed in the horizontal flow liquid tunnel (14), the horizontal flow liquid tunnel (14) is communicated with an ascending flow liquid channel (15), a second refractory material frame (17) is arranged in the ascending flow liquid channel (15), active lime (16) is arranged in the second refractory material frame (17), and the ascending flow liquid channel (15) is communicated with an overflow hole (18).
2. The apparatus for producing cement using liquid steel slag as raw material according to claim 1, wherein the furnace body (2) is made of refractory material (3), and the horizontal flow tunnel (14) is a rectangular pipe and is made of steel plate and refractory material (3).
3. The apparatus for producing cement using liquid steel slag as raw material according to claim 1, wherein the furnace cover (9) is inclined, and the liftable top-firing lance (10) is disposed at the center of the furnace cover (9) through a sleeve.
4. The equipment for producing cement by using liquid steel slag as a raw material according to claim 1, wherein the furnace body (2) is provided with a plurality of mounting holes for mounting furnace wall side-inserted combustion lances (6).
5. A method for producing cement by using the equipment for producing cement by using the liquid steel slag as the raw material according to any one of claims 1 to 4, which is characterized by comprising the following steps:
the method comprises the following steps: hoisting and loading the high-temperature slag liquid discharged by steel making into equipment by using a heat-insulating slag pot; the liquid or molten slag is firstly heated by the top and two side burning spray guns, then flows through the carbon reduction bed, FeOx is reduced into Fe to be discharged, and the RO phase is decomposed;
step two: the decomposed slag liquid flows into a molybdenum electrode heating area, is heated by a molybdenum electrode again, and the heated slag liquid is added with a proper amount of mineral powder, bauxite and iron-selecting tailing sand and then flows into an active lime saturation area;
step three: slag liquid flowing through the active lime saturation zone, C2S is converted to C3S，Fe2O3、Al2O3Reaction to form C3A and C4AF; carrying out pneumatic atomization and rapid cooling solidification on the reacted slag liquid;
step four: adding a proper amount of dihydrate gypsum, monopotassium phosphate and borax to prepare the No. 425 cement.
6. The method for producing cement by using liquid steel slag as raw material through equipment for producing cement according to claim 5, wherein the top and two side combustion lances are used for heating the molten steel slag to a flowing state, so that the liquid slag has a certain degree of superheat and is consumed by heat required by carbothermic reduction, and flue gas formed by combustion is stirred to facilitate dephosphorization and deferrization; the combustion medium is any one of gas, fuel oil, coal and carbon.
7. The method for producing cement by using liquid steel slag as raw material in equipment for producing cement according to claim 5, wherein the carbon reduction bed is formed by filling coke with a high-grade refractory material frame, and the lump size of the coke is 80-150 mm; the slag liquid flows through a carbon reduction bed, FeOx is reduced, an RO phase is disintegrated, iron and manganese are reduced and sink to the bottom of the equipment,periodically discharging, forming periclase from magnesium oxide, and SiO coating fCaO2 Al2O absorption to C2S、CA。
8. The method for producing cement by using liquid steel slag as raw material in equipment for producing cement according to claim 5, wherein the molybdenum electrode area is used for supplementing heat consumed by carbon thermal reduction to slag liquid and facilitating C for slag liquid to flow through a saturated lime area2S to C3S, carrying out endothermic reaction; because the slag liquid is subjected to iron and manganese removal, the molybdenum electrode is reduced from being corroded by active oxides, and the molybdenum electrode is adopted for heating.
9. The method for producing cement by using liquid steel slag as raw material according to claim 5, wherein the adding of a proper amount of mineral powder, bauxite, and iron tailings is based on chemical components of sampled and assayed slag liquid, and the silicon rate and the aluminum rate are corrected by supplementing and adjusting raw materials, and the adjustment principle is to utilize the liquid steel slag as much as possible, so that the silicon rate and the aluminum rate are low; fe2O3、Al2O3The addition of the correction raw materials is to adjust the silicon rate and the aluminum rate and increase the fluidity of the slag liquid.
10. The method for producing cement by using liquid steel slag as raw material in equipment for producing cement according to claim 5, wherein the active lime saturation zone is formed by filling active lime into a high-grade refractory frame; the calcium oxide and the carbon also have the characteristic of high melting points, the temperature in the slag liquid is not enough to melt, and C melted in the slag liquid2S、CA、Fe2O3、Al2O3Flows into an active lime saturation area to react with CaO in a liquid phase and a solid phase to generate C3S、C3A、C4AF cement main minerals; the chemical reaction of the slag liquid in the lime saturation area is similar to the slagging in a steel-making converter, but the iron oxide is much less than the phosphorus oxide, which is more beneficial to C3And (5) generating S.
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| CN113912021B (en) * | 2021-11-16 | 2022-12-20 | 上海驰春节能科技有限公司 | System and process for producing sulfur and cement clinker by using industrial byproduct gypsum in cooperation with metallurgical slag solution |
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